本発明は、フッ素系水性塗料に関する。 The present invention relates to a fluorine-based water-based paint.
橋梁、高速道路、送電鉄塔といった屋外構造物は、過酷な環境に長期に渡って曝されるため、重防食用塗料の塗膜で保護されている。重防食用塗料としては含フッ素重合体と有機溶媒を含むフッ素系溶剤型塗料が用いられるが、有機溶媒を含むため屋外での塗装に際しては細心の注意が必要である。そのため、フッ素系溶剤型塗料にかわるフッ素系水性塗料が求められている（特許文献１参照）。 Outdoor structures such as bridges, highways, and power transmission towers are exposed to harsh environments for a long period of time, so they are protected with a coating of heavy anticorrosion paint. As a heavy anticorrosion paint, a fluorine-based solvent-type paint containing a fluorine-containing polymer and an organic solvent is used. However, since it contains an organic solvent, great care must be taken when painting outdoors. Therefore, there is a demand for a fluorine-based aqueous paint that replaces the fluorine-based solvent-type paint (see Patent Document 1).
しかし、フッ素系水性塗料の塗膜は、フッ素系溶剤型塗料のそれと比較して耐候性に劣る場合がある。
フッ素系水性塗料において含フッ素重合体の粒子は水中に分散しており、その塗膜は含フッ素重合体の粒子間の融着により形成される。しかし、粒子間の融着が密に進行しない場合、形成される塗膜に空隙が生じやすい。その結果、空気中の水分等が塗膜に取り込まれ、割れや剥がれにより塗膜が劣化するため、塗膜の耐候性が低下しやすい。
本発明者らは、特許文献１に記載のフッ素系水性塗料の硬化塗膜を実際に評価した結果、重防食塗料に求められる耐候性を満たさないことを知見した。However, the coating film of the fluorinated water-based paint may have inferior weather resistance as compared with that of the fluorinated solvent-based paint.
In the fluorine-based water-based paint, the fluoropolymer particles are dispersed in water, and the coating film is formed by fusion between the fluoropolymer particles. However, when the fusion between the particles does not proceed densely, voids are likely to occur in the formed coating film. As a result, moisture in the air or the like is taken into the coating film, and the coating film deteriorates due to cracking or peeling, so that the weather resistance of the coating film tends to decrease.
As a result of actually evaluating the cured coating film of the fluorine-based water-based paint described in Patent Document 1, the present inventors have found that the weather resistance required for heavy anticorrosion paint is not satisfied.
本発明者らは、鋭意検討した結果、フッ素系水性塗料に含まれる含フッ素重合体の水酸基価および最低造膜温度を、所定の範囲に制御すれば、その硬化塗膜の造膜性が良好となり、硬化塗膜の割れや剥がれが生じにくく、耐候性に優れる硬化塗膜を形成することを見出した。 As a result of intensive studies, the inventors of the present invention have good film-forming properties of the cured coating film by controlling the hydroxyl value and the minimum film-forming temperature of the fluoropolymer contained in the fluorine-based water-based paint within a predetermined range. Thus, the present inventors have found that a cured coating film that is not easily cracked or peeled off and that has excellent weather resistance is formed.
すなわち、本発明は、以下の発明を提供する。
［１］ フルオロオレフィンに基づく単位および水酸基を有する単量体に基づく単位を含む含フッ素重合体の粒子と、界面活性剤と、硬化剤と、水とを含む水性塗料であって、該含フッ素重合体の水酸基価が１５〜５０ｍｇＫＯＨ／ｇであり、該含フッ素重合体の最低造膜温度が５〜４０℃であることを特徴とする水性塗料。
［２］ 上記粒子の平均粒子径が２００ｎｍ以下である、［１］に記載の水性塗料。
［３］ 上記界面活性剤がノニオン性界面活性剤であり、該ノニオン性界面活性剤のＨＬＢ値が１２〜１８である、［１］または［２］に記載の水性塗料。
［４］ エポキシ樹脂またはウレタン樹脂の塗膜を有する基材の、該塗膜の表面に、請求項１〜３のいずれかに記載の水性塗料を塗布して塗膜を形成し、該塗膜を硬化させて膜厚が２５〜２００μｍの硬化塗膜を形成する、硬化塗膜付き基材の製造方法。
［５］ ［１］〜［３］のいずれかに記載の水性塗料の塗膜を硬化させてなる、膜厚が２５〜２００μｍの硬化塗膜を表面に有する硬化塗膜付き基材。That is, the present invention provides the following inventions.
