本發明係關於一種黏著劑、黏著片及光學構件。The invention relates to an adhesive, an adhesive sheet and an optical component.
光學構件片材使用在基材（聚酯、聚乙烯、聚丙烯及玻璃等極性被黏著體）上積層有黏著劑者，偏光板等光學構件之製造商將其用於光學構件出貨時之表面保護，又，液晶顯示器等影像顯示裝置之製造商將其用於顯示裝置（液晶模組）之製造步驟中之光學構件的保護用途或光學構件彼此之貼附等。Optical component sheets are used with adhesives laminated on base materials (polar adherends such as polyester, polyethylene, polypropylene, and glass). Manufacturers of optical components such as polarizers use them when shipping optical components. Surface protection is also used by manufacturers of image display devices such as liquid crystal displays to protect optical components in the manufacturing steps of display devices (liquid crystal modules) or to adhere optical components to each other.
該等光學構件片材主要使用丙烯酸黏著劑，但由於胺酯黏著劑對被黏著體之追隨性較佳，低溫特性優異等，故亦對其進行了研究（例如專利文獻1）。These optical member sheets mainly use acrylic adhesives, but urethane adhesives have also been studied because they have better followability to adherends and excellent low-temperature characteristics (for example, Patent Document 1).
然而，專利文獻1中揭示之胺酯黏著劑存在如下等問題：為了表現黏著片之強度必須使用大量硬化劑，或增加交聯點，或提高胺酯基濃度；柔軟性不足，低溫特性較差，因被黏著體之種類而黏著力降低。However, the urethane adhesive disclosed in Patent Document 1 has the following problems: in order to express the strength of the adhesive sheet, a large amount of hardener must be used, or the cross-linking points must be increased, or the urethane group concentration must be increased; the flexibility is insufficient, and the low-temperature characteristics are poor. The adhesive force decreases depending on the type of adherend.
又，如專利文獻2所述，於將胺酯黏著劑用作單液硬化型黏著劑之情形時，存在如下等問題：於生產時控制分子量較難而難以提高分子量，因此凝聚力不足，或高溫下之黏著力降低。Furthermore, as described in Patent Document 2, when a urethane adhesive is used as a one-liquid curable adhesive, there are problems such as: it is difficult to control the molecular weight during production and it is difficult to increase the molecular weight, so the cohesive force is insufficient, or the high temperature The adhesion is reduced.
又，專利文獻3所記載之聚胺酯脲樹脂黏著劑存在難以提高分子量，若欲提高分子量則增黏或凝膠化之風險變高的問題。先前技術文獻專利文獻Furthermore, the polyurethane urea resin adhesive described in Patent Document 3 has the problem that it is difficult to increase the molecular weight, and if the molecular weight is increased, the risk of thickening or gelation increases.Prior technical literaturepatent documents
專利文獻1：日本特開2006-182795號公報專利文獻2：日本專利第6480176號公報專利文獻3：日本特開2001-192636號公報Patent Document 1: Japanese Patent Application Publication No. 2006-182795Patent Document 2: Japanese Patent No. 6480176Patent Document 3: Japanese Patent Application Publication No. 2001-192636
[發明所欲解決之課題][Problem to be solved by the invention]
本發明之課題在於提供一種具有均衡性良好之性能之胺酯黏著劑，其顯示優異之柔軟性，自低溫至高溫之黏彈性之溫度依存性較小，對極性被黏著體之黏著力尤其優異，且能夠容易控制高分子量化，因此黏著膜之強度較高，對被黏著體之污染較少。[解決課題之技術手段]The object of the present invention is to provide a urethane adhesive with well-balanced properties, which exhibits excellent softness, has little temperature dependence of viscoelasticity from low to high temperatures, and has particularly excellent adhesion to polar adherends. , and can easily control the high molecular weight, so the adhesive film has higher strength and less pollution to the adherend.[Technical means to solve the problem]
本發明人等為了解決上述課題進行了深入研究，結果完成了本發明。即，本發明係一種黏著劑、使用有上述黏著劑之黏著片、使用有上述黏著劑之光學構件，上述黏著劑含有以不具有胺基之多元醇成分（A）以及異氰酸酯成分（B）作為必需構成單體之聚胺酯樹脂，且上述聚胺酯樹脂之重量平均分子量為5萬～200萬，上述不具有胺基之多元醇成分（A）含有聚氧伸烷基多元醇（polyoxyalkylene polyol）（a1），上述聚氧伸烷基多元醇（a1）之分子末端為羥丙基，並且其一級羥基含有率至少為40%，該黏著劑於一面以2 kg輥進行壓接一面貼合於玻璃板時，於23℃在拉伸速度300 mm/min之條件下的180°剝離強度為5～50 N/25 mm。[發明之效果]The present inventors conducted intensive research in order to solve the above-mentioned problems, and as a result completed the present invention.That is, the present invention is an adhesive, an adhesive sheet using the above-mentioned adhesive, and an optical member using the above-mentioned adhesive. The above-mentioned adhesive contains a polyol component (A) that does not have an amine group and an isocyanate component (B). The polyurethane resin is a necessary monomer, and the weight average molecular weight of the polyurethane resin is 50,000 to 2,000,000. The polyol component (A) without an amine group contains polyoxyalkylene polyol (a1) , the molecular terminal of the above-mentioned polyoxyalkylene polyol (a1) is a hydroxypropyl group, and its primary hydroxyl content is at least 40%, when the adhesive is pressed with a 2 kg roller on one side and bonded to the glass plate on the other. , the 180° peel strength at 23°C at a tensile speed of 300 mm/min is 5~50 N/25 mm.[Effects of the invention]
本發明之黏著劑具有均衡性良好之性能，其顯示優異之柔軟性，自低溫至高溫之黏彈性之溫度依存性較小，對極性被黏著體之黏著力尤其優異，且能夠容易控制高分子量化，因此黏著膜之強度較高，對被黏著體之污染較少。The adhesive of the present invention has well-balanced properties, exhibits excellent softness, has small temperature dependence of viscoelasticity from low temperature to high temperature, is particularly excellent in adhesion to polar adherends, and can easily control high molecular weight. chemical, so the adhesive film has higher strength and less pollution to the adherend.
[黏著劑]本發明之黏著劑含有以不具有胺基之多元醇成分（A）以及異氰酸酯成分（B）作為必需構成單體的聚胺酯樹脂，且上述聚胺酯樹脂之重量平均分子量為5萬～200萬，上述不具有胺基之多元醇成分（A）含有聚氧伸烷基多元醇（a1），上述聚氧伸烷基多元醇（a1）之分子末端為羥丙基，並且其一級羥基含有率至少為40%，該黏著劑於一面以2 kg輥進行壓接一面貼合於玻璃板時，於23℃在拉伸速度300 mm/min之條件下的180°剝離強度為5～50 N/25 mm。以下，說明本發明之黏著劑。[adhesive]The adhesive of the present invention contains a polyurethane resin with polyol component (A) and isocyanate component (B) without amine groups as essential constituent monomers, and the weight average molecular weight of the above-mentioned polyurethane resin is 50,000 to 2,000,000. The polyol component (A) having an amine group contains polyoxyalkylene polyol (a1). The molecular terminal of the polyoxyalkylene polyol (a1) is a hydroxypropyl group, and its primary hydroxyl group content is at least 40 %, when the adhesive is pressed with a 2 kg roller on one side and attached to the glass plate on the other side, the 180° peel strength at 23°C and a stretching speed of 300 mm/min is 5~50 N/25 mm.Next, the adhesive agent of this invention is demonstrated.
本發明之黏著劑含有以不具有胺基之多元醇成分（A）以及異氰酸酯成分（B）作為必需構成單體之聚胺酯樹脂。The adhesive of the present invention contains a polyurethane resin containing a polyol component (A) without an amine group and an isocyanate component (B) as essential constituent monomers.
（不具有胺基之多元醇成分（A））不具有胺基之多元醇成分（A）（以下簡稱多元醇成分（A））含有聚氧伸烷基多元醇（a1），上述聚氧伸烷基多元醇（a1）之分子末端為羥丙基，並且其一級羥基含有率至少為40%。(Polyol component (A) without amine group)The polyol component (A) without an amine group (hereinafter referred to as the polyol component (A)) contains polyoxyalkylene polyol (a1), and the molecular terminal of the polyoxyalkylene polyol (a1) is hydroxypropyl group, and its primary hydroxyl content is at least 40%.
聚氧伸烷基多元醇（a1）之分子末端具有羥丙基例如可藉由1H-NMR法進行確認。The presence of a hydroxypropyl group at the molecular terminal of the polyoxyalkylene polyol (a1) can be confirmed by, for example,a 1 H-NMR method.
羥丙基包含下述化學式（1）所表示之含一級羥基（鍵結於一級碳原子之羥基）之基、以及化學式（1'）所表示之含二級羥基（鍵結於二級碳原子之羥基）之基。聚氧伸烷基多元醇（a1）所含之所有羥丙基中，鍵結於一級碳原子之羥基數的比率（以下稱為一級羥基含有率）為40%以上，較佳為60%以上，進而較佳為70%以上。若聚氧伸烷基多元醇（a1）所含之所有羥丙基之一級羥基含有率未達40%，則無法獲得充分之凝聚力或膜強度。The hydroxypropyl group includes a group containing a primary hydroxyl group (hydroxyl group bonded to a primary carbon atom) represented by the following chemical formula (1), and a group containing a secondary hydroxyl group (bonded to a secondary carbon atom) represented by the chemical formula (1') hydroxyl group).Among all the hydroxypropyl groups contained in the polyoxyalkylene polyol (a1), the ratio of the number of hydroxyl groups bonded to primary carbon atoms (hereinafter referred to as the primary hydroxyl content rate) is 40% or more, preferably 60% or more , and more preferably more than 70%.If the primary hydroxyl content rate of all the hydroxypropyl groups contained in the polyoxyalkylene polyol (a1) is less than 40%, sufficient cohesive force or film strength cannot be obtained.
一級羥基含有率可在預先對試樣進行預處理（酯化）後，藉由1H-NMR法測定而求出。以下說明1H-NMR法之詳情。The primary hydroxyl group content rate can be determined by measuring the sample by the1 H-NMR method after performing pretreatment (esterification) in advance. Details of the1 H-NMR method are explained below.
＜試樣製備法＞將約30 mg之測定試樣稱量至直徑5 mm之NMR用試管，添加約0.5 ml之氘代溶劑使其溶解。其後，添加約0.1 ml之三氟乙酸酐，作為分析用試樣。作為上述氘代溶劑，例如可自氘代氯仿、氘代甲苯、氘代二甲基亞碸、氘代二甲基甲醯胺等中適當選擇能夠使試樣溶解之溶劑。＜Sample Preparation Method＞Weigh approximately 30 mg of the measurement sample into an NMR test tube with a diameter of 5 mm, and add approximately 0.5 ml of deuterated solvent to dissolve it. Thereafter, approximately 0.1 ml of trifluoroacetic anhydride was added to prepare a sample for analysis.As the deuterated solvent, for example, a solvent capable of dissolving the sample can be appropriately selected from deuterated chloroform, deuterated toluene, deuterated dimethyltrisoxide, deuterated dimethylformamide, and the like.
＜NMR測定＞於普通條件下進行1H-NMR測定。<NMR measurement>1 H-NMR measurement was performed under ordinary conditions.
＜一級羥基含有率之計算方法＞藉由如上所述之預處理之方法，聚氧伸烷基多元醇之末端之羥基與添加之三氟乙酸酐反應而形成三氟乙酸酯。其結果，於4.3 ppm附近觀測到源自鍵結有一級羥基之亞甲基之訊號，於5.2 ppm附近觀測到源自鍵結有二級羥基之次甲基之訊號。一級羥基含有率藉由以下計算式算出。一級羥基含有率（%）＝[x/（x＋2×y）]×100其中，x為4.3 ppm附近之源自鍵結有一級羥基之亞甲基的訊號之積分值，y為5.2 ppm附近之源自鍵結有二級羥基之次甲基的訊號之積分值。＜Calculation method of primary hydroxyl content rate＞Through the above-mentioned pretreatment method, the terminal hydroxyl group of the polyoxyalkylene polyol reacts with the added trifluoroacetic anhydride to form trifluoroacetate. As a result, a signal originating from a methylene group bonded to a primary hydroxyl group was observed near 4.3 ppm, and a signal originating from a methine group bonded to a secondary hydroxyl group was observed near 5.2 ppm. The primary hydroxyl group content rate is calculated by the following calculation formula.Primary hydroxyl content rate (%) = [x/(x+2×y)]×100Among them, x is the integrated value of the signal originating from the methylene group bonded with the primary hydroxyl group near 4.3 ppm, and y is the integrated value of the signal originating from the methylene group bonded with the secondary hydroxyl group near 5.2 ppm.
就柔軟性、黏著力之溫度依存性以及黏著力之被黏著體種類依存性及膜厚依存性之觀點而言，上述聚氧伸烷基多元醇（a1）較佳為使用通式（2）所表示之化合物。From the viewpoints of flexibility, temperature dependence of adhesive force, dependence of adhesive force on adherend type and film thickness, the polyoxyalkylene polyol (a1) preferably uses the general formula (2) the compound represented.
R1[-(R2-O)p-(R3-O)q-H]m（2）R1 [-(R2 -O)p -(R3 -O)q -H]m (2)
通式（2）中之R1為自具有m個活性氫原子之化合物去除活性氫原子所得的m價殘基，m較佳為2～20之整數。若m超過20，則存在聚氧伸烷基多元醇（a1）之黏度變高，塗敷胺酯樹脂溶液時之黏度變高之情況。作為構成殘基R1之具有m個活性氫原子之化合物，可列舉：含羥基化合物、含羧基化合物以及硫醇等具有選自羥基、羧基及巰基中之至少1種基之化合物。R1 in the general formula (2) is an m-valent residue obtained by removing active hydrogen atoms from a compound having m active hydrogen atoms, and m is preferably an integer from 2 to 20. If m exceeds 20, the viscosity of the polyoxyalkylene polyol (a1) may become high, and the viscosity when applying the urethane resin solution may become high. Examples of the compound having m active hydrogen atoms constituting the residue R1 include a hydroxyl-containing compound, a carboxyl-containing compound, and a compound having at least one group selected from a hydroxyl group, a carboxyl group, and a mercapto group, such as a thiol.
作為上述含羥基化合物，可列舉：羥基當量為160以下之低分子多元醇[脂肪族多元醇[碳數2～20之脂肪族二元醇{伸烷基二醇，例如乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、3-甲基戊二醇、新戊二醇及1,9-壬二醇等}；碳數3～8之三～八元或其以上之多元醇{甘油、三羥甲基丙烷、新戊四醇、山梨醇、木糖醇及甘露醇等}；其等之分子間或分子內脫水物，例如二新戊四醇、聚甘油（聚合度2～20）及山梨醇酐；糖類及其衍生物（糖苷等），例如葡萄糖、果糖、蔗糖及α-甲基葡萄糖苷等；碳數6～15之(雙)伸環烷基二醇（（bi）cycloalkylene diol）{例如1,4-二羥基環己烷、1,4-雙(羥甲基)環己烷及2,2-雙(4,4'-羥基環己基)丙烷等}]；碳數8～15之含芳香環之多元醇[間或對苯二甲醇及1,4-雙(羥乙基)苯等]等]；蓖麻油系多元醇（蓖麻油、部分脫水蓖麻油及部分醯化蓖麻油等）；具有m個羥基之數量平均分子量（以下簡稱Mn）2,000以下之聚合物或低聚物[聚二烯烴(碳數4～10)多元醇，例如聚丁二烯多元醇及其氫化物；(甲基)丙烯酸羥基烷基(碳數2～4)酯之(共)聚合物；聚乙烯醇（皂化度60%以上）等]；多酚類[單環多酚類（鄰苯三酚、鄰苯二酚及對苯二酚等）、雙酚類（雙酚A、雙酚F及雙酚S等）等]；磷酸化合物（磷酸、亞磷酸及膦酸等）；及其等之2種以上混合物。Examples of the above-mentioned hydroxyl-containing compound include: low-molecular polyols with a hydroxyl equivalent of 160 or less [aliphatic polyols [aliphatic diols with 2 to 20 carbon atoms]; alkylene glycols, such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, neopentyl glycol and 1,9-nonanediol, etc.}; carbon number 3 ~Polyhydric alcohols of three to eight yuan or above {glycerol, trimethylolpropane, neopenterythritol, sorbitol, xylitol, mannitol, etc.}; their intermolecular or intramolecular dehydrated products, For example, dipenterythritol, polyglycerol (degree of polymerization 2 to 20) and sorbitan; sugars and their derivatives (glycosides, etc.), such as glucose, fructose, sucrose and α-methylglucoside, etc.; carbon number 6 to 15. (Bis) cycloalkylene diol ((bi) cycloalkylene diol) {such as 1,4-dihydroxycyclohexane, 1,4-bis(hydroxymethyl)cyclohexane and 2,2-bis( 4,4'-Hydroxycyclohexyl)propane, etc.}]; Polyols containing aromatic rings with 8 to 15 carbon atoms [m- or terephthalenedimethanol and 1,4-bis(hydroxyethyl)benzene, etc.], etc.]; Castor oil polyols (castor oil, partially dehydrated castor oil, partially chelated castor oil, etc.); polymers or oligomers with m hydroxyl groups and a number average molecular weight (hereinafter referred to as Mn) of less than 2,000 [polydiene (carbon Numbers 4 to 10) polyols, such as polybutadiene polyols and their hydrogenates; (co)polymers of (meth)acrylic acid hydroxyalkyl (carbon number 2 to 4) esters; polyvinyl alcohol (saponification degree 60 % or more), etc.]; Polyphenols [monocyclic polyphenols (pyrogallol, catechol, hydroquinone, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) etc.]; phosphate compounds (phosphoric acid, phosphorous acid, phosphonic acid, etc.); and mixtures of two or more thereof.