[1] A water-based paint comprising a fluoropolymer particle containing a unit based on a fluoroolefin and a unit based on a monomer having a hydroxyl group, a surfactant, a curing agent, and water, A water-based paint, wherein the polymer has a hydroxyl value of 15 to 50 mgKOH / g, and the minimum film-forming temperature of the fluoropolymer is 5 to 40 ° C.
[2] The water-based paint according to [1], wherein the average particle size of the particles is 200 nm or less.
[3] The aqueous paint according to [1] or [2], wherein the surfactant is a nonionic surfactant, and the HLB value of the nonionic surfactant is 12 to 18.
[4] A coating film is formed by applying the water-based paint according to any one of claims 1 to 3 on the surface of the coating film of a base material having a coating film of an epoxy resin or a urethane resin. The manufacturing method of the base material with a cured coating film which cures and forms a cured coating film with a film thickness of 25-200 micrometers.
[5] A substrate with a cured coating film having a cured coating film with a film thickness of 25 to 200 μm on the surface, which is formed by curing the coating film of the water-based paint according to any one of [1] to [3].
本発明によれば、硬化塗膜の割れや剥がれが生じにくく、耐候性に優れる硬化塗膜を形成する水性塗料を提供できる。
また本発明は、本発明の水性塗料を硬化させてなる硬化塗膜を表面に有する硬化塗膜付き基材、およびその製造方法も提供できる。ADVANTAGE OF THE INVENTION According to this invention, the aqueous coating material which forms the cured coating film which is hard to produce a crack and peeling of a cured coating film, and is excellent in a weather resistance can be provided.
Moreover, this invention can also provide the base material with a cured coating film which has the cured coating film which hardens the water-based coating material of this invention on the surface, and its manufacturing method.
本発明における用語の意味は以下の通りである。
「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
「単位」とは、単量体の重合により直接形成される原子団と、単量体の重合により形成される原子団の一部を化学変換して得られる単位との総称である。重合体が含む全単位に対する、それぞれの単位の含有量（モル％）は、含フッ素重合体の製造に際して使用する成分の仕込み量から決定できる。
「（メタ）アクリル」とは、「アクリル」および「メタクリル」の総称である。
「含フッ素重合体の粒子」とは、水中で粒子状に分散している含フッ素重合体を意味する。
「平均粒子径」は、ＥＬＳ−８０００（大塚電子株式会社製）を用いて動的光散乱法により求められるＤ５０の値である。なお、Ｄ５０は、動的光散乱法により測定した粒子の粒度分布において、小さな粒子側から起算した体積累計５０体積％の粒子直径を表す。
「水酸基価」は、ＪＩＳ Ｋ ００７０（１９９２）の方法にしたがって測定される値である。
「最低造膜温度」は、含フッ素重合体を乾燥させたとき、亀裂のない均一な塗膜が形成される最低温度であり、造膜温度測定装置ＩＭＣ−１５３５型（株式会社井元製作所製）を用いて測定される値である。The meanings of terms in the present invention are as follows.
The numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The “unit” is a general term for an atomic group directly formed by polymerization of a monomer and a unit obtained by chemically converting a part of the atomic group formed by polymerization of a monomer. The content (mol%) of each unit with respect to all the units contained in the polymer can be determined from the amounts of components used in the production of the fluoropolymer.
“(Meth) acryl” is a general term for “acryl” and “methacryl”.