再者，本說明書中之Mn可藉由凝膠滲透層析法例如於以下條件下進行測定。裝置：「Waters Alliance 2695」[Waters公司製造]管柱：「Guardcolumn Super H-L」（1根），「將TSKgel SuperH2000、TSKgel SuperH3000、TSKgel SuperH4000[均為東曹股份有限公司製造]各連接1根而成者」試樣溶液：0.25重量%之四氫呋喃（以下簡稱THF）溶液溶液注入量：10 μl流量：0.6 ml/min測定溫度：40℃檢測裝置：折射率檢測器基準物質：標準聚乙二醇In addition, Mn in this specification can be measured by gel permeation chromatography, for example, under the following conditions.Device: "Waters Alliance 2695" [manufactured by Waters Corporation]Column: "Guardcolumn Super H-L" (1 piece), "Connected 1 piece each of TSKgel SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 [all manufactured by Tosoh Co., Ltd.]"Sample solution: 0.25% by weight tetrahydrofuran (hereinafter referred to as THF) solutionSolution injection volume: 10 μlFlow rate: 0.6 ml/minMeasuring temperature: 40℃Detection device: refractive index detectorReference material: standard polyethylene glycol
再者，本說明書中之下述重量平均分子量（Mw）能夠藉由凝膠滲透層析法例如於以下條件下進行測定。裝置：「HLC-8320」[東曹股份有限公司製造]保護管柱：Guardcolumn α[東曹股份有限公司製造]管柱：TSKgel α-M[東曹股份有限公司製造]試樣溶液：0.125重量%之二甲基甲醯胺（含有0.01 M LiBr）溶液溶液注入量：100 μl流量：1 ml/min測定溫度：40℃檢測裝置：折射率檢測器基準物質：標準聚苯乙烯In addition, the weight average molecular weight (Mw) mentioned below in this specification can be measured by gel permeation chromatography, for example, under the following conditions.Device: "HLC-8320" [manufactured by Tosoh Co., Ltd.]Guard column: Guardcolumn α [manufactured by Tosoh Co., Ltd.]Column: TSKgel α-M [manufactured by Tosoh Co., Ltd.]Sample solution: 0.125% by weight dimethylformamide (containing 0.01 M LiBr) solutionSolution injection volume: 100 μlFlow rate: 1 ml/minMeasuring temperature: 40℃Detection device: refractive index detectorReference material: Standard polystyrene
作為含羧基化合物，可列舉：碳數2～36之脂肪族多羧酸（琥珀酸、戊二酸、己二酸、癸二酸、順丁烯二酸、反丁烯二酸及二體化亞麻油酸（dimerized linoleic acid）等）、碳數8～15之芳香族多羧酸（鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,4-苯三甲酸及1,2,4,5-苯四甲酸等）、不飽和羧酸聚合物[Mn為2,000以下之(甲基)丙烯酸(共)聚合物等]及其等之2種以上之混合物。Examples of the carboxyl group-containing compound include aliphatic polycarboxylic acids having 2 to 36 carbon atoms (succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and dimerized Linoleic acid (dimerized linoleic acid, etc.), aromatic polycarboxylic acids with 8 to 15 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid and 1, 2,4,5-pyromellitic acid, etc.), unsaturated carboxylic acid polymers [(meth)acrylic acid (co)polymers with Mn of 2,000 or less, etc.] and mixtures of two or more thereof.
作為硫醇，可列舉：碳數2～6或其以上之2～8元之聚硫醇（乙二硫醇、丙二硫醇、1,3-或1,4-丁二硫醇、1,6-己二硫醇及3-甲基-1,5-戊二硫醇等）等。Examples of thiols include 2- to 8-membered polythiols having 2 to 6 carbon atoms or more (ethylene dithiol, propylene dithiol, 1,3- or 1,4-butanedithiol, 1 , 6-hexanedithiol and 3-methyl-1,5-pentanedithiol, etc.), etc.
其中，就硬化性之觀點而言，較佳為含羥基化合物，進而較佳為羥基當量為160以下之脂肪族多元醇及蓖麻油系多元醇，尤佳為丙二醇、甘油、新戊四醇、二新戊四醇、聚甘油（聚合度2～10）及蓖麻油。Among them, from the viewpoint of sclerosis, hydroxyl-containing compounds are preferred, aliphatic polyols and castor oil-based polyols having a hydroxyl equivalent of 160 or less are more preferred, and propylene glycol, glycerol, neopentyl erythritol, dipenterythritol, polyglycerol (degree of polymerization 2 to 10) and castor oil.
通式（2）中之R2為可經苯基或鹵素原子取代之碳數2～12之伸烷基，可列舉：碳數2～12之直鏈或支鏈伸烷基、碳數6～10之伸環烷基及其等經苯基、鹵苯基或鹵素原子（Cl及Br等）取代而成者。R2 in the general formula (2) is an alkylene group with 2 to 12 carbon atoms that may be substituted by a phenyl group or a halogen atom. Examples include: linear or branched alkylene groups with 2 to 12 carbon atoms, and alkylene groups with 6 carbon atoms. ~10 cycloalkyl groups and the like are substituted by phenyl, halophenyl or halogen atoms (Cl, Br, etc.).
作為R2之具體例，可列舉：伸乙基、1,2-或1,3-伸丙基、1,2-、2,3-、1,3-或1,4-伸丁基、碳數5～12之1,2-伸烷基（1,2-伸十二基等）、1,2-伸環己基、氯伸丙基、溴伸丙基、苯基伸乙基及氯苯基伸乙基等。Specific examples of R2 include: ethylene group, 1,2- or 1,3-propylene group, 1,2-, 2,3-, 1,3- or 1,4-butylene group, 1,2-Alkylene group with 5 to 12 carbon atoms (1,2-dodecylene group, etc.), 1,2-cyclohexylene group, chloropropylene group, bromopropylene group, phenyl ethylene group and chlorobenzene Ethyl group, etc.
通式（2）中之(R2-O)係對構成殘基R1之具有m個活性氫原子的化合物加成環氧烷（alkylene oxide）（以下簡稱AO）而得。作為使用之AO，可列舉：環氧乙烷（以下簡稱EO）、1,2-環氧丙烷（以下簡稱PO）、1,3-環氧丙烷、1,2-、1,3-、2,3-或1,4-環氧丁烷（以下環氧丁烷簡稱BO）、碳胺酯基濃度數5～12之α-烯烴氧化物、表鹵醇（epihalohydrin）（表氯醇、表溴醇（epibromohydrin）等）、苯環氧乙烷（styrene oxide）、1,2-環氧環己烷（1,2-cyclohexene oxide）及其等之2種以上之併用，於p個(R2-O)由2種以上氧伸烷基所構成之情形時，鍵結式樣可為嵌段或無規之任一者。其中，就柔軟性之觀點而言，較佳為PO及1,2-BO。(R2 -O) in the general formula (2) is obtained by adding alkylene oxide (hereinafter referred to as AO) to a compound having m active hydrogen atoms constituting the residue R1 . Examples of AO used include: ethylene oxide (hereinafter referred to as EO), 1,2-propylene oxide (hereinafter referred to as PO), 1,3-propylene oxide, 1,2-, 1,3-, 2 , 3- or 1,4-epoxybutane (hereinafter referred to as epoxybutane as BO), α-olefin oxide with a carbon amine ester group concentration of 5 to 12, epihalohydrin (epihalohydrin) (epichlorohydrin, epihalohydrin) Bromohydrin (epibromohydrin, etc.), styrene oxide (styrene oxide), 1,2-cyclohexene oxide (1,2-cyclohexene oxide), and a combination of two or more of them, used in p (R When2 -O) is composed of two or more types of oxyalkylene groups, the bonding pattern may be either block or random. Among them, from the viewpoint of softness, PO and 1,2-BO are preferred.
通式（2）中之R3為伸丙基。p較佳為0～199之整數，進而較佳為1～100之整數，最佳為3～30之整數。q為1～200之整數，較佳為滿足1≦p＋q≦200，進而較佳為滿足3≦p＋q≦100。R3 in the general formula (2) is propyl group. p is preferably an integer from 0 to 199, further preferably an integer from 1 to 100, and most preferably an integer from 3 to 30. q is an integer from 1 to 200, and preferably satisfies 1≦p+q≦200, and more preferably satisfies 3≦p+q≦100.
聚氧伸烷基多元醇（a1）例如可藉由日本特開2000-344881號公報所記載之方法進行製造。作為聚氧伸烷基多元醇（a1）之較佳例，可列舉於三(五氟苯基)硼烷（tris(pentafluorophenyl)borane）觸媒（以下簡稱TPB）之存在下，使PO開環與下述通式（3）所表示之含活性氫之化合物（a0）加成聚合所得者等。若藉由通常之觸媒使PO開環加成聚合，則β裂解占絕對優勢，因此二級羥基之比率變高，但利用上述方法使PO開環加成聚合，藉此可提高使PO進行α裂解之比率，因此可獲得滿足特定之一級羥基含有率之聚氧伸烷基多元醇（a1）。The polyoxyalkylene polyol (a1) can be produced by the method described in Japanese Patent Application Laid-Open No. 2000-344881, for example. Preferable examples of the polyoxyalkylene polyol (a1) include ring-opening PO in the presence of tris(pentafluorophenyl)borane catalyst (hereinafter referred to as TPB). Those obtained by addition polymerization with the active hydrogen-containing compound (a0) represented by the following general formula (3), etc. If PO ring-opening addition polymerization is carried out using a normal catalyst, β-cleavage will dominate, so the ratio of secondary hydroxyl groups becomes higher. However, by using the above method to perform ring-opening addition polymerization of PO, the polymerization rate of PO can be increased. α-cleavage ratio, it is possible to obtain a polyoxyalkylene polyol (a1) that satisfies a specific primary hydroxyl content ratio.
R1[-(R2-O)p-H]m（3）R1 [-(R2 -O)p -H]m (3)
通式（3）中之R1、R2及m與上述通式（2）相同，p為0或1～199之整數。R1 , R2 and m in the general formula (3) are the same as in the above general formula (2), and p is 0 or an integer from 1 to 199.
作為(R2-O)之具體例，於p為0之情形時，可列舉與上述通式（2）之構成殘基之具有m個活性氫原子的化合物所例示者相同者。Specific examples of (R2 -O) when p is 0 include the same compounds as those exemplified for the compound having m active hydrogen atoms constituting the residue of the general formula (2).
p為1以上之情形時之含活性氫的化合物（a0）為使用先前公知之觸媒（鹼金屬氫氧化物等）使R2-O與構成殘基R1之化合物（共）加成所得的多元醇，作為較佳例，可列舉：丙二醇之PO加成物、甘油之PO加成物、聚甘油之PO加成物、丙二醇之1,2-BO加成物、甘油之1,2-BO加成物、聚甘油之1,2-BO加成物、甘油之PO/1,2-BO共加成物（嵌段或無規）等。When p is 1 or more, the active hydrogen-containing compound (a0) is obtained by (co)addition of R2 -O and the compound constituting the residue R1 using a conventionally known catalyst (alkali metal hydroxide, etc.) Preferred examples of polyols include: propylene glycol PO adduct, glycerin PO adduct, polyglycerol PO adduct, propylene glycol 1,2-BO adduct, glycerin 1,2 -BO adduct, 1,2-BO adduct of polyglycerol, PO/1,2-BO co-adduct of glycerol (block or random), etc.
於使PO開環與含活性氫之化合物（a0）加成聚合而製造聚氧伸烷基多元醇（a1）時，TPB之使用量並無特別限定，基於聚氧伸烷基多元醇（a1）之重量，較佳為0.00005～10重量%，進而較佳為0.0001～1重量%。When PO ring-opening and the active hydrogen-containing compound (a0) are added and polymerized to produce polyoxyalkylene polyol (a1), the amount of TPB used is not particularly limited. Based on the polyoxyalkylene polyol (a1) ) is preferably 0.00005 to 10% by weight, and more preferably 0.0001 to 1% by weight.
PO之加成莫耳數為含活性氫之化合物（a0）之每個活性氫原子為1～200莫耳，較佳為2～100莫耳，進而較佳為3～30莫耳。構成殘基R1之化合物之每個活性氫原子的總AO（第1階段之AO及第2階段之PO之合計）之加成莫耳數為1～200莫耳，較佳為3～100莫耳。若該等之加成莫耳數超過200莫耳，則聚氧伸烷基多元醇（a1）之黏度變高，塗敷主劑與硬化劑之混合液時的黏度變高。The added molar number of PO is 1 to 200 moles per active hydrogen atom of the active hydrogen-containing compound (a0), preferably 2 to 100 moles, and further preferably 3 to 30 moles. The molar addition number of each active hydrogen atom of the compound constituting the residue R1 (the sum of the AO in the first stage and the PO in the second stage) is 1 to 200 moles, preferably 3 to 100 More. If the added mole number exceeds 200 moles, the viscosity of the polyoxyalkylene polyol (a1) becomes high, and the viscosity when coating the mixture of the main agent and the hardener becomes high.
使PO開環加成聚合時之反應溫度較佳為0～250℃，進而較佳為20～180℃。就控制反應溫度之觀點而言，較佳為於含活性氫之化合物（a0）與TPB之混合物中滴加PO，或者於含活性氫之化合物（a0）中滴加PO與TPB之混合物的方法。The reaction temperature when performing ring-opening addition polymerization of PO is preferably 0 to 250°C, and more preferably 20 to 180°C. From the viewpoint of controlling the reaction temperature, a method in which PO is added dropwise to the mixture of the active hydrogen-containing compound (a0) and TPB, or a mixture of PO and TPB is added dropwise to the active hydrogen-containing compound (a0) is preferred. .
製造之加成聚合物包含TPB，因此使用合成矽酸鹽（矽酸鎂及矽酸鋁等）及活性白土等吸附劑進行吸附去除處理。The manufactured addition polymer contains TPB, so adsorbents such as synthetic silicate (magnesium silicate, aluminum silicate, etc.) and activated clay are used for adsorption and removal treatment.
作為聚氧伸烷基多元醇（a1）之較佳之具體例，可列舉聚丙二醇、聚丙三醇等。聚氧伸烷基多元醇（a1）可單獨使用1種，亦可併用2種以上。Preferable specific examples of the polyoxyalkylene polyol (a1) include polypropylene glycol, polyglycerol, and the like.One type of polyoxyalkylene polyol (a1) may be used alone, or two or more types may be used in combination.
聚氧伸烷基多元醇（a1）之總不飽和度較佳為0.025 meq/g以下，更佳為0.015 meq/g以下，進而較佳為0.010 meq/g以下。藉由使聚氧伸烷基多元醇（a1）之總不飽和度為0.025 meq/g以下，而使胺酯黏著劑之硬化物之凝聚力提高，又使低分子量成分減少，藉此可減少被黏著體之污染。再者，本發明中之總不飽和度可藉由JIS K1557-3所記載之方法進行測定。The total degree of unsaturation of the polyoxyalkylene polyol (a1) is preferably 0.025 meq/g or less, more preferably 0.015 meq/g or less, further preferably 0.010 meq/g or less.By making the total unsaturation of the polyoxyalkylene polyol (a1) 0.025 meq/g or less, the cohesion of the hardened product of the urethane adhesive is increased and the low molecular weight components are reduced, thereby reducing the amount of Adhesive contamination. In addition, the total degree of unsaturation in the present invention can be measured by the method described in JIS K1557-3.
不具有胺基之多元醇成分（A）所含之全部多元醇成分的總不飽和度較佳為0.001～0.025 meq/g，進而較佳為0.003～0.020 meq/g，尤佳為0.005～0.015 meq/g。藉由使多元醇成分（A）所含之全部多元醇成分之總不飽和度為0.025 meq/g以下，而使胺酯黏著劑之硬化物之凝聚力提高，又藉由使（A）之總不飽和度為0.001 meq/g以上，而獲得較強之黏著力。即，藉由設為上述範圍，可適宜地兼顧凝聚力與黏著力之性能。The total degree of unsaturation of all the polyol components contained in the polyol component (A) without an amine group is preferably 0.001 to 0.025 meq/g, more preferably 0.003 to 0.020 meq/g, and particularly preferably 0.005 to 0.015 meq/g.By making the total degree of unsaturation of all the polyol components contained in the polyol component (A) 0.025 meq/g or less, the cohesion of the cured product of the urethane adhesive is improved, and by making the total amount of (A) The degree of unsaturation is above 0.001 meq/g, resulting in strong adhesion. That is, by setting it as the said range, the performance of cohesive force and adhesive force can be suitably balanced.
就黏著劑之黏著力及黏彈特性之觀點而言，聚氧伸烷基多元醇（a1）之羥值因有無併用下述除聚氧伸烷基多元醇（a1）以外之多元醇（a2）以及併用的多元醇之種類而異，較佳為5～800 mgKOH/g，進而較佳為10～450 mgKOH/g，尤佳為20～300 mgKOH/g。From the viewpoint of the adhesive force and viscoelastic properties of the adhesive, the hydroxyl value of polyoxyalkylene polyol (a1) depends on whether or not the following polyols (a2) other than polyoxyalkylene polyol (a1) are used in combination. ) and the type of polyol used in combination, 5 to 800 mgKOH/g is preferred, 10 to 450 mgKOH/g is more preferred, and 20 to 300 mgKOH/g is particularly preferred.
多元醇成分（A）中之聚氧伸烷基多元醇（a1）之含量基於多元醇成分（A）的重量較佳為20重量%以上，進而較佳為50重量%以上，尤佳為70重量%以上。若聚氧伸烷基多元醇（a1）之含量為20重量%以上，則柔軟性、黏著力之溫度依存性以及黏著力之被黏著體種類依存性及膜厚依存性良好。The content of the polyoxyalkylene polyol (a1) in the polyol component (A) is preferably 20% by weight or more based on the weight of the polyol component (A), more preferably 50% by weight or more, and particularly preferably 70% by weight. More than % by weight. When the content of polyoxyalkylene polyol (a1) is 20% by weight or more, the temperature dependence of flexibility and adhesive force, and the dependence of adhesive force on adherend type and film thickness will be good.
多元醇成分（A）可含有除聚氧伸烷基多元醇（a1）以外之多元醇（a2）[以下簡稱多元醇（a2）]。The polyol component (A) may contain a polyol (a2) other than the polyoxyalkylene polyol (a1) [hereinafter referred to as the polyol (a2)].
作為上述多元醇（a2），可列舉：除上述聚氧伸烷基多元醇（a1）以外之聚氧伸烷基多元醇（a21）、作為上述構成殘基R1之具有m個活性氫原子之化合物所記載的含羥基化合物（a22）、聚酯多元醇（a23）等。Examples of the polyoxyalkylene polyol (a2) include polyoxyalkylene polyol (a21) other than the polyoxyalkylene polyol (a1), and a polyoxyalkylene polyol (a21) having m active hydrogen atoms as the constituent residueR1 . The hydroxyl-containing compound (a22), polyester polyol (a23), etc. described in the compound.
作為除上述聚氧伸烷基多元醇（a1）以外之聚氧伸烷基多元醇（a21），可列舉：分子末端並非羥丙基之聚氧伸烷基多元醇、分子末端為羥丙基，且其一級羥基含有率未達40%之聚氧伸烷基多元醇等。Examples of the polyoxyalkylene polyol (a21) other than the above-mentioned polyoxyalkylene polyol (a1) include polyoxyalkylene polyols whose molecular terminals are not hydroxypropyl groups and polyoxyalkylene polyols whose molecular terminals are hydroxypropyl groups. , and polyoxyalkylene polyols whose primary hydroxyl content does not reach 40%.
作為聚酯多元醇（a23），可列舉：蓖麻油脂肪酸酯多元醇（例如蓖麻油、部分脫水蓖麻油及蓖麻油脂肪酸酯）；由多（n＝2～3或其以上）羧酸[脂肪族飽和或不飽和多羧酸（碳數2～40，例如草酸、己二酸、壬二酸、十二酸、順丁烯二酸、反丁烯二酸、伊康酸及二體化亞麻油酸）、含芳香環之多羧酸（碳數8～15，例如鄰苯二甲酸、間苯二甲酸、對苯二甲酸及2,6-萘二甲酸）及含脂環之多羧酸（碳數7～15，例如1,3-戊二羧酸及1,4-己二羧酸）等]與多元醇[例如上述含羥基化合物、聚氧伸烷基多元醇（a1）及多元醇（a2）等]所形成之線性或支鏈狀聚酯多元醇；聚內酯多元醇[例如以上述含羥基化合物（二～三元）之1種或2種以上之混合物為起始劑使其與（經取代）己內酯（碳數6～10，例如ε-己內酯、α-甲基-ε-己內酯及ε-甲基-ε-己內酯）於觸媒（有機金屬化合物、金屬螯合物化合物及脂肪酸金屬醯基化合物等）之存在下進行加成聚合所得之多元醇（例如聚己內酯多元醇）]；使AO（EO及PO等）與末端具有羧基及/或羥基之聚酯進行加成聚合所得之聚醚酯多元醇；聚碳酸酯多元醇等。Examples of polyester polyols (a23) include: castor oil fatty acid ester polyols (such as castor oil, partially dehydrated castor oil, and castor oil fatty acid esters); polyols composed of poly(n=2 to 3 or more) carboxylic acids [Aliphatic saturated or unsaturated polycarboxylic acid (carbon number 2 to 40, such as oxalic acid, adipic acid, azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid and disacid Linoleic acid), polycarboxylic acids containing aromatic rings (8 to 15 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid) and polycarboxylic acids containing alicyclic rings Carboxylic acids (carbon number 7 to 15, such as 1,3-pentanedicarboxylic acid and 1,4-hexanedicarboxylic acid), etc.] and polyols [such as the above-mentioned hydroxyl-containing compounds, polyoxyalkylene polyol (a1) and polyol (a2), etc.] formed by linear or branched polyester polyol; polylactone polyol [for example, starting from one or a mixture of two or more of the above-mentioned hydroxyl-containing compounds (di- to tri-valent) The starting agent brings it into contact with (substituted) caprolactone (carbon number 6 to 10, such as ε-caprolactone, α-methyl-ε-caprolactone and ε-methyl-ε-caprolactone). Polyols (such as polycaprolactone polyols) obtained by addition polymerization in the presence of solvents (organometallic compounds, metal chelate compounds, fatty acid metal chelate compounds, etc.)]; making AO (EO and PO, etc.) and Polyetherester polyols obtained by addition polymerization of polyesters with carboxyl and/or hydroxyl groups at the terminals; polycarbonate polyols, etc.
多元醇（a2）中，就硬化性以及黏著劑之硬化物之柔軟性及韌性之觀點而言，較佳為上述含羥基化合物（a22）中之羥基當量為160以下之低分子多元醇、由碳數2～6之脂肪族多羧酸與碳數2～8之烷二醇所構成的聚酯二醇。多元醇（a2）可單獨使用1種，亦可併用2種以上。Among the polyols (a2), from the viewpoint of curability and the softness and toughness of the cured product of the adhesive, a low-molecular polyol in which the hydroxyl equivalent weight of the hydroxyl group equivalent in the above-mentioned hydroxyl-containing compound (a22) is 160 or less is preferred. Polyester diol composed of aliphatic polycarboxylic acid with 2 to 6 carbon atoms and alkylene glycol with 2 to 8 carbon atoms.One type of polyol (a2) may be used alone, or two or more types may be used in combination.
就柔軟性與硬化性之觀點而言，多元醇（a2）之羥值較佳為10～1500 mgKOH/g，進而較佳為20～500 mgKOH/g，尤佳為30～150 mgKOH/g。From the viewpoint of flexibility and hardening properties, the hydroxyl value of the polyol (a2) is preferably 10 to 1500 mgKOH/g, more preferably 20 to 500 mgKOH/g, and particularly preferably 30 to 150 mgKOH/g.
就硬化性之觀點而言，多元醇（a2）之數量平均官能基數較佳為2～5，進而較佳為2～4，尤佳為2～3。From the viewpoint of curability, the number average functional group number of the polyol (a2) is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3.
於使用多元醇（a2）之情形時，就黏著劑之黏彈特性之觀點而言，多元醇（a2）之含量基於多元醇成分（A）之重量較佳為5～95重量%，進而較佳為10～90重量%，尤佳為20～80重量%。When polyol (a2) is used, from the viewpoint of the viscoelastic properties of the adhesive, the content of polyol (a2) is preferably 5 to 95% by weight based on the weight of polyol component (A), and further preferably Preferably, it is 10-90 weight%, especially 20-80 weight%.
只要不影響本案發明之效果，多元醇成分（A）可含有一元醇。作為一元醇，可列舉甲醇、乙醇等。As long as the effect of the present invention is not affected, the polyol component (A) may contain a monohydric alcohol. Examples of the monohydric alcohol include methanol, ethanol, and the like.
（異氰酸酯成分（B））作為異氰酸酯成分（B），可列舉：具有2～3個或其以上之異氰酸基之碳數4～22的鏈狀脂肪族多異氰酸酯（b1）、碳數8～18之脂環式多異氰酸酯（b2）、碳數8～26之芳香族多異氰酸酯（b3）、碳數10～18之芳香脂肪族多異氰酸酯（b4）及該等多異氰酸酯的改質物（b5）等。異氰酸酯成分（B）可單獨使用1種，亦可併用2種以上。(Isocyanate component (B))Examples of the isocyanate component (B) include chain aliphatic polyisocyanates (b1) having 2 to 3 isocyanate groups or more and having 2 to 3 isocyanate groups or more. Isocyanate (b2), aromatic polyisocyanate with 8 to 26 carbon atoms (b3), aromatic aliphatic polyisocyanate with 10 to 18 carbon atoms (b4), modified products of these polyisocyanates (b5), etc. One type of isocyanate component (B) may be used alone, or two or more types may be used in combination.
作為碳數4～22之鏈狀脂肪族多異氰酸酯（b1），例如可列舉：二異氰酸乙二酯（ethylene diisocyanate）、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯（以下簡稱HDI）、十二亞甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、2,6-二異氰酸基己酸甲酯、反丁烯二酸雙(2-異氰酸基乙基)酯、碳酸雙(2-異氰酸基乙基)酯及2,6-二異氰酸基己酸2-異氰酸基乙酯等。Examples of the chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate (hereinafter referred to as HDI). ), dodedecane diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanurate Methyl cyanatocaproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate and 2,6-diisocyanatohexane Acid 2-isocyanatoethyl, etc.
作為碳數8～18之脂環式多異氰酸酯（b2），例如可列舉：異佛酮二異氰酸酯（以下簡稱IPDI）、4,4'-二環己基甲烷二異氰酸酯（以下簡稱氫化MDI）、環己二異氰酸酯（cyclohexylene diisocyanate）、甲基環己二異氰酸酯、4-環己烯-1,2-二甲酸雙(2-異氰酸基乙基)酯及2,5-或2,6-降莰烷二異氰酸酯等。Examples of the alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter referred to as IPDI), 4,4'-dicyclohexylmethane diisocyanate (hereinafter referred to as hydrogenated MDI), cyclohexylmethane diisocyanate (hereinafter referred to as hydrogenated MDI), and cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, 4-cyclohexene-1,2-dicarboxylic acid bis(2-isocyanatoethyl) ester and 2,5- or 2,6-diisocyanate Bornane diisocyanate, etc.
作為碳數8～26之芳香族多異氰酸酯（b3），例如可列舉：1,3-或1,4-苯二異氰酸酯（1,3- or 1,4-phenylene diisocyanate）、2,4-或2,6-甲苯二異氰酸酯（以下簡稱TDI）、粗製TDI、4,4'-或2,4'-二苯基甲烷二異氰酸酯（以下簡稱MDI）、粗製MDI、多芳基多異氰酸酯、4,4'-二異氰酸基聯苯、3,3'-二甲基-4,4'-二異氰酸基聯苯、3,3'-二甲基-4,4'-二異氰酸基二苯基甲烷、1,5-萘二異氰酸酯（1,5-naphthylene diisocyanate）、4,4',4''-三苯基甲烷三異氰酸酯及間或對異氰酸基苯基磺醯基異氰酸酯等。Examples of the aromatic polyisocyanate (b3) having 8 to 26 carbon atoms include: 1,3- or 1,4-phenylene diisocyanate (1,3- or 1,4-phenylene diisocyanate), 2,4- or 2,6-Toluene diisocyanate (hereinafter referred to as TDI), crude TDI, 4,4'- or 2,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI), crude MDI, polyaryl polyisocyanate, 4, 4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Acid diphenylmethane, 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate and m-or p-isocyanatophenyl sulfonate isocyanate, etc.
作為碳數10～18之芳香脂肪族多異氰酸酯（b4），例如可列舉：間或對苯二甲基二異氰酸酯（m- or p-xylylene diisocyanate）及α,α,α',α'-四甲基苯二甲基二異氰酸酯等。Examples of the aromatic aliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate (m- or p-xylylene diisocyanate) and α, α, α', α'-tetrakis Tolyxylylene diisocyanate, etc.
作為多異氰酸酯（b1）～（b4）之多異氰酸酯之改質物（b5），可列舉：上述多異氰酸酯之改質物（含胺酯基、碳二亞胺基、脲基甲酸酯基、脲基、縮二脲基、脲二酮（uretdione）基、脲亞胺（uretonimine）基、異氰尿酸酯基或唑啶酮基之改質物等；游離異氰酸基含量較佳為8～33重量%、進而較佳為10～30重量%、尤佳為12～29重量%之多異氰酸酯之改質物）；例如改質MDI（胺酯改質MDI、碳二亞胺改質MDI及磷酸三烴基酯（trihydrocarbyl phosphate）改質MDI等）、胺酯改質TDI、縮二脲改質HDI、異氰尿酸酯改質HDI及異氰尿酸酯改質IPDI等多異氰酸酯之改質物等。Examples of modified products (b5) of polyisocyanates (b1) to (b4) include modified products of the above polyisocyanates (containing amine ester group, carbodiimide group, allophanate group, and urea group). , biuret group, uretdione group, uretonimine group, isocyanurate group or Modified products of oxazolidinone groups, etc.; modified products of polyisocyanate with a free isocyanate group content of preferably 8 to 33 wt%, more preferably 10 to 30 wt%, and especially 12 to 29 wt%); For example, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, biuret-modified HDI, isocyanuric acid Modified products of polyisocyanates such as ester-modified HDI and isocyanurate-modified IPDI.
該等有機多異氰酸酯中，就黏著劑之硬化物之色相的觀點而言，較佳為碳數4～22之鏈狀脂肪族多異氰酸酯（b1）及碳數8～18之脂環式多異氰酸酯（b2），進而較佳為碳數4～22之鏈狀脂肪族多異氰酸酯（b1）。Among these organic polyisocyanates, from the viewpoint of the hue of the cured product of the adhesive, chain aliphatic polyisocyanates (b1) having 4 to 22 carbon atoms and alicyclic polyisocyanates having 8 to 18 carbon atoms are preferred. (b2), more preferably a chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms.
（具有羥基之胺（C））聚胺酯樹脂進而含有具有羥基之胺（C）作為構成單體，較佳為具有羥基之胺（C）之羥值為50～1200 mgKOH/g，胺值為50～1200 mgKOH/g。(Amine (C) with hydroxyl group)The polyurethane resin further contains an amine (C) having a hydroxyl group as a constituent monomer. The amine (C) having a hydroxyl group preferably has a hydroxyl value of 50 to 1200 mgKOH/g and an amine value of 50 to 1200 mgKOH/g.
就黏著劑之凝聚力及黏著力之觀點而言，具有羥基之胺（C）之羥值較佳為50～1200 mgKOH/g，進而較佳為100～1100 mgKOH/g，尤佳為200～1000 mgKOH/g。本發明中之羥值可藉由JIS K 1557-1所記載之方法進行測定。From the viewpoint of the cohesion and adhesive force of the adhesive, the hydroxyl value of the amine (C) having a hydroxyl group is preferably 50 to 1200 mgKOH/g, more preferably 100 to 1100 mgKOH/g, and particularly preferably 200 to 1000 mgKOH/g.The hydroxyl value in the present invention can be measured by the method described in JIS K 1557-1.
就黏著劑之凝聚力及黏著力之觀點而言，具有羥基之胺（C）之胺值較佳為50～1200 mgKOH/g，進而較佳為100～1150 mgKOH/g，尤佳為200～1100 mgKOH/g。本發明中之胺值可藉由JIS K 7237之方法進行測定。From the viewpoint of the cohesion and adhesive force of the adhesive, the amine value of the amine (C) having a hydroxyl group is preferably 50 to 1200 mgKOH/g, more preferably 100 to 1150 mgKOH/g, and particularly preferably 200 to 1100 mgKOH/g. The amine value in the present invention can be measured according to the method of JIS K 7237.
較佳為具有羥基之胺（C）含有具有羥基之單胺（c1）以及具有羥基之二胺（c2），具有羥基之單胺（c1）之含量基於具有羥基的胺（C）之合計重量為0.5～50重量%，具有羥基之二胺（c2）之含量基於具有羥基的胺（C）之合計重量為50～99.5重量%。Preferably, the amine (C) with a hydroxyl group contains a monoamine (c1) with a hydroxyl group and a diamine (c2) with a hydroxyl group. The content of the monoamine (c1) with a hydroxyl group is based on the total weight of the amine (C) with a hydroxyl group. The content of the diamine (c2) having a hydroxyl group is 0.5 to 50% by weight, and the content of the diamine (c2) having a hydroxyl group is 50 to 99.5% by weight based on the total weight of the amine (C) having a hydroxyl group.
作為具有羥基之單胺（c1），可列舉羥烷基之碳數為2～18之單或二烷醇單胺等。作為羥烷基之碳數為2～18之單或二烷醇單胺的具體例，可列舉：單乙醇胺、二乙醇胺、丙醇胺及單異丙醇胺等。具有羥基之單胺（c1）可單獨使用1種，亦可併用2種以上。其中，就黏著劑之黏著力及凝聚力等觀點而言，較佳為羥烷基之碳數為2～18之單或二烷醇單胺，進而較佳為羥烷基之碳數為2～18之單烷醇單胺。Examples of the monoamine (c1) having a hydroxyl group include mono- or dialkyl monoamines having a hydroxyalkyl group having 2 to 18 carbon atoms.Specific examples of mono- or di-alkanol monoamines whose hydroxyalkyl group has 2 to 18 carbon atoms include monoethanolamine, diethanolamine, propanolamine, and monoisopropanolamine.The monoamine (c1) having a hydroxyl group may be used alone or in combination of two or more types.Among them, from the viewpoint of the adhesive force and cohesive force of the adhesive, mono- or dialkyl monoamines having a hydroxyalkyl group having a carbon number of 2 to 18 are more preferred, and even more preferred are those having a hydroxyalkyl group having a carbon number of 2 to 18. 18. Monoalkanol monoamine.
作為具有羥基之二胺（c2），可列舉羥烷基之碳數為2～18之單或二烷醇二胺。作為羥烷基之碳數為2～18之單烷醇二胺的具體例，可列舉N-(2-胺基乙基)乙醇胺及N-(2-羥基丙基)乙二胺等。具有羥基之二胺（c2）可單獨使用1種，亦可併用2種以上。其中，就聚胺酯樹脂之高分子量化之容易度、黏著劑之黏著力及凝聚力等觀點而言，較佳為羥烷基之碳數為2～18之單或二烷醇二胺，進而較佳為羥烷基之碳數為2～18之單烷醇二胺。Examples of the diamine (c2) having a hydroxyl group include mono- or dialkanol diamines whose hydroxyalkyl group has 2 to 18 carbon atoms.Specific examples of monoalkanol diamines having a hydroxyalkyl group having 2 to 18 carbon atoms include N-(2-aminoethyl)ethanolamine, N-(2-hydroxypropyl)ethylenediamine, and the like.One type of diamine (c2) having a hydroxyl group may be used alone, or two or more types may be used in combination.Among them, from the viewpoint of the ease of high molecularization of the polyurethane resin, the adhesive force and cohesive force of the adhesive, mono- or dialkyl diamines with a carbon number of 2 to 18 in the hydroxyalkyl group are preferred, and further preferred It is a monoalkanol diamine with a carbon number of 2 to 18 in the hydroxyalkyl group.
作為具有羥基之胺（C），亦可含有具有羥基以及3官能以上之胺基之胺（c3）。The amine (C) having a hydroxyl group may include an amine (c3) having a hydroxyl group and a trifunctional or higher amino group.
作為具有羥基以及3官能以上之胺基之胺（c3），可列舉：N,N'-雙(羥乙基)二伸乙基三胺、N,N'-雙(羥乙基)三乙四胺等。具有羥基以及3官能以上之胺基之胺（c3）可單獨使用1種，亦可併用2種以上。Examples of the amine (c3) having a hydroxyl group and a trifunctional or higher amino group include: N,N'-bis(hydroxyethyl)diethylenetriamine, N,N'-bis(hydroxyethyl)triethyl Tetraamine etc.One type of amine (c3) having a hydroxyl group and a trifunctional or higher amino group may be used alone, or two or more types may be used in combination.
就聚胺酯樹脂之高分子量化之容易度、黏著劑之黏著力及凝聚力等觀點而言，具有羥基之胺（C）較佳為含有具有羥基之二胺（c2），進而較佳為含有具有羥基之單胺（c1）以及具有羥基之二胺（c2）。From the viewpoints of the ease of high molecularization of the polyurethane resin, the adhesive force and cohesion of the adhesive, etc., the amine (C) having a hydroxyl group is preferably a diamine (c2) having a hydroxyl group, and further preferably a diamine (c2) having a hydroxyl group. Monoamine (c1) and diamine (c2) with hydroxyl group.