“Fluoropolymer particles” means a fluoropolymer dispersed in water in the form of particles.
“Average particle diameter” is a value of D50 determined by a dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.). In addition, D50 represents the particle diameter of 50 volume% of cumulative volume calculated from the small particle side in the particle size distribution of the particle measured by the dynamic light scattering method.
The “hydroxyl value” is a value measured according to the method of JIS K 0070 (1992).
“Minimum film-forming temperature” is the lowest temperature at which a uniform coating film without cracks is formed when the fluoropolymer is dried. Film-forming temperature measuring device IMC-1535 type (manufactured by Imoto Seisakusho Co., Ltd.) Is a value measured using.
本発明の水性塗料は、フルオロオレフィンに基づく単位および水酸基を有する単量体に基づく単位を含む含フッ素重合体の粒子と、界面活性剤と、硬化剤と、水とを含む水性塗料であって、該含フッ素重合体の水酸基価が１５〜５０ｍｇＫＯＨ／ｇであり、該含フッ素重合体の最低造膜温度が５〜４０℃である。 The water-based paint of the present invention is a water-based paint comprising fluoropolymer particles containing a unit based on a fluoroolefin and a unit based on a monomer having a hydroxyl group, a surfactant, a curing agent, and water. The hydroxyl value of the fluoropolymer is 15 to 50 mg KOH / g, and the minimum film-forming temperature of the fluoropolymer is 5 to 40 ° C.
本発明の水性塗料は、割れや剥がれが生じにくく、耐候性に優れる硬化塗膜を形成できる。この理由は、本発明の水性塗料に含まれる含フッ素重合体の水酸基価および最低造膜温度が、所定の範囲にあることによる。
前述の通り、水性塗料において、含フッ素重合体の粒子は水中に分散している。水性塗料を基材の表面に塗布して塗膜を形成させ、硬化させると、水の蒸発に伴い含フッ素重合体の粒子が融着して硬化塗膜が形成される。この際、空隙のない密な硬化塗膜が形成されるには、水の蒸発と、含フッ素重合体の粒子の融着および硬化剤による含フッ素重合体間の架橋とが、バランスして進行する必要がある。本発明者らは、含フッ素重合体の水酸基価および最低造膜温度が所定の範囲にあれば、密な硬化塗膜が形成され、耐候性に優れる硬化塗膜が得られることを見出したのである。The water-based paint of the present invention is less susceptible to cracking and peeling, and can form a cured coating film having excellent weather resistance. This is because the hydroxyl value and the minimum film-forming temperature of the fluoropolymer contained in the water-based paint of the present invention are within a predetermined range.
As described above, in the water-based paint, the fluoropolymer particles are dispersed in water. When a water-based paint is applied to the surface of a substrate to form a coating film and cured, the particles of the fluoropolymer are fused together with the evaporation of water to form a cured coating film. At this time, in order to form a dense cured coating film without voids, water evaporation and fusion of the fluoropolymer particles and crosslinking between the fluoropolymers by a curing agent proceed in a balanced manner. There is a need to. The present inventors have found that if the hydroxyl value and the minimum film-forming temperature of the fluoropolymer are within a predetermined range, a dense cured coating film is formed and a cured coating film having excellent weather resistance can be obtained. is there.
本発明における含フッ素重合体は、フルオロオレフィンに基づく単位（以下、「単位Ｆ」ともいう。）、および水酸基を有する単量体（以下、「単量体１」ともいう。）に基づく単位（以下、「単位１」ともいう。）を含む。
フルオロオレフィンは、オレフィンの水素原子の１個以上がフッ素原子で置換された化合物である。フルオロオレフィンは、フッ素原子で置換されていない水素原子の１個以上が塩素原子で置換されていてもよい。The fluoropolymer in the present invention is a unit based on a fluoroolefin unit (hereinafter also referred to as “unit F”) and a unit based on a monomer having a hydroxyl group (hereinafter also referred to as “monomer 1”). Hereinafter, also referred to as “unit 1”).