就聚胺酯樹脂溶液之黏度及黏著力之觀點而言，具有羥基之單胺（c1）之含量基於具有羥基的胺（C）之合計重量較佳為0.5～50重量%，進而較佳為1～40重量%，尤佳為3～30重量%。From the viewpoint of the viscosity and adhesive force of the polyurethane resin solution, the content of the monoamine (c1) having a hydroxyl group is preferably 0.5 to 50% by weight based on the total weight of the amine (C) having a hydroxyl group, and further preferably 1 to 50% by weight. 40% by weight, preferably 3 to 30% by weight.
就聚胺酯樹脂溶液之膜強度及黏著力之觀點而言，具有羥基之二胺（c2）之含量基於具有羥基的胺（C）之合計重量較佳為50～99.5重量%，進而較佳為60～99重量%，尤佳為70～97重量%。From the viewpoint of the film strength and adhesive force of the polyurethane resin solution, the content of the diamine (c2) having a hydroxyl group is preferably 50 to 99.5% by weight based on the total weight of the amine (C) having a hydroxyl group, and further preferably 60% ~99% by weight, especially 70-97% by weight.
就聚胺酯樹脂溶液之黏度之觀點而言，具有羥基以及3官能以上之胺基之胺（c3）的含量基於具有羥基之胺（C）之合計重量較佳為0～30重量%，進而較佳為0～15重量%，尤佳為0～5重量%。From the viewpoint of the viscosity of the polyurethane resin solution, the content of the amine (c3) having a hydroxyl group and a trifunctional or higher amine group is preferably 0 to 30% by weight based on the total weight of the amine (C) having a hydroxyl group, and more preferably The content is 0 to 15% by weight, particularly preferably 0 to 5% by weight.
（聚胺酯樹脂）本發明之黏著劑所含有之聚胺酯樹脂能夠藉由利用公知之方法使上述多元醇成分（A）、上述有機多異氰酸酯成分（B）、以及視需要上述具有羥基之胺（C）聚合而獲得。其中，較佳為上述聚胺酯樹脂係胺酯預聚物（P）與鏈伸長劑（X）之反應物，該胺酯預聚物（P）係使上述多元醇成分（A）及上述異氰酸酯成分（B）反應而獲得，該鏈伸長劑（X）包含上述具有羥基之胺（C），具有羥基之胺（C）係含有具有羥基之單胺（c1）及具有羥基之二胺（c2）的混合物，具有羥基之單胺（c1）之含量與具有羥基之二胺（c2）之含量的合計基於包含具有羥基之胺（C）之鏈伸長劑（X）之合計重量為5～100重量%。(polyurethane resin)The polyurethane resin contained in the adhesive of the present invention can be obtained by polymerizing the above-mentioned polyol component (A), the above-mentioned organic polyisocyanate component (B), and if necessary, the above-mentioned amine having a hydroxyl group (C) using a known method.Among them, the reaction product of the above-mentioned polyurethane resin-based urethane prepolymer (P) and the chain extender (X) is preferred. The urethane prepolymer (P) is a mixture of the above-mentioned polyol component (A) and the above-mentioned isocyanate component. (B) obtained by the reaction, the chain extender (X) includes the above-mentioned amine with a hydroxyl group (C), the amine with a hydroxyl group (C) contains a monoamine with a hydroxyl group (c1) and a diamine with a hydroxyl group (c2) The mixture, the total content of the monoamine (c1) having a hydroxyl group and the content of the diamine (c2) having a hydroxyl group is 5 to 100 weight based on the total weight of the chain extender (X) containing the amine (C) having a hydroxyl group %.
上述胺酯預聚物（P）能夠藉由利用慣例使多元醇成分（A）與異氰酸酯成分（B）反應而獲得。The above-mentioned urethane prepolymer (P) can be obtained by reacting the polyol component (A) and the isocyanate component (B) using conventional methods.
上述胺酯預聚物（P）之異氰酸基濃度較佳為0.4～15重量%，進而較佳為0.6～8.4重量%，尤佳為0.8～4.2重量%，最佳為1.1～2.8重量%。若胺酯預聚物（P）之異氰酸基濃度超過15重量%，則有獲得之聚胺酯樹脂之彈性模數變得過高而使黏著力降低之情況，若未達0.4重量%，則有因極性基之量減少而使黏著力降低之情況。The isocyanate group concentration of the above-mentioned urethane prepolymer (P) is preferably 0.4 to 15% by weight, more preferably 0.6 to 8.4% by weight, particularly preferably 0.8 to 4.2% by weight, and most preferably 1.1 to 2.8% by weight. %.If the isocyanate group concentration of the urethane prepolymer (P) exceeds 15% by weight, the elastic modulus of the polyurethane resin obtained may become too high and the adhesive force may decrease. If it is less than 0.4% by weight, the elastic modulus may become too high. The adhesion force may decrease due to the decrease in the amount of polar groups.
作為胺酯預聚物（P）之製造方法，可使用已知之胺酯之製造方法，例如可列舉於溶劑（甲苯、二甲苯、乙酸乙酯、乙酸丁酯、二甲基甲醯胺、丙酮、甲基乙基酮及THF等）之存在或不存在下，使多元醇成分（A）與異氰酸酯成分（B）反應之方法。藉由調整多元醇成分（A）之含活性氫之基的莫耳數相對於異氰酸酯成分（B）之異氰酸酯之莫耳數的比率，可製造末端具有羥基之胺酯預聚物或末端具有異氰酸基之胺酯預聚物。As a method for producing the urethane prepolymer (P), a known method for producing an urethane can be used, and examples thereof include solvents (toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone). , methyl ethyl ketone, THF, etc.), a method of reacting the polyol component (A) and the isocyanate component (B) in the presence or absence of the polyol component (A). By adjusting the ratio of the molar number of the active hydrogen-containing group of the polyol component (A) to the molar number of the isocyanate of the isocyanate component (B), it is possible to produce an urethane prepolymer having a hydroxyl group at the terminal or an isocyanate at the terminal. Cyanate-based urethane prepolymer.
多元醇成分（A）與異氰酸酯成分（B）之反應可使用公知之反應裝置（具備攪拌機之混合槽及靜態混合器等），就反應性及抑制熱劣化之觀點而言，反應溫度較佳為10～160℃，進而較佳為25～120℃，就穩定性之觀點而言，較佳為用氮氣置換氣相部。The reaction between the polyol component (A) and the isocyanate component (B) can use a known reaction device (a mixing tank equipped with a stirrer, a static mixer, etc.). From the viewpoint of reactivity and suppression of thermal deterioration, the reaction temperature is preferably 10 to 160°C, more preferably 25 to 120°C, and from the viewpoint of stability, it is preferred to replace the gas phase part with nitrogen.
就獲得之黏著劑之硬化物之強度及黏著力之觀點而言，使多元醇成分（A）與異氰酸酯成分（B）反應之情形時，異氰酸酯成分（B）之異氰酸基之莫耳數相對於（A）的含活性氫之基之莫耳數的比率（異氰酸基之莫耳數/含活性氫之基之莫耳數）較佳為0.5～2.0，進而較佳為0.6～1.9，最佳為0.7～1.8。From the viewpoint of the strength and adhesive force of the cured adhesive obtained, when the polyol component (A) and the isocyanate component (B) are reacted, the molar number of the isocyanate group of the isocyanate component (B) The ratio of the molar number of the active hydrogen-containing group to (A) (the molar number of the isocyanate group/the molar number of the active hydrogen-containing group) is preferably 0.5 to 2.0, and further preferably 0.6 to 1.9, the best is 0.7~1.8.
本發明之黏著劑所含有之聚胺酯樹脂較佳為使包含具有羥基之胺（C）的鏈伸長劑（X）與上述胺酯預聚物（P）反應，使上述胺酯預聚物（P）鏈伸長而獲得。The polyurethane resin contained in the adhesive of the present invention is preferably made by reacting a chain extender (X) containing an amine (C) with a hydroxyl group and the above-mentioned urethane prepolymer (P), so that the above-mentioned urethane prepolymer (P) ) obtained by chain elongation.
作為使鏈伸長劑（X）與胺酯預聚物（P）反應之方法，可列舉於溶劑（甲苯、二甲苯、乙酸乙酯、乙酸丁酯、二甲基甲醯胺、丙酮、異丙醇、甲基乙基酮及四氫呋喃等）之存在或不存在下，使鏈伸長劑（X）與胺酯預聚物（P）反應之方法。Examples of methods for reacting the chain extender (X) with the urethane prepolymer (P) include solvents (toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone, isopropyl A method of reacting the chain extender (X) with the urethane prepolymer (P) in the presence or absence of alcohol, methyl ethyl ketone, tetrahydrofuran, etc.).
鏈伸長劑（X）中之上述具有羥基之胺（C）較佳為含有上述具有羥基之單胺（c1）及上述具有羥基之二胺（c2）的混合物。The amine (C) having a hydroxyl group in the chain extender (X) is preferably a mixture containing the monoamine (c1) having a hydroxyl group and the diamine (c2) having a hydroxyl group.
鏈伸長劑（X）除上述具有羥基之胺（C）以外，亦可包含不具有羥基之胺（x1）及不具有胺基之含羥基化合物（x2）。The chain extender (X) may include, in addition to the above-mentioned amine (C) having a hydroxyl group, an amine (x1) not having a hydroxyl group and a hydroxyl-containing compound (x2) not having an amine group.
作為不具有羥基之胺（x1），可列舉：碳數2～12之單或二胺、聚（n＝2～6）伸烷基（碳數2～6）聚（n＝3～7）胺及聚氧伸烷基二醇多胺（polyoxyalkylene glycol polyamine）等。Examples of the amine (x1) that does not have a hydroxyl group include mono- or diamines having 2 to 12 carbon atoms, poly(n=2-6)alkylene (carbon number 2-6) poly(n=3-7) Amine and polyoxyalkylene glycol polyamine (polyoxyalkylene glycol polyamine), etc.
作為碳數2～12之單或二胺之例，可列舉：正丁胺、二正丁胺、乙二胺、丙二胺、六亞甲基二胺、異佛酮二胺、甲苯二胺及哌等。Examples of mono- or diamines having 2 to 12 carbon atoms include n-butylamine, di-n-butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, and toluenediamine. and pipe wait.
作為聚（n＝2～6）伸烷基（碳數2～6）聚（n＝3～7）胺之例，可列舉：二伸乙基三胺、二伸丙基三胺、二伸己基三胺、三伸乙基四胺、四伸乙基五胺、五伸乙基六胺及六伸乙基七胺等。Examples of poly(n=2-6)alkylene (carbon number 2-6) poly(n=3-7)amine include: diethylenetriamine, dipropyltriamine, dipropyltriamine, Hexyltriamine, triethylenetetramine, tetraethylenepentamine, pentethylhexamine and hexaethylheptamine, etc.
作為聚氧伸烷基二醇多胺之例，可列舉聚丙二醇二胺及聚四亞甲基醚二醇二胺等。Examples of polyoxyalkylene glycol polyamines include polypropylene glycol diamine, polytetramethylene ether glycol diamine, and the like.
作為不具有胺基之含羥基化合物（x2），可列舉：碳數2～20之脂肪族二元醇（伸烷基二醇，例如乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、3-甲基戊二醇、新戊二醇及1,9-壬二醇等）。Examples of the hydroxyl-containing compound (x2) that does not have an amine group include aliphatic diols having 2 to 20 carbon atoms (alkylene glycols, such as ethylene glycol, propylene glycol, 1,3-butanediol, 1 , 4-butanediol, 1,6-hexanediol, 3-methylpentanediol, neopentyl glycol and 1,9-nonanediol, etc.).
不具有羥基之胺（x1）及不具有胺基之含羥基化合物（x2）可單獨使用1種，亦可併用2種以上。The amine (x1) which does not have a hydroxyl group and the hydroxyl-containing compound (x2) which does not have an amine group may be used individually by 1 type, and may use 2 or more types together.
不具有羥基之胺（x1）及不具有胺基之含羥基化合物（x2）中，就聚胺酯樹脂之高分子量化之容易度及黏著劑之硬化物之色相的觀點而言，較佳為不具有羥基之胺（x1），進而較佳為碳數2～12之單或二胺，尤佳為碳數6～10之脂肪族或脂環族二胺。Among the amine (x1) that does not have a hydroxyl group and the hydroxyl-containing compound (x2) that does not have an amine group, from the viewpoint of the ease of high molecularization of the polyurethane resin and the hue of the cured product of the adhesive, it is preferable that it does not have the hydroxyl group. The hydroxyl amine (x1) is more preferably a mono or diamine having 2 to 12 carbon atoms, and particularly preferably an aliphatic or alicyclic diamine having 6 to 10 carbon atoms.
就獲得之胺酯樹脂之硬化性的觀點而言，鏈伸長劑（X）所含有之上述具有羥基之胺（C）為含有具有羥基之單胺（c1）及具有羥基之二胺（c2）的混合物，上述具有羥基之單胺（c1）之含量與上述具有羥基之二胺（c2）之含量的合計基於包含上述具有羥基之胺（C）之鏈伸長劑（X）的合計重量較佳為5～100重量%，進而較佳為10～100重量%，尤佳為20～100重量%，最佳為30～100重量%。From the viewpoint of the curability of the obtained urethane resin, the above-mentioned amine (C) having a hydroxyl group contained in the chain extender (X) contains a monoamine (c1) having a hydroxyl group and a diamine (c2) having a hydroxyl group. The mixture, the total content of the above-mentioned monoamine having a hydroxyl group (c1) and the above-mentioned content of the diamine having a hydroxyl group (c2) is preferably based on the total weight of the chain extender (X) including the above-mentioned amine having a hydroxyl group (C). The content is 5 to 100% by weight, more preferably 10 to 100% by weight, even more preferably 20 to 100% by weight, and most preferably 30 to 100% by weight.
於使鏈伸長劑（X）與胺酯預聚物（P）反應之情形時，鏈伸長劑（X）與胺酯預聚物（P）之重量比[鏈伸長劑（X）/胺酯預聚物（P）]較佳為0.01/1～1/1，進而較佳為0.015/1～0.7/1，最佳為0.02/1～0.5/1。若鏈伸長劑（X）與胺酯預聚物（P）之重量比[鏈伸長劑（X）/胺酯預聚物（P）]超過1/1或未達0.01/1，則胺酯樹脂之分子量不足而導致黏著劑之黏著力及凝聚力不足。When the chain extender (X) and the urethane prepolymer (P) are reacted, the weight ratio of the chain extender (X) and the urethane prepolymer (P) [chain extender (X)/urethane Prepolymer (P)] is preferably 0.01/1 to 1/1, further preferably 0.015/1 to 0.7/1, most preferably 0.02/1 to 0.5/1.If the weight ratio of chain extender (X) to urethane prepolymer (P) [chain extender (X)/urethane prepolymer (P)] exceeds 1/1 or does not reach 0.01/1, the urethane The molecular weight of the resin is insufficient, resulting in insufficient adhesion and cohesion of the adhesive.
於使鏈伸長劑（X）與胺酯預聚物（P）反應之情形時，鏈伸長劑（X）所含有之上述具有羥基之胺（C）較佳為含有上述具有羥基之單胺（c1）與上述具有羥基之二胺（c2）的混合物，就控制分子量之觀點而言，上述具有羥基之單胺（c1）與上述具有羥基之二胺（c2）的重量比{具有羥基之單胺（c1）/具有羥基之二胺（c2）}較佳為0.001/1～1/1，進而較佳為0.01/1～0.7/1，最佳為0.03/1～0.5/1。When the chain extender (X) and the urethane prepolymer (P) are reacted, the above-mentioned amine (C) having a hydroxyl group contained in the chain extender (X) preferably contains the above-mentioned monoamine (C) having a hydroxyl group. The mixture of c1) and the above-mentioned diamine having a hydroxyl group (c2), from the viewpoint of controlling the molecular weight, the weight ratio of the above-mentioned monoamine having a hydroxyl group (c1) to the above-mentioned diamine having a hydroxyl group (c2) {monoamine having a hydroxyl group (c2) Amine (c1)/diamine (c2) having a hydroxyl group} is preferably 0.001/1 to 1/1, more preferably 0.01/1 to 0.7/1, and most preferably 0.03/1 to 0.5/1.
聚胺酯樹脂之重量平均分子量為5萬～200萬，較佳為8萬～200萬，進而較佳為10萬～100萬，尤佳為15萬～80萬，最佳為20萬～60萬。若聚胺酯樹脂之重量平均分子量超過200萬，則存在黏度變得過高而損害生產性及塗敷時之作業性之問題，若未達5萬，則存在黏著劑之黏著力或凝聚力不足之問題。The weight average molecular weight of the polyurethane resin is 50,000 to 2,000,000, preferably 80,000 to 2,000,000, more preferably 100,000 to 1,000,000, more preferably 150,000 to 800,000, most preferably 200,000 to 600,000.If the weight average molecular weight of the polyurethane resin exceeds 2 million, there is a problem that the viscosity becomes too high, which impairs productivity and workability during coating. If it is less than 50,000, there is a problem that the adhesive force or cohesive force of the adhesive is insufficient. .
就黏著劑之黏著力與凝聚力之觀點而言，聚胺酯樹脂之羥值較佳為1～50 mgKOH/g，進而較佳為2～40 mgKOH/g，尤佳為3～30 mgKOH/g，最佳為5～20 mgKOH/g。From the viewpoint of the adhesive force and cohesion of the adhesive, the hydroxyl value of the polyurethane resin is preferably 1 to 50 mgKOH/g, more preferably 2 to 40 mgKOH/g, and most preferably 3 to 30 mgKOH/g. The optimal range is 5 to 20 mgKOH/g.
就黏著力之觀點而言，聚胺酯樹脂之胺酯基濃度較佳為1～40重量%，進而較佳為2～30重量%，尤佳為3～20重量%，最佳為5～15重量%。From the viewpoint of adhesion, the urethane group concentration of the polyurethane resin is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, particularly preferably 3 to 20% by weight, and most preferably 5 to 15% by weight. %.
就黏著力之觀點而言，聚胺酯樹脂之脲基濃度較佳為0.5～15重量%，進而較佳為1～10重量%，尤佳為1.5～7重量%，最佳為2～5重量%。From the viewpoint of adhesion, the urea group concentration of the polyurethane resin is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, particularly preferably 1.5 to 7% by weight, and most preferably 2 to 5% by weight. .