A fluoroolefin is a compound in which one or more hydrogen atoms of the olefin are substituted with fluorine atoms. In the fluoroolefin, one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.
フルオロオレフィンは、ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ、ＣＨ２＝ＣＦ２、ＣＦ２＝ＣＦＣＦ３またはＣＨ２＝ＣＦＣＦ３が好ましく、本発明の水性塗料から形成される硬化塗膜（以下、「本塗膜」ともいう。）の耐候性の観点から、ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌがより好ましい。また、フルオロオレフィンは、１種を単独使用してもよく、２種以上を併用してもよい。
単位Ｆの含有量は、含フッ素重合体が含む全単位に対して、２０〜７０モル％が好ましく、本発明における含フッ素重合体の粒子（以下、「本粒子」ともいう。）の水中分散性と、本塗膜の耐候性の観点から、３０〜６０モル％がより好ましい。The fluoroolefin is preferably CF2 ═CF2 , CF2 ═CFCl, CF2 ═CHF, CH2 ═CF2 , CF2 ═CFCF3, or CH2 ═CFCF3 , a cure formed from the aqueous paint of the present invention. From the viewpoint of the weather resistance of the coating film (hereinafter also referred to as “main coating film”), CF2 = CF2 or CF2 = CFCl is more preferable. Moreover, fluoroolefin may be used individually by 1 type and may use 2 or more types together.
The content of the unit F is preferably 20 to 70 mol% with respect to the total units contained in the fluoropolymer, and the fluoropolymer particles (hereinafter also referred to as “the present particles”) in the present invention are dispersed in water. From the viewpoint of the property and the weather resistance of the coating film, 30 to 60 mol% is more preferable.
単量体１は、水酸基を有する、ビニルエーテル、ビニルエステル、アリルエーテルまたは（メタ）アクリル酸エステルが好ましい。単量体１の含有量を調節すれば、含フッ素重合体の水酸基価を好適に制御できる。
単量体１の具体例としては、ヒドロキシアルキルビニルエーテル（シクロヘキサンジメタノールモノビニルエーテル、２−ヒドロキシエチルビニルエーテル、４−ヒドロキシブチルビニルエーテル等。）、ポリオキシアルキレンヒドロキシアルキルビニルエーテル、エチレングリコールモノビニルエーテル（ジエチレングリコールモノビニルエーテル等。）、ヒドロキシアルキルアリルエーテル（ヒドロキシエチルアリルエーテル等。）、ヒドロキシアルキルビニルエステル（ヒドロキシエチルカルボン酸ビニルエステル等。）（メタ）アクリル酸ヒドロキシアルキルエステル（（メタ）アクリル酸ヒドロキシエチル等。）が挙げられる。
単位１の含有量は、含フッ素重合体が含む全単位に対して、１〜３０モル％が好ましく、含フッ素重合体の水酸基価と架橋性の観点から、５〜１５モル％がより好ましい。The monomer 1 is preferably a vinyl ether, vinyl ester, allyl ether or (meth) acrylic acid ester having a hydroxyl group. If the content of monomer 1 is adjusted, the hydroxyl value of the fluoropolymer can be suitably controlled.
Specific examples of the monomer 1 include hydroxyalkyl vinyl ether (cyclohexanedimethanol monovinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc.), polyoxyalkylene hydroxyalkyl vinyl ether, ethylene glycol monovinyl ether (diethylene glycol monovinyl ether). Etc.), hydroxyalkyl allyl ether (hydroxyethyl allyl ether, etc.), hydroxyalkyl vinyl ester (hydroxyethyl carboxylic acid vinyl ester, etc.) (meth) acrylic acid hydroxyalkyl ester (hydroxy (meth) acrylate, etc.) Is mentioned.
The content of unit 1 is preferably 1 to 30 mol% with respect to all units contained in the fluoropolymer, and more preferably 5 to 15 mol% from the viewpoint of the hydroxyl value and crosslinkability of the fluoropolymer.