（黏著劑）本發明之黏著劑可為單液硬化型黏著劑，亦可為以上述聚胺酯樹脂為主劑之二液硬化型黏著劑。(adhesive)The adhesive of the present invention can be a single-liquid curing adhesive, or a two-liquid curing adhesive using the above-mentioned polyurethane resin as the main agent.
本發明之黏著劑於一面藉由2 kg輥進行壓接一面貼合於玻璃板時，於23℃在拉伸速度300 mm/min之條件下的180°剝離強度為5～50 N/25 mm。關於上述剝離強度，例如將裁剪成200 mm×25 mm之大小之黏著片一面藉由2 kg輥進行壓接一面貼合於玻璃板而製作剝離試驗用片材。其後，使用拉伸試驗機，於拉伸速度300 mm/min之條件下對剝離試驗用片材測定180°剝離強度（單位：N/25 mm）。本發明之黏著劑之剝離強度為5 N/25 mm以上，較佳為10 N/25 mm以上，進而較佳為15 N/25 mm以上。When the adhesive of the present invention is pressed with a 2 kg roller and bonded to a glass plate on one side, the 180° peel strength at 23°C under the condition of a stretching speed of 300 mm/min is 5 to 50 N/25 mm. .Regarding the above-mentioned peel strength, for example, an adhesive sheet cut into a size of 200 mm × 25 mm is pressed with a 2 kg roller and bonded to a glass plate on one side to prepare a sheet for a peel test. Thereafter, the 180° peel strength (unit: N/25 mm) of the peel test sheet was measured using a tensile testing machine at a tensile speed of 300 mm/min.The peel strength of the adhesive of the present invention is 5 N/25 mm or more, preferably 10 N/25 mm or more, and further preferably 15 N/25 mm or more.
於將本發明之黏著劑設為單液硬化型黏著劑之情形時，進而視需要可含有抗氧化劑、紫外線吸收劑、塑化劑、黏著賦予劑、填充劑、顏料、抗靜電劑及防膠凝劑等添加劑。When the adhesive of the present invention is a single-liquid hardening adhesive, it may further contain antioxidants, ultraviolet absorbers, plasticizers, adhesion-imparting agents, fillers, pigments, antistatic agents and anti-adhesive agents as necessary. Coagulant and other additives.
作為抗氧化劑，可列舉：受阻酚（hindered phenol）化合物[三乙二醇雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,2-硫基-二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]等]及亞磷酸酯化合物[亞磷酸三(2,4-二-第三丁基苯基)酯、2,2-亞甲基雙(4,6-二-第三丁基苯基)辛基亞磷酸酯、雙(2,6-二-第三丁基苯基)新戊四醇二亞磷酸酯、四(2,4-二-第三丁基苯基)4,4'-伸聯苯基-二亞膦酸酯等]。該等抗氧化劑可單獨使用1種，亦可併用2種以上。就抗氧化效果及黏著力之觀點而言，抗氧化劑之使用量基於單液硬化型黏著劑之重量較佳為5重量%以下，進而較佳為0.05～1重量%。Examples of antioxidants include hindered phenol compounds [triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl -4-hydroxyphenyl)propionate] and phosphite compounds [tris(2,4-di-tert-butylphenyl)phosphite, 2,2-methylenebis(4, 6-Di-tert-butylphenyl)octyl phosphite, bis(2,6-di-tert-butylphenyl)nepentylerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl) Tributylphenyl) 4,4'-biphenyl-diphosphonite, etc.].One type of these antioxidants may be used alone, or two or more types may be used in combination.From the viewpoint of antioxidant effect and adhesive strength, the amount of antioxidant used is preferably 5% by weight or less based on the weight of the single-liquid hardening adhesive, and more preferably 0.05 to 1% by weight.
作為紫外線吸收劑，可列舉：水楊酸衍生物（水楊酸苯酯、水楊酸對辛基苯酯、水楊酸對第三丁基苯酯等）、二苯甲酮化合物[2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2,2'-二羥基-4-甲氧基二苯甲酮、2,2'-二羥基-4,4'-二甲氧基二苯甲酮、2,2'-二羥基-4,4'-二甲氧基-5-磺基二苯甲酮、2-羥基-4-甲氧基-2'-羧基二苯甲酮、2-羥基-4-甲氧基-5-磺基二苯甲酮三水合物、2-羥基-4-正辛氧基二苯甲酮、2-羥基-4-十八烷氧基二苯甲酮、2,2',4,4'-四羥基二苯甲酮、4-十二烷氧基-2-羥基二苯甲酮、2-羥基-4-(2-羥基-3-甲基丙烯醯氧基)丙氧基二苯甲酮、雙(2-甲氧基-4-羥基-5-苯甲醯基苯基)甲烷等]、苯并三唑化合物{2-(2'-羥基-5'-甲基-苯基)苯并三唑、2-(2'-羥基-3',5'-二-第三丁基-苯基)苯并三唑、2-(2'-羥基-3'-第三丁基-5'-甲基-苯基)-5-氯苯并三唑、2-(2'-羥基-3',5'-二-第三丁基-苯基)-5-氯苯并三唑、2-(2'-羥基-4'-正辛氧基苯基)苯并三唑、2-(2'-羥基-5'-第三丁基苯基)苯并三唑、2-(2'-羥基-3',5'-二-第三戊基苯基)苯并三唑、2-[2'-羥基-3'-(3'',4'',5'',6''-四氫鄰苯二甲醯亞胺甲基)-5'-甲基苯基]苯并三唑、2,2-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并三唑-2-基)苯酚]等}、氰基丙烯酸酯化合物（2-氰基-3,3'-二苯基丙烯酸2-乙基己酯、2-氰基-3,3'-二苯基丙烯酸乙酯等）等。紫外線吸收劑可單獨使用1種，亦可併用2種以上。就紫外線吸收效果及接著力之觀點而言，紫外線吸收劑之使用量基於單液硬化型黏著劑之重量較佳為5重量%以下，進而較佳為0.1～1重量%。Examples of ultraviolet absorbers include: salicylic acid derivatives (phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc.), benzophenone compounds [2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 ,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy- 2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy- 4-octadecyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -(2-hydroxy-3-methacryloxy)propoxybenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, etc.], benzo Triazole compound {2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl) Benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5'-Di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-4'-n-octyloxyphenyl)benzotriazole, 2-(2' -Hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-[2 '-Hydroxy-3'-(3'',4'',5'',6''-tetrahydrophthalimidemethyl)-5'-methylphenyl]benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], etc.}, cyanoacrylate Compounds (2-ethylhexyl 2-cyano-3,3'-diphenylacrylate, ethyl 2-cyano-3,3'-diphenylacrylate, etc.), etc.One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.From the viewpoint of ultraviolet absorption effect and adhesive strength, the usage amount of the ultraviolet absorber is preferably 5% by weight or less based on the weight of the single-liquid curable adhesive, and more preferably 0.1 to 1% by weight.
作為塑化劑，可列舉：烴[加工處理油、液狀聚丁二烯、液狀聚異丁烯、液狀聚異戊二烯、液態石蠟、氯化石蠟、石蠟、乙烯與α-烯烴（碳數3～20）之共聚（重量比99.9/0.1～0.1/99.9）低聚物（重量平均分子量5,000～100,000）、丙烯與除乙烯以外之α-烯烴（碳數4～20）之共聚低聚物（重量比99.9/0.1～0.1/99.9）低聚物（重量平均分子量5,000～100,000）]；氯化石蠟；酯[鄰苯二甲酸酯[鄰苯二甲酸二乙酯（DEP）、鄰苯二甲酸二丁酯（DBP）、鄰苯二甲酸二(2-乙基己基)酯（DOP）、鄰苯二甲酸二癸酯、鄰苯二甲酸二月桂酯、鄰苯二甲酸二硬脂酯、鄰苯二甲酸二異壬酯等]、己二酸酯[己二酸二(2-乙基己基)酯（DOA）、己二酸二辛酯等]及癸二酸酯（癸二酸二辛酯等）等]；動植物油脂（亞麻油酸、次亞麻油酸等）；及其中具有能夠氫化之不飽和雙鍵者之氫化物；脂肪酸酯（硬脂酸丁酯、棕櫚酸2-乙基己酯、硬脂酸2-乙基己酯、二十二酸單甘油酯、2-乙基己酸鯨蠟酯、棕櫚酸異丙酯、膽固醇異硬脂酸酯、椰子油脂肪酸甲酯、月桂酸甲酯、油酸甲酯、硬脂酸甲酯、肉豆蔻酸異丙酯、肉豆蔻酸辛基十二烷基酯、肉豆蔻酸肉豆蔻酯、硬脂酸硬脂酯、硬脂酸2-乙基己酯、硬脂酸異十三烷基酯、三(2-乙基己酸)甘油酯、月桂酸丁酯、油酸辛酯）等。塑化劑可單獨使用1種，亦可併用2種以上。就黏著劑之凝聚力之觀點而言，塑化劑之使用量基於單液硬化型黏著劑之重量較佳為100重量%以下，進而較佳為1～50重量%，尤佳為3～40重量%，特佳為5～35重量%，最佳為10～30重量%。Examples of plasticizers include: hydrocarbons [processing oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, chlorinated paraffin, paraffin, ethylene and α-olefins (carbon Copolymerization of oligomers (weight ratio 99.9/0.1～0.1/99.9) (weight average molecular weight 5,000～100,000), copolymerization of propylene and α-olefins (carbon number 4～20) other than ethylene (weight ratio 99.9/0.1～0.1/99.9) oligomer (weight average molecular weight 5,000～100,000)]; chlorinated paraffin; ester [phthalate ester [diethyl phthalate (DEP), phthalate Dibutyl phthalate (DBP), di(2-ethylhexyl) phthalate (DOP), didecyl phthalate, dilauryl phthalate, distearyl phthalate esters, diisononyl phthalate, etc.], adipate esters [di(2-ethylhexyl) adipate (DOA), dioctyl adipate, etc.] and sebacate esters (sebacic acid ester acid dioctyl ester, etc.]; animal and vegetable oils and fats (linoleic acid, linolenic acid, etc.); and hydrogenated products of those with unsaturated double bonds that can be hydrogenated; fatty acid esters (butyl stearate, palmitic acid, etc.) 2-Ethylhexyl stearate, 2-ethylhexyl stearate, monoglyceryl behenate, cetyl 2-ethylhexanoate, isopropyl palmitate, cholesterol isostearate, coconut oil Fatty acid methyl ester, methyl laurate, methyl oleate, methyl stearate, isopropyl myristate, octyldodecyl myristate, myristyl myristate, stearyl stearate , 2-ethylhexyl stearate, isotridecyl stearate, tris(2-ethylhexanoic acid)glyceride, butyl laurate, octyl oleate), etc. One type of plasticizer may be used alone, or two or more types may be used in combination. From the viewpoint of the cohesion of the adhesive, the usage amount of the plasticizer is preferably 100% by weight or less based on the weight of the single-liquid hardening adhesive, more preferably 1 to 50% by weight, and particularly preferably 3 to 40% by weight. %, particularly preferably 5 to 35 wt%, and most preferably 10 to 30 wt%.
作為黏著性賦予劑，例如可列舉：萜烯樹脂、萜酚樹脂、酚樹脂、芳香族烴改質萜烯樹脂、松香樹脂、改質松香樹脂、合成石油樹脂（脂肪族、芳香族或脂環式合成石油樹脂等）、薰草哢-茚樹脂、二甲苯樹脂、苯乙烯系樹脂、二環戊二烯樹脂、及其中具有能夠氫化之不飽和雙鍵者之氫化物等。黏著性賦予劑可單獨使用1種，亦可併用2種以上。其中，就黏著力之觀點而言，較佳為具有極性者，進而較佳為松香樹脂、酚樹脂、萜酚樹脂、二甲苯樹脂及其等之氫化物，尤佳為萜酚樹脂及其氫化物。就黏著力及耐熱性之觀點而言，黏著性賦予劑之使用量基於單液硬化型黏著劑之重量較佳為100重量%以下，進而較佳為1～50重量%，尤佳為3～40重量%，特佳為5～35重量%，最佳為10～30重量%。Examples of the tackifier include: terpene resin, terpenol resin, phenol resin, aromatic hydrocarbon modified terpene resin, rosin resin, modified rosin resin, synthetic petroleum resin (aliphatic, aromatic or alicyclic Formula synthetic petroleum resin, etc.), lavenderindene resin, xylene resin, styrenic resin, dicyclopentadiene resin, and hydrides of those with unsaturated double bonds capable of hydrogenation, etc. One type of tackiness imparting agent may be used alone, or two or more types may be used in combination.Among them, from the viewpoint of adhesion, those having polarity are preferred, and rosin resins, phenol resins, terpenol resins, xylene resins and hydrogenated products thereof are more preferred, and terpene phenol resins and hydrogenated products thereof are particularly preferred. things. From the viewpoint of adhesion and heat resistance, the usage amount of the tackiness-imparting agent is preferably 100% by weight or less based on the weight of the single-liquid curable adhesive, more preferably 1 to 50% by weight, and particularly preferably 3 to 3% by weight. 40% by weight, particularly preferably 5% to 35% by weight, and most preferably 10% to 30% by weight.
作為填充劑，可列舉：碳酸鹽（碳酸鎂、碳酸鈣等）、硫酸鹽（硫酸鋁、硫酸鈣、硫酸鋇等）、亞硫酸鹽（亞硫酸鈣等）、二硫化鉬、矽酸鹽（矽酸鋁、矽酸鈣等）、矽藻土、矽石粉、滑石、二氧化矽、沸石等。上述填充劑係體積平均粒徑較佳為0.01～5 μm左右之微粒子，可單獨使用1種，亦可併用2種以上。就黏著劑之凝聚力之觀點而言，填充劑之使用量基於單液硬化型黏著劑之重量較佳為250重量%以下，進而較佳為0.5～100重量%。Examples of fillers include carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, calcium sulfate, barium sulfate, etc.), sulfites (calcium sulfite, etc.), molybdenum disulfide, and silicates ( Aluminum silicate, calcium silicate, etc.), diatomaceous earth, silica powder, talc, silica, zeolite, etc. The above-mentioned fillers are fine particles having a volume average particle diameter of preferably about 0.01 to 5 μm. One type may be used alone, or two or more types may be used in combination. From the viewpoint of the cohesion of the adhesive, the usage amount of the filler is preferably 250% by weight or less based on the weight of the single-liquid hardening adhesive, and more preferably 0.5 to 100% by weight.
作為顏料，可列舉：無機顏料（鋁白、石墨、氧化鈦、超微粒子氧化鈦、鋅白、黑色氧化鐵、雲母狀氧化鐵、鉛白、白碳、鉬白、碳黑、氧化鉛、鋅鋇白、重晶石、鎘紅、鎘汞紅、赤鐵氧化物、鉬紅、鉛丹、鉻黃、鎘黃、鋇黃、鍶黃、鈦黃、鈦黑、氧化鉻綠、氧化鈷、鈷綠、鈷鉻綠、群青、深青、鈷青、天藍、錳紫、鈷紫等）及有機顏料（蟲膠、不溶性偶氮顏料、溶性偶氮顏料、縮合偶氮顏料、酞青藍、染色色澱等）。上述顏料係體積平均粒徑較佳為0.01～5 μm左右之微粒子，可單獨使用1種，亦可併用2種以上。就黏著劑之凝聚力之觀點而言，顏料之使用量基於單液硬化型黏著劑之重量較佳為250重量%以下，進而較佳為0.1～50重量%。Examples of pigments include inorganic pigments (aluminum white, graphite, titanium oxide, ultrafine particle titanium oxide, zinc white, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, lead oxide, zinc Barium white, barite, cadmium red, cadmium mercury red, hematite oxide, molybdenum red, lead red, chrome yellow, cadmium yellow, barium yellow, strontium yellow, titanium yellow, titanium black, chromium oxide green, cobalt oxide, Cobalt green, cobalt chrome green, ultramarine blue, dark cyan, cobalt blue, sky blue, manganese violet, cobalt violet, etc.) and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dyeing color lake, etc.). The above-mentioned pigments are fine particles having a volume average particle diameter of preferably about 0.01 to 5 μm. One type may be used alone, or two or more types may be used in combination. From the viewpoint of the cohesion of the adhesive, the amount of pigment used is preferably 250% by weight or less based on the weight of the single-liquid hardening adhesive, and more preferably 0.1 to 50% by weight.
作為抗靜電劑，可列舉：聚醚多元醇、界面活性劑、金屬系導電性填充劑、碳黑、重量平均分子量未達5000之四級銨鹽等。Examples of antistatic agents include polyether polyols, surfactants, metallic conductive fillers, carbon black, and quaternary ammonium salts with a weight average molecular weight of less than 5,000.
作為防膠凝劑（胺酯化延遲劑），可列舉通式（4）所表示之化合物。防膠凝劑發揮如下效果：防止由於胺酯化時之副反應而導致凝膠化、確保二液硬化時之使用時間以及縮短硬化時之固化時間。Examples of the antigelling agent (urethane esterification retardant) include compounds represented by general formula (4).The anti-gelling agent has the following effects: preventing gelation due to side reactions during urethane esterification, ensuring the use time during two-liquid hardening, and shortening the curing time during hardening.
通式（4）中之R4及R5分別獨立表示碳數1～6之烴基、碳數1～6之烷氧基或碳數3～5之雜環基。R4 and R5 in the general formula (4) each independently represent a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a heterocyclic group having 3 to 5 carbon atoms.
防膠凝劑可單獨使用1種，亦可併用2種以上。One type of anti-gelling agent may be used alone, or two or more types may be used in combination.
作為通式（4）所表示之化合物之具體例，可列舉：β-二酮、β-酮酯及丙二酸二烷基酯等。Specific examples of the compound represented by the general formula (4) include β-diketone, β-ketoester, dialkyl malonate, and the like.
作為β-二酮，可列舉：2,4-戊二酮（乙醯丙酮）、3-甲基-2,4-戊二酮、2,4-己二酮、2,2-二甲基-3,5-己二酮、2,4-庚二酮、3,5-庚二酮、2,2,6,6-四甲基-3,5-庚二酮、2,4-辛二酮、2,2,7-三甲基-3,5-辛二酮、2,4-壬二酮、3-甲基-2,4-壬二酮、2-甲基-4,6-壬二酮、1-苯基-1,3-丁二酮（苯甲醯丙酮）、二苯甲醯基甲烷及2-呋喃甲醯基苯甲醯基甲烷等。Examples of β-diketone include: 2,4-pentanedione (acetylacetone), 3-methyl-2,4-pentanedione, 2,4-hexanedione, and 2,2-dimethyl -3,5-Hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 2,4-octanedione Dione, 2,2,7-trimethyl-3,5-octanedione, 2,4-nonanedione, 3-methyl-2,4-nonanedione, 2-methyl-4,6 - Nonanedione, 1-phenyl-1,3-butanedione (benzoyl acetone), diphenyl methane and 2-furyl benzyl methane, etc.
作為β-酮酯，可列舉：乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸丙酯、乙醯乙酸丁酯、丙醯乙酸甲酯、丙醯乙酸乙酯、丙醯乙酸丙酯、丙醯乙酸異丙酯、丙醯乙酸丁酯、丁醯乙酸甲酯、丁醯乙酸乙酯、丁醯乙酸丙酯、己醯乙酸甲酯、己醯乙酸乙酯、己醯乙酸丙酯及己醯乙酸丁酯等。Examples of β-ketoesters include: methyl acetyl acetate, ethyl acetyl acetate, propyl acetyl acetate, butyl acetyl acetate, methyl propyl acetate, ethyl acetyl acetate, and propyl acetyl acetate. , isopropyl propyl acetate, butyl propyl acetate, methyl butyl acetate, ethyl butyl acetate, propyl butyl acetate, methyl hexanoyl acetate, ethyl hexanoyl acetate, propyl hexanoyl acetate and Hexanobutyl acetate, etc.
作為丙二酸二烷基酯，可列舉：丙二酸二甲酯、丙二酸二乙酯、丙二酸甲酯乙酯、丙二酸二異丙酯及丙二酸二丁酯等。Examples of dialkyl malonates include dimethyl malonate, diethyl malonate, ethyl methyl malonate, diisopropyl malonate, dibutyl malonate, and the like.
防膠凝劑可單獨使用1種，亦可併用2種以上。One type of anti-gelling agent may be used alone, or two or more types may be used in combination.
防膠凝劑之使用量根據所需之反應速度及使用時間適當進行選擇，就由硬化及滲出所導致之對被黏著體之污染的觀點而言，基於聚胺酯樹脂之重量，較佳為0.01～1重量%，進而較佳為0.02～0.5重量%，尤佳為0.03～0.3重量%。The amount of anti-gelling agent used is appropriately selected based on the required reaction speed and usage time. From the perspective of contamination to the adherend caused by hardening and exudation, based on the weight of the polyurethane resin, it is preferably 0.01~ 1% by weight, more preferably 0.02 to 0.5% by weight, particularly preferably 0.03 to 0.3% by weight.
添加劑之添加時期並無特別限制，可於製造聚胺酯樹脂時預先添加至多元醇成分（A），亦可於聚胺酯樹脂之任意製造步驟中添加。The addition period of the additive is not particularly limited. It can be added to the polyol component (A) in advance when producing the polyurethane resin, or it can be added in any production step of the polyurethane resin.
於本發明之黏著劑係上述主劑為聚胺酯樹脂之二液硬化型黏著劑的情形時，較佳為使用含有具有活性氫基或異氰酸基之交聯劑（D）之硬化劑。When the adhesive of the present invention is a two-component curable adhesive in which the main ingredient is polyurethane resin, it is preferable to use a curing agent containing a cross-linking agent (D) having an active hydrogen group or an isocyanate group.
作為具有活性氫基或異氰酸基之交聯劑（D），可列舉具有活性氫基之交聯劑（D1）以及具有異氰酸基之交聯劑（D2）。Examples of the cross-linking agent (D) having an active hydrogen group or an isocyanate group include a cross-linking agent (D1) having an active hydrogen group and a cross-linking agent (D2) having an isocyanate group.
於作為主劑之聚胺酯樹脂具有異氰酸基之情形時，較佳為使用含有具有活性氫基之交聯劑（D1）之硬化劑。另一方面，於作為主劑之聚胺酯樹脂具有活性氫基之情形時，較佳為使用含有具有異氰酸基之交聯劑（D2）之硬化劑。When the polyurethane resin as the main agent has an isocyanate group, it is preferable to use a hardener containing a cross-linking agent (D1) having an active hydrogen group. On the other hand, when the polyurethane resin as the main agent has an active hydrogen group, it is preferable to use a hardener containing a cross-linking agent (D2) having an isocyanate group.
作為具有活性氫基之交聯劑（D1），可列舉：上述含羥基化合物（作為構成殘基R1之具有m個活性氫原子之化合物所記載的含羥基化合物）、上述具有羥基之胺（C）、上述硫醇（作為構成殘基R1之具有m個活性氫原子之化合物所記載的硫醇）、上述聚氧伸烷基多元醇（a1）、上述多元醇（a2）及上述其他多元醇（a3）以及該等與作為異氰酸酯成分（B）所例示之有機多異氰酸酯之反應物且末端具有活性氫基的化合物等。Examples of the crosslinking agent (D1) having an active hydrogen group include the above-mentioned hydroxyl-containing compound (a hydroxyl-containing compound described as a compound having m active hydrogen atoms constituting the residue R1 ), the above-mentioned amine having a hydroxyl group ( C), the above-mentioned thiol (thiol described as a compound having m active hydrogen atoms constituting the residue R1 ), the above-mentioned polyoxyalkylene polyol (a1), the above-mentioned polyol (a2) and the above-mentioned others Polyol (a3) and compounds that are reactants with the organic polyisocyanate exemplified as the isocyanate component (B) and have an active hydrogen group at the terminal, etc.
作為具有異氰酸基之交聯劑（D2），可列舉作為異氰酸酯成分（B）所例示之異氰酸酯及作為上述交聯劑（D1）所例示者與作為異氰酸酯成分（B）所例示之異氰酸酯的反應物且末端具有異氰酸基之化合物等。Examples of the crosslinking agent (D2) having an isocyanate group include the isocyanates exemplified as the isocyanate component (B) and those exemplified as the crosslinking agent (D1) and the isocyanates exemplified as the isocyanate component (B). Reactants and compounds with an isocyanate group at the end, etc.
就硬化性之觀點而言，交聯劑（D）之數量平均官能基數較佳為2～6或其以上，進而較佳為2～5，尤佳為3～4。From the viewpoint of curability, the number average functional group number of the cross-linking agent (D) is preferably 2 to 6 or more, more preferably 2 to 5, and particularly preferably 3 to 4.
於將本發明之黏著劑用作二液硬化型黏著劑之情形時，於不阻礙本發明之效果之範圍內可進而含有上述溶劑、抗氧化劑、紫外線吸收劑、塑化劑、黏著賦予劑、填充劑、顏料、抗靜電劑及防膠凝劑（胺酯化延遲劑）等添加劑。具體而言，係關於單液硬化型胺酯黏著劑所敍述之添加劑。添加劑可添加至主劑、硬化劑之任一者，亦可於摻合主劑與硬化劑時添加，較佳為預先添加至使用有具有羥基之胺酯預聚物之主劑或使用有具有活性氫基之交聯劑（D1）的硬化劑中。When the adhesive of the present invention is used as a two-liquid curable adhesive, the above-mentioned solvent, antioxidant, ultraviolet absorber, plasticizer, tackifier, and Additives such as fillers, pigments, antistatic agents and anti-gelling agents (amine esterification retarder). Specifically, it is the additive described for the one-component hardening type urethane adhesive. The additive can be added to either the main agent or the hardener, or can be added when the main agent and the hardener are blended. It is preferable to add it in advance to the main agent using an urethane prepolymer having a hydroxyl group or to use a urethane prepolymer having a hydroxyl group. In the hardener of active hydrogen group cross-linking agent (D1).
就獲得之黏著劑之硬化物的強度及黏著力之觀點而言，混合主劑與硬化劑時之NCO/OH比率（異氰酸基之莫耳數相對於羥基之莫耳數的比率）較佳為0.01～2.0，進而較佳為0.02～1.5，尤佳為0.05～1.3。From the viewpoint of the strength and adhesive force of the hardened product of the adhesive obtained, the NCO/OH ratio (the ratio of the molar number of the isocyanate group to the molar number of the hydroxyl group) when mixing the main agent and the hardener is relatively Preferably, it is 0.01-2.0, More preferably, it is 0.02-1.5, Most preferably, it is 0.05-1.3.
本發明之黏著劑之用途並無特別限定，例如可塗佈於聚酯膜及聚烯烴膜等基材膜使其硬化而獲得黏著片，貼合於光學構件而用作表面保護膜等。使用有本發明之黏著劑之黏著片或使用有本發明之黏著劑的光學構件亦包含於本發明。The use of the adhesive of the present invention is not particularly limited. For example, it can be coated on a base film such as a polyester film or a polyolefin film and hardened to obtain an adhesive sheet, which can be bonded to optical components and used as a surface protective film.The present invention also includes adhesive sheets using the adhesive of the present invention or optical components using the adhesive of the present invention.
於製造上述胺酯預聚物（P）、二液硬化型黏著劑、使用有二液硬化型黏著劑之黏著片及使用有單液硬化型黏著劑之黏著片時，根據用途及硬化性之要求度，可使用胺酯化觸媒。When manufacturing the above-mentioned urethane prepolymer (P), two-component curable adhesive, adhesive sheet using two-component curable adhesive, and adhesive sheet using one-component curable adhesive, the following are determined according to the application and curability. If required, amine esterification catalyst can be used.
作為胺酯化觸媒，可列舉金屬觸媒及胺觸媒等。作為金屬觸媒，可列舉：錫系觸媒[月桂酸三甲基錫、三甲基氫氧化錫、二月桂酸二甲基錫、二乙酸二丁基錫、二月桂酸二丁基錫、辛酸亞錫及順丁烯二酸二丁基錫等]、鉛系觸媒[油酸鉛、2-乙基己酸鉛、環烷酸鉛及辛烯酸鉛等]、鉍系觸媒[鉍與碳數1～12之單羧酸之鹽、鉍烷氧化物（bismuth alkoxide）及鉍與乙醯丙酮等β-二酮之螯合物化合物等]、鈦系觸媒[異丙氧基三-N-乙基胺基乙基胺化鈦（isopropoxy tri N-ethylaminoethylaminato titanium）、鈦酸四丁酯及四異丙氧基雙二辛基亞磷酸鈦（tetraisopropyl bis dioctyl phosphite titanium）等]、鐵系觸媒[鐵之羧酸鹽化合物（乳酸鐵及蓖麻油酸鐵等）、二茂鐵系化合物（二茂鐵及乙醯基二茂鐵等）及酞青鐵（phthalocyanine iron）等]及其他金屬觸媒[環烷酸鈷等環烷酸金屬鹽及丙酸苯汞鹽等]。Examples of the amine esterification catalyst include metal catalysts, amine catalysts, and the like.Examples of metal catalysts include tin-based catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, and Dibutyltin maleate, etc.], lead-based catalysts [lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], bismuth-based catalysts [bismuth and carbon number 1~ Salts of 12 monocarboxylic acids, bismuth alkoxides and chelate compounds of bismuth and β-diketones such as acetyl acetone, etc.], titanium catalysts [isopropoxy tri-N-ethyl Aminoethylaminated titanium (isopropoxy tri N-ethylaminoethylaminato titanium), tetrabutyl titanate and tetraisopropyl bis dioctyl phosphite titanium (tetraisopropyl bis dioctyl phosphite titanium), etc.], iron-based catalysts [iron Carboxylate compounds (iron lactate, iron ricinoleate, etc.), ferrocene compounds (ferrocene, acetyl ferrocene, etc.), phthalocyanine iron, etc.] and other metal catalysts [ Naphthenate metal salts such as cobalt naphthenate and phenylmercuric propionate, etc.].
作為胺觸媒，可列舉：三乙二胺、四甲基乙二胺、二氮雜雙環烯烴[1,8-二氮雜雙環[5,4,0]十一碳烯-7[DBU（San-Apro股份有限公司製造，註冊商標）]等]、二烷基（碳數1～3）胺基烷基（碳數2～4）胺[二甲胺基乙基胺、二甲胺基丙基胺、二乙胺基丙基胺、二丙胺基丙基胺等]、雜環式胺基烷基（碳數2～6）胺[2-(1-氮丙啶基)乙基胺、4-(1-哌啶基)-2-己基胺等]以及N-甲基及N-乙基啉等。Examples of amine catalysts include: triethylenediamine, tetramethylethylenediamine, diazabicycloolefin [1,8-diazabicyclo[5,4,0]undecene-7[DBU ( Manufactured by San-Apro Co., Ltd., registered trademark)], etc.], dialkyl (carbon number 1 to 3) aminoalkyl (carbon number 2 to 4) amine [dimethylaminoethylamine, dimethylaminoethylamine Propylamine, diethylaminopropylamine, dipropylaminopropylamine, etc.], heterocyclic aminoalkyl (carbon number 2 to 6) amine [2-(1-aziridinyl)ethylamine , 4-(1-piperidyl)-2-hexylamine, etc.] and N-methyl and N-ethyl Phenoline etc.
其中較佳為二氮雜雙環烯烴、鉍觸媒及錫觸媒，進而較佳為DBU、鉍與碳數1～12之單羧酸之鹽及二月桂酸二丁基錫。Among them, diazabicycloolefins, bismuth catalysts, and tin catalysts are preferred, and DBU, salts of bismuth and monocarboxylic acids having 1 to 12 carbon atoms, and dibutyltin dilaurate are more preferred.
胺酯化觸媒之使用量因用途而異，於要求較高之速硬化性之情形時，基於二液硬化型胺酯黏著劑之重量，較佳為5000 ppm以下，進而較佳為1～3000 ppm，尤佳為10～1000 ppm。胺酯化觸媒可單獨使用1種，亦可併用2種以上。The usage amount of the urethane esterification catalyst varies depending on the application. When high rapid hardening is required, based on the weight of the two-component hardening urethane adhesive, it is preferably 5000 ppm or less, and further preferably 1~ 3000 ppm, preferably 10-1000 ppm. One type of amine esterification catalyst may be used alone, or two or more types may be used in combination.
作為應用黏著劑及黏著片之光學構件，可列舉：液晶顯示器、有機EL顯示器、電漿顯示器、場發射顯示器等中使用之偏光板、相位差板、光擴散板、抗反射膜、電磁波屏蔽膜及玻璃基板等。Examples of optical components to which adhesives and adhesive sheets are applied include: polarizing plates, phase difference plates, light diffusion plates, anti-reflection films, and electromagnetic wave shielding films used in liquid crystal displays, organic EL displays, plasma displays, field emission displays, etc. and glass substrates, etc.
作為形成黏著片之方法之具體例，可列舉以下之方法等。為了將胺酯黏著劑塗佈於基材膜，可使用凹版塗佈機、逆輥塗佈機、缺角輪塗佈機、旋轉塗佈機、簾幕式塗佈機、狹縫式塗佈機、棒式塗佈機、缺角輪塗佈機、模嘴塗佈機或刮刀塗佈機等。塗佈時之黏著劑之塗佈量（固形物成分）較佳為0.5～300 g/m2，進而較佳為1～200 g/m2，尤佳為10～100 g/m2。Specific examples of the method of forming the adhesive sheet include the following methods. In order to apply the urethane adhesive to the base film, you can use a gravure coater, a reverse roll coater, a notched wheel coater, a spin coater, a curtain coater, or a slot coater. machine, rod coater, notch wheel coater, die nozzle coater or blade coater, etc. The coating amount (solid content) of the adhesive during coating is preferably 0.5 to 300 g/m2 , more preferably 1 to 200 g/m2 , and particularly preferably 10 to 100 g/m2 .
就塗敷性及抑制熱劣化之觀點而言，應用於基材膜時之黏著劑之塗敷溫度較佳為10～160℃，進而較佳為25～120℃，就成形性（能夠厚塗，且硬化後無翹曲及凹痕等外觀不良）及塗敷性之觀點而言，塗敷溫度下之黏著劑之黏度較佳為0.01～100 Pa・s，進而較佳為0.02～50 Pa・s，尤佳為0.03～10 Pa・s。層壓使用普通之乾式貼合機或擠出貼合機。層壓後，藉由於10～50℃固化20～150小時，使黏著劑完全硬化。From the viewpoint of coating properties and suppression of thermal deterioration, the coating temperature of the adhesive when applied to the base film is preferably 10 to 160°C, and more preferably 25 to 120°C. In terms of formability (capable of thick coating) , and from the viewpoint of appearance defects such as warping and dents after hardening) and coating properties, the viscosity of the adhesive at the coating temperature is preferably 0.01 to 100 Pa·s, and further preferably 0.02 to 50 Pa. ·s, preferably 0.03～10 Pa·s.For lamination, use an ordinary dry laminating machine or extrusion laminating machine. After lamination, the adhesive is completely hardened by curing at 10 to 50°C for 20 to 150 hours.
本發明之黏著劑之硬化物的儲存模數（以下記為G'）於-30℃較佳為0.01～5 MPa，進而較佳為0.02～2 MPa，尤佳為0.05～1 MPa，於100℃較佳為0.005～3 MPa，進而較佳為0.01～1 MPa，尤佳為0.05～0.5 MPa。-30℃之G'相對於100℃之G'的比率[-30℃之G'/100℃之G']較佳為10以下，進而較佳為8以下，尤佳為5以下，最佳為3以下。若-30℃與100℃之G'之比率為10以下，則能夠自低溫至高溫獲得更良好之黏著力。The storage modulus (hereinafter referred to as G') of the hardened material of the adhesive of the present invention is preferably 0.01 to 5 MPa at -30°C, more preferably 0.02 to 2 MPa, especially 0.05 to 1 MPa, and at 100 ℃ is preferably 0.005 to 3 MPa, more preferably 0.01 to 1 MPa, and particularly preferably 0.05 to 0.5 MPa. The ratio of G' at -30°C to G' at 100°C [G' at -30°C/G' at 100°C] is preferably 10 or less, more preferably 8 or less, particularly preferably 5 or less, most preferably is 3 or less.If the ratio of G' between -30°C and 100°C is 10 or less, better adhesion can be obtained from low temperature to high temperature.