本発明における含フッ素重合体は、必要に応じて、単量体Ｆおよび単量体１以外の単量体（以下、「単量体２」ともいう。）に基づく単位（以下、「単位２」ともいう。）をさらに含んでいてもよい。 The fluorine-containing polymer in the present invention, if necessary, is a unit based on a monomer other than the monomer F and the monomer 1 (hereinafter also referred to as “monomer 2”) (hereinafter “unit 2”). May also be included.
単量体２の具体例としては、オレフィン（エチレン、プロピレン等。）、アルキルビニルエーテル（エチルビニルエーテル、ブチルビニルエーテル、２−エチルヘキシルビニルエーテル等。）、シクロアルキルビニルエーテル（シクロヘキシルビニルエーテル等。）、アルキルビニルエステル（ピバリン酸ビニルエステル等。）、アルキルアリルエステル（ピバリン酸アリルエステル等。）、芳香族ビニル（スチレン、ビニルトルエン等。）、アリルエーテル（エチルアリルエーテル等。）、（メタ）アクリル酸エステル（メチル（メタ）アクリル酸等。）が挙げられる。
なお、単量体２は、含フッ素重合体の親水性等の物性を損なわない範囲で、水酸基以外の架橋性基を有する単量体であってもよい。該架橋性基の具体例としては、加水分解性シリル基、カルボキシ基、アミノ基、イソシアネート基、エポキシ基、またはオキセタニル基が挙げられ、本塗膜の基材密着性の観点から、カルボキシ基が好ましい。
また、単量体２は、１種を単独使用してもよく、２種以上を併用してもよい。Specific examples of the monomer 2 include olefins (ethylene, propylene, etc.), alkyl vinyl ethers (ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, etc.), cycloalkyl vinyl ethers (cyclohexyl vinyl ether, etc.), alkyl vinyl esters ( Pivalic acid vinyl ester, etc.), alkyl allyl ester (pivalic acid allyl ester, etc.), aromatic vinyl (styrene, vinyl toluene, etc.), allyl ether (ethyl allyl ether, etc.), (meth) acrylic acid ester (methyl) (Meth) acrylic acid, etc.).
The monomer 2 may be a monomer having a crosslinkable group other than a hydroxyl group as long as the physical properties such as hydrophilicity of the fluoropolymer are not impaired. Specific examples of the crosslinkable group include a hydrolyzable silyl group, a carboxy group, an amino group, an isocyanate group, an epoxy group, or an oxetanyl group. From the viewpoint of substrate adhesion of the coating film, the carboxy group is preferable.
Moreover, the monomer 2 may be used individually by 1 type, and may use 2 or more types together.
本発明における含フッ素重合体が単量体２を含む場合の、単量体２の含有量は、含フッ素重合体が含む全単位に対して、１５〜７５モル％が好ましく、単位１の反応性の観点から、２０〜６０モル％がより好ましく、３０〜５０モル％が特に好ましい。
本発明における含フッ素重合体は、単位Ｆの含有量、単位１の含有量、および単位２の含有量が、含フッ素重合体が含む全単位に対してこの順に、２０〜７０モル％、１〜３０モル％、０〜７５モル％であるのが好ましい。単位Ｆ、単位１および単位２の含有量を調節すれば、本発明の水性塗料の水酸基価および最低造膜温度を、所定の範囲に制御できる。When the fluorinated polymer in the present invention contains the monomer 2, the content of the monomer 2 is preferably 15 to 75 mol% with respect to the total units contained in the fluorinated polymer. From a viewpoint of property, 20-60 mol% is more preferable, and 30-50 mol% is especially preferable.
In the fluorine-containing polymer of the present invention, the content of the unit F, the content of the unit 1, and the content of the unit 2 are 20 to 70 mol% in this order with respect to all units contained in the fluorine-containing polymer. It is preferably -30 mol% and 0-75 mol%. By adjusting the content of unit F, unit 1 and unit 2, the hydroxyl value and the minimum film-forming temperature of the water-based paint of the present invention can be controlled within a predetermined range.