本說明書中之儲存模數G'藉由以下方法進行測定。＜儲存模數測定方法＞測定裝置：Rheogel-E4000[UBM股份有限公司製造]測定治具：固體剪切測定溫度：-50～180℃升溫速度：5℃/min測定頻率：1 Hz實施例The storage modulus G' in this specification is measured by the following method.＜Measurement method of storage modulus＞Measuring device: Rheogel-E4000 [manufactured by UBM Co., Ltd.]Measuring fixture: solid shearMeasuring temperature: -50～180℃Heating rate: 5℃/minMeasuring frequency: 1 HzExample
以下，藉由實施例具體地說明本發明，但本發明並不限定於該等實施例。Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
實施例中使用之原料之組成、符號等如下所述。＜多元醇成分＞（a1-1）下述製造例1所記載之聚氧伸烷基多元醇。（a1-2）下述製造例2所記載之聚氧伸烷基多元醇。（a1-3）下述製造例3所記載之聚氧伸烷基多元醇。（a2-1）下述製造例4所記載之聚氧伸烷基多元醇。（a1-4）下述製造例5所記載之聚氧伸烷基多元醇。（a2-2）聚丙二醇[三洋化成工業股份有限公司製造之「SANNIX PP-1000」，一級羥基含有率＝2%，羥值112 mgKOH/g，總不飽和度＝0.010 meq/g]（a2-3）聚丙二醇[三洋化成工業股份有限公司製造之「SANNIX PP-2000」，一級羥基含有率＝2%，羥值56 mgKOH/g，總不飽和度＝0.04 meq/g]（a2-4）聚丙二醇[三洋化成工業股份有限公司製造之「SANNIX PP-4000」，一級羥基含有率＝2%，羥值28 mgKOH/g，總不飽和度＝0.12 meq/g]（a2-5）丙二醇之PO/EO嵌段加成物[三洋化成工業股份有限公司製造之「SANNIX PL-910」，一級羥基含有率＝2%，羥值125 mgKOH/g，總不飽和度＝0.010 meq/g]（a2-6）聚四亞甲基醚二醇[三菱化學股份有限公司製造之「PTMG2000」，羥值56 mgKOH/g，總不飽和度＝0.000 meq/g]（a2-7）四氫呋喃與甲基化四氫呋喃之共聚物[保土谷化學股份有限公司製造之「PTGL-2000」，羥值56 mgKOH/g，總不飽和度＝0.000 meq/g]＜異氰酸酯成分＞（b1-1）HDI[旭化成股份有限公司製造之「Duranate50M」]＜胺＞（c1-1）單乙醇胺（羥值：918 mgKOH/g，胺值：918 mgKOH/g）（c2-1）N-(2-胺基乙基)乙醇胺（羥值：539 mgKOH/g，胺值：1077 mgKOH/g）（x1-1）異佛酮二胺（x1-2）六亞甲基二胺（x1-3）聚(丙二醇)二胺[Huntsman Japan股份有限公司製造之「JEFFAMINE D-2000」]（x1-4）正丁胺＜交聯劑＞（d-1）HDI之異氰尿酸酯體[旭化成股份有限公司製造之Duranate TKA-100]The compositions, symbols, etc. of the raw materials used in the examples are as follows.＜Polyol component＞(a1-1) The polyoxyalkylene polyol described in Production Example 1 below.(a1-2) The polyoxyalkylene polyol described in Production Example 2 below.(a1-3) The polyoxyalkylene polyol described in Production Example 3 below.(a2-1) The polyoxyalkylene polyol described in Production Example 4 below.(a1-4) The polyoxyalkylene polyol described in Production Example 5 below.(a2-2) Polypropylene glycol ["SANNIX PP-1000" manufactured by Sanyo Chemical Industry Co., Ltd., primary hydroxyl content rate = 2%, hydroxyl value 112 mgKOH/g, total unsaturation = 0.010 meq/g](a2-3) Polypropylene glycol ["SANNIX PP-2000" manufactured by Sanyo Chemical Industry Co., Ltd., primary hydroxyl content rate = 2%, hydroxyl value 56 mgKOH/g, total unsaturation = 0.04 meq/g](a2-4) Polypropylene glycol ["SANNIX PP-4000" manufactured by Sanyo Chemical Industry Co., Ltd., primary hydroxyl content rate = 2%, hydroxyl value 28 mgKOH/g, total unsaturation = 0.12 meq/g](a2-5) PO/EO block adduct of propylene glycol ["SANNIX PL-910" manufactured by Sanyo Chemical Industry Co., Ltd., primary hydroxyl group content = 2%, hydroxyl value 125 mgKOH/g, total unsaturation =0.010 meq/g](a2-6) Polytetramethylene ether glycol ["PTMG2000" manufactured by Mitsubishi Chemical Co., Ltd., hydroxyl value 56 mgKOH/g, total unsaturation = 0.000 meq/g](a2-7) Copolymer of tetrahydrofuran and methylated tetrahydrofuran ["PTGL-2000" manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value 56 mgKOH/g, total unsaturation = 0.000 meq/g]＜Isocyanate component＞(b1-1) HDI ["Duranate50M" manufactured by Asahi Kasei Co., Ltd.]＜Amine＞(c1-1) Monoethanolamine (hydroxyl value: 918 mgKOH/g, amine value: 918 mgKOH/g)(c2-1) N-(2-aminoethyl)ethanolamine (hydroxyl value: 539 mgKOH/g, amine value: 1077 mgKOH/g)(x1-1) Isophorone diamine(x1-2) Hexamethylenediamine(x1-3) Poly(propylene glycol) diamine ["JEFFAMINE D-2000" manufactured by Huntsman Japan Co., Ltd.](x1-4) n-butylamine＜Cross-linking agent＞(d-1) Isocyanurate body of HDI [Duranate TKA-100 manufactured by Asahi Kasei Co., Ltd.]
[聚氧伸烷基多元醇之製造]＜製造例1＞將藉由以丙二醇為起始劑於KOH觸媒之存在下使PO反應而製得之聚氧丙二醇（一級羥基含有率＝2%，羥值204 mgKOH/g，總不飽和度＝0.004 meq/g）1100 g添加至具備攪拌裝置、溫度控制裝置、作為冷凝設備之熱交換器、原料供給管線及排氣管線的不鏽鋼製高壓釜中，添加三(五氟苯基)硼烷0.09 g後，一面以反應溫度保持為70～80℃之方式進行控制，一面將PO連續地投入液相中。於高壓釜內液量成為2000 ml之時間點停止PO之投入，於70℃熟成4小時後，添加水200 g，於130～140℃加熱1小時。加熱1小時後，耗費2小時於常壓下蒸餾去除水後，繼而一面通入蒸汽將壓力保持為30～50 torr，一面耗費3小時於減壓下蒸餾去除剩餘之水及低沸點化合物。其後加入30 g合成矽酸鹽[協和化學工業股份有限公司製造之「KYOWAAD600」]與水40 g，於60℃攪拌3小時，自高壓釜取出後，藉由1微米之過濾器進行過濾後加以脫水，獲得聚氧伸烷基多元醇（a1-1）。該聚氧伸烷基多元醇（a1-1）之羥值為112 mgKOH/g，黏度為150 mPa・s/25℃，一級羥基含有率為71%，總不飽和度為0.004 meq/g。[Manufacture of polyoxyalkylene polyol]＜Manufacturing Example 1＞Polyoxypropylene glycol (primary hydroxyl content = 2%, hydroxyl value 204 mgKOH/g, total unsaturation = 0.004 meq/ g) 1100 g was added to a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line and an exhaust line, and after adding 0.09 g of tris(pentafluorophenyl)borane, PO was continuously added to the liquid phase while controlling the reaction temperature to be maintained at 70 to 80°C. Stop adding PO when the liquid volume in the autoclave reaches 2000 ml. After aging at 70°C for 4 hours, add 200 g of water and heat at 130 to 140°C for 1 hour. After heating for 1 hour, it took 2 hours to distill the water under normal pressure. Then, while feeding steam to maintain the pressure at 30 to 50 torr, it took 3 hours to distill under reduced pressure to remove the remaining water and low-boiling point compounds. Then, 30 g of synthetic silicate [KYOWAAD600 manufactured by Kyowa Chemical Industry Co., Ltd.] and 40 g of water were added, stirred at 60°C for 3 hours, removed from the autoclave, and filtered through a 1-micron filter. After dehydration, polyoxyalkylene polyol (a1-1) is obtained. The hydroxyl value of this polyoxyalkylene polyol (a1-1) is 112 mgKOH/g, the viscosity is 150 mPa·s/25℃, the primary hydroxyl content is 71%, and the total unsaturation is 0.004 meq/g.
＜製造例2＞將藉由以丙二醇為起始劑於KOH觸媒之存在下使PO反應而製得之聚氧丙二醇（一級羥基含有率＝2%，羥值173 mgKOH/g，總不飽和度＝0.006 meq/g）1300 g添加至具備攪拌裝置、溫度控制裝置、作為冷凝設備之熱交換器、原料供給管線及排氣管線的不鏽鋼製高壓釜中，添加三(五氟苯基)硼烷0.09 g後，一面以反應溫度保持為70～80℃之方式進行控制，一面將PO連續地投入液相中。於高壓釜內液量成為2000 ml之時間點停止PO之投入，於70℃熟成4小時後，添加水200 g並於130～140℃加熱1小時。加熱1小時後，耗費2小時於常壓蒸餾去除水後，繼而一面通入蒸汽將壓力保持為30～50 torr，一面耗費3小時於減壓下蒸餾去除剩餘之水及低沸點化合物。其後添加30 g之合成矽酸鹽[協和化學工業股份有限公司製造之「KYOWAAD600」]及40 g之水，於60℃攪拌3小時，自高壓釜取出後，藉由1微米之過濾器進行過濾後加以脫水，獲得聚氧伸烷基多元醇（a1-2）。該聚氧伸烷基多元醇（a1-2）之羥值為112 mgKOH/g，黏度為150 mPa・s/25℃，一級羥基含有率為63%，總不飽和度為0.006 meq/g。＜Manufacturing Example 2＞Polyoxypropylene glycol (primary hydroxyl content = 2%, hydroxyl value 173 mgKOH/g, total unsaturation = 0.006 meq/ g) 1300 g was added to a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line and an exhaust line. After adding 0.09 g of tris(pentafluorophenyl)borane, PO was continuously added to the liquid phase while controlling the reaction temperature to be maintained at 70 to 80°C. Stop adding PO when the liquid volume in the autoclave reaches 2000 ml. After aging at 70°C for 4 hours, add 200 g of water and heat at 130 to 140°C for 1 hour. After heating for 1 hour, it took 2 hours to distill the water under normal pressure. Then, while feeding steam to maintain the pressure at 30 to 50 torr, it took 3 hours to distill under reduced pressure to remove the remaining water and low-boiling point compounds. Then, 30 g of synthetic silicate [KYOWAAD600 manufactured by Kyowa Chemical Industry Co., Ltd.] and 40 g of water were added, stirred at 60°C for 3 hours, removed from the autoclave, and filtered through a 1-micron filter. After filtration, it is dehydrated to obtain polyoxyalkylene polyol (a1-2). The hydroxyl value of this polyoxyalkylene polyol (a1-2) is 112 mgKOH/g, the viscosity is 150 mPa·s/25℃, the primary hydroxyl content is 63%, and the total unsaturation is 0.006 meq/g.
＜製造例3＞將藉由以丙二醇為起始劑於KOH觸媒之存在下使PO反應而製得之聚氧丙二醇（一級羥基含有率＝2%，羥值132 mgKOH/g，總不飽和度＝0.009 meq/g）1700 g添加至具備攪拌裝置、溫度控制裝置、作為冷凝設備之熱交換器、原料供給管線及排氣管線的不鏽鋼製高壓釜中，添加三(五氟苯基)硼烷0.09 g後，一面以反應溫度保持為70～80℃之方式進行控制，一面將PO連續地投入液相中。於高壓釜內液量成為2000 ml之時間點停止PO之投入，於70℃熟成4小時後，添加水200 g並於130～140℃加熱1小時。加熱1小時後，耗費2小時於常壓下蒸餾去除水後，繼而一面通入蒸汽將壓力保持為30～50 torr，一面耗費3小時於減壓下蒸餾去除剩餘之水及低沸點化合物。其後添加30 g之合成矽酸鹽[協和化學工業股份有限公司製造之「KYOWAAD600」]及40 g之水，於60℃攪拌3小時，自高壓釜取出後，藉由1微米之過濾器進行過濾後加以脫水，獲得聚氧伸烷基多元醇（a1-3）。該聚氧伸烷基多元醇（a1-3）之羥值為112 mgKOH/g，黏度為150 mPa・s/25℃，一級羥基含有率為45%，總不飽和度為0.009 meq/g。＜Manufacturing Example 3＞Polyoxypropylene glycol (primary hydroxyl content = 2%, hydroxyl value 132 mgKOH/g, total unsaturation = 0.009 meq/ g) 1700 g was added to a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line and an exhaust line. After adding 0.09 g of tris(pentafluorophenyl)borane, PO was continuously added to the liquid phase while controlling the reaction temperature to be maintained at 70 to 80°C. Stop adding PO when the liquid volume in the autoclave reaches 2000 ml. After aging at 70°C for 4 hours, add 200 g of water and heat at 130 to 140°C for 1 hour. After heating for 1 hour, it took 2 hours to distill the water under normal pressure. Then, while feeding steam to maintain the pressure at 30 to 50 torr, it took 3 hours to distill under reduced pressure to remove the remaining water and low-boiling point compounds. Then, 30 g of synthetic silicate [KYOWAAD600 manufactured by Kyowa Chemical Industry Co., Ltd.] and 40 g of water were added, stirred at 60°C for 3 hours, removed from the autoclave, and filtered through a 1-micron filter. After filtration, it is dehydrated to obtain polyoxyalkylene polyol (a1-3). The hydroxyl value of this polyoxyalkylene polyol (a1-3) is 112 mgKOH/g, the viscosity is 150 mPa·s/25℃, the primary hydroxyl content is 45%, and the total unsaturation is 0.009 meq/g.
＜製造例4＞將藉由以丙二醇為起始劑於KOH觸媒之存在下使PO反應而製得之聚氧丙二醇（一級羥基含有率＝2%，羥值125 mgKOH/g，總不飽和度＝0.011 meq/g）1800 g添加至具備攪拌裝置、溫度控制裝置、作為冷凝設備之熱交換器、原料供給管線及排氣管線的不鏽鋼製高壓釜中，添加三(五氟苯基)硼烷0.09 g後，一面以反應溫度保持為70～80℃之方式進行控制，一面將PO連續地投入液相中。於高壓釜內液量成為2000 ml之時間點停止PO之投入，於70℃熟成4小時後，添加水200 g並於130～140℃加熱1小時。加熱1小時後，耗費2小時於常壓蒸餾去除水後，繼而一面通入蒸汽將壓力保持為30～50 torr，一面耗費3小時於減壓下蒸餾去除剩餘之水及低沸點化合物。其後添加30 g之合成矽酸鹽[協和化學工業股份有限公司製造之「KYOWAAD600」]及40 g之水，於60℃攪拌3小時，自高壓釜取出後，藉由1微米之過濾器進行過濾後加以脫水，獲得聚氧伸烷基多元醇（a2-1）。該聚氧伸烷基多元醇（a2-1）之羥值為112 mgKOH/g，黏度為150 mPa・s/25℃，一級羥基含有率為35%，總不飽和度為0.011 meq/g。＜Manufacturing Example 4＞Polyoxypropylene glycol (primary hydroxyl content = 2%, hydroxyl value 125 mgKOH/g, total unsaturation = 0.011 meq/ g) 1800 g was added to a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line, and an exhaust line. After adding 0.09 g of tris(pentafluorophenyl)borane, PO was continuously added to the liquid phase while controlling the reaction temperature to be maintained at 70 to 80°C. Stop adding PO when the liquid volume in the autoclave reaches 2000 ml. After aging at 70°C for 4 hours, add 200 g of water and heat at 130 to 140°C for 1 hour. After heating for 1 hour, it took 2 hours to distill the water under normal pressure. Then, while feeding steam to maintain the pressure at 30 to 50 torr, it took 3 hours to distill under reduced pressure to remove the remaining water and low-boiling point compounds. Then, 30 g of synthetic silicate [KYOWAAD600 manufactured by Kyowa Chemical Industry Co., Ltd.] and 40 g of water were added, stirred at 60°C for 3 hours, removed from the autoclave, and filtered through a 1-micron filter. After filtration, it is dehydrated to obtain polyoxyalkylene polyol (a2-1). The hydroxyl value of this polyoxyalkylene polyol (a2-1) is 112 mgKOH/g, the viscosity is 150 mPa·s/25℃, the primary hydroxyl content is 35%, and the total unsaturation is 0.011 meq/g.
＜製造例5＞於具備攪拌裝置、溫度控制裝置、作為冷凝設備之熱交換器、原料供給管線及排氣管線之不鏽鋼製高壓釜中添加丙二醇116 g及三(五氟苯基)硼烷0.09 g後，一面以反應溫度保持為70～80℃之方式進行控制，一面將PO連續地投入液相中。於高壓釜內液量成為2000 ml之時間點停止PO之投入，於70℃熟成4小時後，添加水200 g並於130～140℃加熱1小時。加熱1小時後，耗費2小時於常壓蒸餾去除水後，繼而一面通入蒸汽將壓力保持為30～50 torr，一面耗費3小時於減壓下蒸餾去除剩餘之水及低沸點化合物。其後添加30 g之合成矽酸鹽[協和化學工業股份有限公司製造之「KYOWAAD600」]及40 g之水，於60℃攪拌3小時，自高壓釜取出後，藉由1微米之過濾器進行過濾後加以脫水，獲得聚氧伸烷基多元醇（a1-4）。該聚氧伸烷基多元醇（a1-4）之羥值為112 mgKOH/g，黏度為150 mPa・s/25℃，一級羥基含有率為85%，總不飽和度為0.000 meq/g。＜Manufacturing Example 5＞Add 116 g of propylene glycol and 0.09 g of tris(pentafluorophenyl)borane to a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line, and an exhaust line. The reaction temperature was controlled to be maintained at 70 to 80°C while PO was continuously added to the liquid phase. Stop adding PO when the liquid volume in the autoclave reaches 2000 ml. After aging at 70°C for 4 hours, add 200 g of water and heat at 130 to 140°C for 1 hour. After heating for 1 hour, it took 2 hours to distill the water under normal pressure. Then, while feeding steam to maintain the pressure at 30 to 50 torr, it took 3 hours to distill under reduced pressure to remove the remaining water and low-boiling point compounds. Then, 30 g of synthetic silicate [KYOWAAD600 manufactured by Kyowa Chemical Industry Co., Ltd.] and 40 g of water were added, stirred at 60°C for 3 hours, removed from the autoclave, and filtered through a 1-micron filter. After filtration, it is dehydrated to obtain polyoxyalkylene polyol (a1-4). The polyoxyalkylene polyol (a1-4) has a hydroxyl value of 112 mgKOH/g, a viscosity of 150 mPa·s/25°C, a primary hydroxyl content of 85%, and a total unsaturation of 0.000 meq/g.
[胺酯預聚物之製造]＜製造例6＞於設置有攪拌棒及溫度計之四口燒瓶中投入藉由製造例1獲得之聚氧伸烷基多元醇（a1-1）100重量份、HDI（b1-1）21重量份，於氮氣氣流下，於110℃使其反應15小時，而獲得胺酯預聚物（P-1）。[Manufacture of urethane prepolymer]<Manufacturing Example 6>100 parts by weight of the polyoxyalkylene polyol (a1-1) obtained in Production Example 1 and 21 parts by weight of HDI (b1-1) were put into a four-necked flask equipped with a stirring rod and a thermometer, and placed under nitrogen gas flow. , and reacted at 110° C. for 15 hours to obtain an urethane prepolymer (P-1).
＜製造例7～18＞將原料及摻合量如表1所示進行變更，除此以外與製造例6同樣地獲得胺酯預聚物（P-2）～（P-13）。<Manufacturing Examples 7 to 18>Urethane prepolymers (P-2) to (P-13) were obtained in the same manner as in Production Example 6 except that the raw materials and blending amounts were changed as shown in Table 1.
[表1]
＜實施例1＞於設置有攪拌棒及溫度計之四口燒瓶中添加胺酯預聚物（P-1）20重量份及作為溶劑之乙酸乙酯50重量份，均勻攪拌後，添加單乙醇胺（c1-1）0.021重量份、N-(2-胺基乙基)乙醇胺（c2-1）0.3重量份、異佛酮二胺（x1-1）0.12重量份，一面於室溫攪拌1小時一面使其反應，獲得聚胺酯樹脂溶液。該聚胺酯樹脂之重量平均分子量為25萬，聚胺酯樹脂之羥值為8.7 mgKOH/g。繼而，於所得之聚胺酯樹脂溶液中混合交聯劑（d-1）0.1重量份及作為觸媒之二月桂酸二丁基錫0.004重量份，以固形物成分換算之膜厚成為30 μm之方式使用棒式塗佈機塗佈於38 μm厚的聚對苯二甲酸乙二酯膜。於120℃使其乾燥3分鐘後，於50℃固化2天，獲得使用有含有聚胺酯樹脂之黏著劑之黏著片。<Example 1>In a four-necked flask equipped with a stirring rod and a thermometer, add 20 parts by weight of urethane prepolymer (P-1) and 50 parts by weight of ethyl acetate as a solvent. After stirring evenly, add 0.021% of monoethanolamine (c1-1). Parts by weight, 0.3 parts by weight of N-(2-aminoethyl)ethanolamine (c2-1), and 0.12 parts by weight of isophorone diamine (x1-1) were reacted while stirring at room temperature for 1 hour to obtain Polyurethane resin solution. The weight average molecular weight of the polyurethane resin is 250,000, and the hydroxyl value of the polyurethane resin is 8.7 mgKOH/g. Next, 0.1 part by weight of the cross-linking agent (d-1) and 0.004 part by weight of dibutyltin dilaurate as the catalyst were mixed into the obtained polyurethane resin solution, and a rod was used so that the film thickness in terms of solid content became 30 μm. The coating machine is used to coat 38 μm thick polyethylene terephthalate film. After drying at 120°C for 3 minutes, it was cured at 50°C for 2 days to obtain an adhesive sheet using an adhesive containing polyurethane resin.
＜實施例2～15、比較例1～6＞將胺酯預聚物、原料及摻合量如表2所示進行變更，除此以外，與實施例1同樣地獲得聚胺酯樹脂溶液及使用有含有聚胺酯樹脂之黏著劑之黏著片。將所得之聚胺酯樹脂之重量平均分子量及羥值示於表2。再者，比較例5之胺酯樹脂溶液由於聚胺酯樹脂凝膠化，故而未進行分析及下述評估。<Examples 2 to 15, Comparative Examples 1 to 6>Except that the urethane prepolymer, raw materials, and blending amounts were changed as shown in Table 2, a polyurethane resin solution and an adhesive sheet using an adhesive agent containing a polyurethane resin were obtained in the same manner as in Example 1.Table 2 shows the weight average molecular weight and hydroxyl value of the obtained polyurethane resin. In addition, since the polyurethane resin of the urethane resin solution of Comparative Example 5 gelled, analysis and the following evaluation were not performed.
[表2]
（1）黏著力及低污染性之測定方法將藉由實施例1～15及比較例1～4、6獲得之黏著片裁剪成200 mm×25 mm之大小，以不鏽鋼板、玻璃板或PET片材（東麗股份有限公司製造之Lumirror T60）作為被黏著體，一面藉由2 kg輥進行壓接一面進行貼合，使用拉伸試驗機（Autograph AG-IS 島津製作所股份有限公司製造），於23℃、拉伸速度300 mm/min之條件下測定180°剝離強度（單位：N/25 mm）。測定係針對5個試樣進行，將其平均值作為黏著力之值，根據以下基準評估黏著力。又，藉由目視觀察黏著片剝離後之被黏著體，根據以下基準評估對被黏著體之低污染性。將該等結果記載於表3中。＜黏著力＞◎：180°剝離強度為15 N/25 mm以上50 N/25 mm以下。○：180°剝離強度為10 N/25 mm以上且未達15 N/25 mm。△：180°剝離強度為5 N/25 mm以上且未達10 N/25 mm。×：180°剝離強度未達5 N/25 mm。＜低污染性＞○：被黏著體上未殘留黏著劑，亦無混濁。△：於被黏著體之貼合有黏著劑之部分的一部分殘留黏著劑或混濁。×：於被黏著體之貼合有黏著劑之部分的幾乎整個面殘留黏著劑或混濁。(1) Determination method of adhesion and low pollutionThe adhesive sheets obtained in Examples 1 to 15 and Comparative Examples 1 to 4 and 6 were cut into a size of 200 mm × 25 mm and plated with stainless steel plates, glass plates or PET sheets (Lumirror T60 manufactured by Toray Co., Ltd. ) as the adherend, press it with a 2 kg roller while laminating it, using a tensile testing machine (Autograph AG-IS manufactured by Shimadzu Corporation) at 23°C and a tensile speed of 300 mm/min. Measure the 180° peel strength (unit: N/25 mm) under these conditions. The measurement was performed on 5 samples, and the average value was used as the value of adhesion. The adhesion was evaluated based on the following standards. In addition, by visually observing the adherend after peeling off the adhesive sheet, the low contamination to the adherend was evaluated based on the following criteria. The results are listed in Table 3.＜Adhesion＞◎: 180° peel strength is 15 N/25 mm or more and 50 N/25 mm or less.○: 180° peel strength is 10 N/25 mm or more and less than 15 N/25 mm.△: 180° peel strength is 5 N/25 mm or more and less than 10 N/25 mm.×: 180° peel strength does not reach 5 N/25 mm.＜Low pollution＞○: No adhesive remains on the adherend, and there is no turbidity.△: Adhesive residue or turbidity remains in a part of the adherend where the adhesive is attached.×: Adhesive remains or becomes cloudy on almost the entire surface of the adherend where the adhesive is attached.
（2）儲存模數之評估方法於實施例1～15及比較例1～4、6之黏著片之製作中，將38 μm厚之聚對苯二甲酸乙二酯膜變更為100 μm之OPP膜，將固形物成分換算之膜厚30 μm變更為1000 μm，除此以外，以相同之方式進行製作，然後將黏著劑自OPP膜剝離，獲得膜厚1000 μm之胺酯黏著劑之硬化物。藉由上述方法測定所得之胺酯黏著劑之硬化物的儲存模數，根據以下基準評估-30℃及100℃之黏彈性。將其結果記載於表3中。＜-30℃之黏彈性＞◎：於-30℃，G'未達0.5 MPa。○：於-30℃，G'為0.5 MPa以上且未達1.5 MPa。△：於-30℃，G'為1.5 MPa以上且未達2.5 MPa。×：於-30℃，G'為2.5 MPa以上。＜100℃之黏彈性＞◎：於100℃，G'為0.1 MPa以上。○：於100℃，G'為0.04 MPa以上且未達0.1 MPa。△：於100℃，G'為0.02 MPa以上且未達0.04 MPa。×：於100℃，G'未達0.02 MPa。(2) Evaluation method of storage moduleIn the preparation of the adhesive sheets of Examples 1 to 15 and Comparative Examples 1 to 4 and 6, the 38 μm thick polyethylene terephthalate film was changed to a 100 μm OPP film, and the solid content of the film was converted Except for changing the thickness from 30 μm to 1000 μm, it was produced in the same manner, and then the adhesive was peeled off from the OPP film to obtain a hardened product of the urethane adhesive with a film thickness of 1000 μm. The storage modulus of the cured product of the urethane adhesive obtained was measured by the above method, and the viscoelasticity at -30°C and 100°C was evaluated based on the following standards. The results are listed in Table 3.＜Viscoelasticity at -30℃＞◎: At -30℃, G' does not reach 0.5 MPa.○: At -30°C, G' is 0.5 MPa or more and less than 1.5 MPa.△: At -30°C, G' is 1.5 MPa or more and less than 2.5 MPa.×: At -30°C, G' is 2.5 MPa or more.＜Viscoelasticity at 100℃＞◎: At 100℃, G' is 0.1 MPa or more.○: At 100°C, G' is 0.04 MPa or more and less than 0.1 MPa.△: At 100°C, G' is 0.02 MPa or more and less than 0.04 MPa.×: At 100°C, G' does not reach 0.02 MPa.
（3）黏著劑硬化物之斷裂強度及斷裂伸長率之評估方法於實施例1～15及比較例1～4、6之黏著片之製作中，將38 μm厚之聚對苯二甲酸乙二酯膜變更為100 μm之OPP膜，將固形物成分換算之膜厚30 μm變更為100 μm，除此以外，以相同之方式進行製作，然後將黏著劑自OPP膜剝離，獲得膜厚100 μm之胺酯黏著劑之硬化物。由所得之胺酯黏著劑之硬化物製作啞鈴狀3號型試片，使用拉伸試驗機，於23℃、50%RH之環境，於拉伸速度100 mm/min之條件下測定斷裂強度及斷裂伸長率。測定係針對5片試片進行，算出其平均值，根據以下之基準評估斷裂強度及斷裂伸長率。將其結果記載於表3中。＜斷裂強度＞◎：2 MPa以上。○：1 MPa以上且未達2 MPa。△：0.5 MPa以上且未達1 MPa。×：未達0.5 MPa。＜斷裂伸長率＞◎：1000%以上。○：500%以上且未達1000%。△：200%以上且未達500%。×：未達200%。(3) Evaluation method of breaking strength and breaking elongation of adhesive hardened materialsIn the preparation of the adhesive sheets of Examples 1 to 15 and Comparative Examples 1 to 4 and 6, the 38 μm thick polyethylene terephthalate film was changed to a 100 μm OPP film, and the solid content of the film was converted Except for changing the thickness from 30 μm to 100 μm, it was produced in the same manner, and then the adhesive was peeled off from the OPP film to obtain a hardened product of the urethane adhesive with a film thickness of 100 μm. A dumbbell-shaped No. 3 test piece was made from the hardened product of the obtained urethane adhesive. A tensile testing machine was used to measure the breaking strength and Elongation at break. The measurement was performed on 5 test pieces, the average value was calculated, and the breaking strength and breaking elongation were evaluated based on the following standards. The results are listed in Table 3.＜Breaking strength＞◎: 2 MPa or more.○: 1 MPa or more and less than 2 MPa.△: 0.5 MPa or more and less than 1 MPa.×: Less than 0.5 MPa.＜Elongation at break＞◎: More than 1000%.○: More than 500% but less than 1000%.△: More than 200% and less than 500%.×: Less than 200%.
[表3]
根據表3之評估結果可知，與比較例之黏著劑相比，實施例之胺酯黏著劑於製造聚胺酯樹脂時凝膠化之風險較低，且能夠穩定地控制分子量，-30℃之儲存模數較低，柔軟性優異，且100℃之彈性模數降低量較少，因此能夠於範圍較廣之溫度使用，進而對PET片材、不鏽鋼板及玻璃板之任一者均發揮較高之黏著力，黏著膜之斷裂強度或斷裂伸長率亦得到提高，對被黏著體之污染亦較少。[產業上之可利用性]According to the evaluation results in Table 3, it can be seen that compared with the adhesive of the comparative example, the urethane adhesive of the example has a lower risk of gelation when producing polyurethane resin, and can stably control the molecular weight. The storage mold at -30°C The number is low, the flexibility is excellent, and the elastic modulus decreases at 100°C is small, so it can be used in a wide range of temperatures, and it exerts high effectiveness on any of PET sheets, stainless steel plates, and glass plates. The adhesion, breaking strength or breaking elongation of the adhesive film are also improved, and there is less pollution to the adherend.[Industrial availability]
本發明之胺酯黏著劑可作為偏光板、相位差板及光擴散板等各種光學構件與玻璃基板之貼合用黏著劑用於液晶顯示器、有機EL顯示器、電漿顯示器及場發射顯示器等各種影像顯示裝置等廣泛之用途，故極其有用。The urethane adhesive of the present invention can be used as an adhesive for bonding various optical components such as polarizing plates, phase difference plates, and light diffusion plates to glass substrates, and can be used in liquid crystal displays, organic EL displays, plasma displays, field emission displays, etc. It is extremely useful for a wide range of applications such as image display devices.
無without
無without
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP2019-190688 | 2019-10-18 | ||
| JP2019190688 | 2019-10-18 |
| Publication Number | Publication Date |
|---|---|
| TW202124652A TW202124652A (en) | 2021-07-01 |
| TWI819244Btrue TWI819244B (en) | 2023-10-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW109136002ATWI819244B (en) | 2019-10-18 | 2020-10-16 | Adhesives, adhesive sheets and optical components |
| Country | Link |
|---|---|
| JP (1) | JP7198943B2 (en) |
| KR (1) | KR102671540B1 (en) |
| CN (1) | CN114555751B (en) |
| TW (1) | TWI819244B (en) |
| WO (1) | WO2021075558A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025164353A1 (en)* | 2024-01-31 | 2025-08-07 | 東レ株式会社 | Laminate, resin composition, laminate with semiconductor element, and semiconductor device manufacturing method using same |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010180290A (en)* | 2009-02-04 | 2010-08-19 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition and adherent laminate obtained by using the same |
| CN101052663B (en)* | 2004-09-30 | 2010-09-22 | 旭硝子株式会社 | Method of making polyurethane resin and pressure sensitive adhesive |
| WO2018179608A1 (en)* | 2017-03-28 | 2018-10-04 | バンドー化学株式会社 | Optically clear adhesive sheet, method for manufacturing optically clear adhesive sheet, laminate, and bonded structure |
| JP2019104901A (en)* | 2017-12-12 | 2019-06-27 | 三洋化成工業株式会社 | Main agent for two-component curable urethane adhesive and two-component curable urethane adhesive |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192636A (en) | 1999-08-30 | 2001-07-17 | Toyo Ink Mfg Co Ltd | Adhesive and pressure-sensitive adhesive sheet using the same |
| JP2006182795A (en) | 2004-12-24 | 2006-07-13 | Mitsubishi Chemicals Corp | Polyurethane adhesive composition, and adhesive sheet or surface protective film |
| JP6891412B2 (en) | 2016-07-07 | 2021-06-18 | 東ソー株式会社 | Urethane-forming composition and urethane adhesive using it |
| JP6892412B2 (en)* | 2017-06-02 | 2021-06-23 | 三洋化成工業株式会社 | Main agent for two-component curable urethane adhesive and two-component curable urethane adhesive |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101052663B (en)* | 2004-09-30 | 2010-09-22 | 旭硝子株式会社 | Method of making polyurethane resin and pressure sensitive adhesive |
| JP2010180290A (en)* | 2009-02-04 | 2010-08-19 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition and adherent laminate obtained by using the same |
| WO2018179608A1 (en)* | 2017-03-28 | 2018-10-04 | バンドー化学株式会社 | Optically clear adhesive sheet, method for manufacturing optically clear adhesive sheet, laminate, and bonded structure |
| JP2019104901A (en)* | 2017-12-12 | 2019-06-27 | 三洋化成工業株式会社 | Main agent for two-component curable urethane adhesive and two-component curable urethane adhesive |
| Publication number | Publication date |
|---|---|
| TW202124652A (en) | 2021-07-01 |
| CN114555751A (en) | 2022-05-27 |
| WO2021075558A1 (en) | 2021-04-22 |
| KR102671540B1 (en) | 2024-05-31 |
| JP7198943B2 (en) | 2023-01-04 |
| CN114555751B (en) | 2023-09-08 |
| JPWO2021075558A1 (en) | 2021-12-23 |
| KR20220053636A (en) | 2022-04-29 |
| Publication | Publication Date | Title |
|---|---|---|
| JP7244544B2 (en) | Two-liquid curing urethane adhesive | |
| JP6892412B2 (en) | Main agent for two-component curable urethane adhesive and two-component curable urethane adhesive | |
| JP6814781B2 (en) | Main agent for two-component curable urethane adhesive and two-component curable urethane adhesive | |
| CN101384637B (en) | Process for production of urethane resin and adhesive agent | |
| CN101052663B (en) | Method of making polyurethane resin and pressure sensitive adhesive | |
| JP5394450B2 (en) | Adhesive for dry lamination | |
| CN114901774B (en) | Two-part curable polyurethane adhesive, cured product of two-part curable polyurethane adhesive, and polyurethane adhesive sheet | |
| JP2006307197A (en) | Pressure-sensitive adhesive composition | |
| TWI819244B (en) | Adhesives, adhesive sheets and optical components | |
| JP2015004052A (en) | Two-component type curable composition for forming adhesive coating film | |
| JP6023506B2 (en) | Adhesion improver and adhesive using the same | |
| JP7295933B2 (en) | Curable urethane composition | |
| JP7181912B2 (en) | Adhesion improver and adhesive using the same | |
| JP2019206661A (en) | Polyurethane urea resin-forming composition | |
| JP2022134107A (en) | Curable urethane composition, and cured product thereof | |
| JP2025032980A (en) | Base for two-component curing urethane adhesive | |
| WO2025047318A1 (en) | Surface protection film | |
| JP2024024542A (en) | Urethane prepolymer and its manufacturing method | |
| CN118791722A (en) | Polycarbonate polyol copolymer | |
| JP2023080861A (en) | Adhesives for sticking to skin and adhesive tapes for sticking to skin |