本発明における含フッ素重合体の水酸基価は、１５〜５０ｍｇＫＯＨ／ｇが好ましく、２０〜５０ｍｇＫＯＨ／ｇがより好ましく、２５〜５０ｍｇＫＯＨ／ｇが特に好ましい。水酸基価が１５ｍｇＫＯＨ／ｇ以上であれば、本粒子間の融着が密に進行し、耐候性に優れた硬化塗膜を形成できる。水酸基価が５０ｍｇＫＯＨ／ｇ以下であれば、本粒子の水中分散性に優れる。 The hydroxyl value of the fluoropolymer in the present invention is preferably 15 to 50 mgKOH / g, more preferably 20 to 50 mgKOH / g, and particularly preferably 25 to 50 mgKOH / g. When the hydroxyl value is 15 mgKOH / g or more, fusion between the particles proceeds densely, and a cured coating film having excellent weather resistance can be formed. When the hydroxyl value is 50 mgKOH / g or less, the particles are excellent in dispersibility in water.
本発明における含フッ素重合体の最低造膜温度は、５〜４０℃が好ましく、１０〜４０℃がより好ましく、１５〜４０℃が特に好ましく、２０〜３５℃がさらに好ましい。最低造膜温度が５℃以上であれば、本粒子間の融着が密に進行し、本塗膜の割れや剥がれが抑制される。最低造膜温度が４０℃以下であれば、本塗膜中の空隙が軽減される。 5-40 degreeC is preferable, as for the minimum film forming temperature of the fluoropolymer in this invention, 10-40 degreeC is more preferable, 15-40 degreeC is especially preferable, and 20-35 degreeC is further more preferable. When the minimum film-forming temperature is 5 ° C. or higher, fusion between the particles proceeds densely, and cracking and peeling of the coating film are suppressed. If the minimum film forming temperature is 40 ° C. or lower, the voids in the coating film are reduced.
本粒子の平均粒子径は、本塗膜中の空隙軽減の観点から、２００ｎｍ以下が好ましく、１９０ｎｍ以下がより好ましく、１８５ｎｍ以下が特に好ましい。本粒子の平均粒子径の下限は、通常５０ｎｍである。
本発明における含フッ素重合体の含有量は、水性塗料の全質量に対して、１０〜７０質量％が好ましく、２０〜６５質量％がより好ましい。The average particle size of the present particles is preferably 200 nm or less, more preferably 190 nm or less, and particularly preferably 185 nm or less, from the viewpoint of reducing voids in the coating film. The lower limit of the average particle size of the particles is usually 50 nm.
10-70 mass% is preferable with respect to the total mass of a water-based coating material, and, as for content of the fluoropolymer in this invention, 20-65 mass% is more preferable.
本発明における界面活性剤は、本粒子の水中分散性の観点から、ＨＬＢ値が１２〜１８のノニオン性界面活性剤が好ましい。なお、必要に応じて、アニオン性界面活性剤、カチオン性界面活性剤、中性界面活性剤等を併用してもよい。また、界面活性剤は、１種を単独使用してもよく、２種以上を併用してもよい。
ノニオン性界面活性剤の具体例としては、アルキルフェノールエチレンオキシド付加物、高級アルコールエチレンオキシド付加物、エチレンオキシドとプロピレンオキシドのブロック二元共重合体が挙げられる。
本発明における界面活性剤の含有量は、本粒子の水中分散性の観点から、含フッ素重合体の全質量に対して、０．０１〜１５質量％が好ましく、０．１〜１０質量％がより好ましい。The surfactant in the present invention is preferably a nonionic surfactant having an HLB value of 12 to 18 from the viewpoint of dispersibility of the particles in water. In addition, you may use together an anionic surfactant, a cationic surfactant, a neutral surfactant, etc. as needed. Moreover, surfactant may be used individually by 1 type and may use 2 or more types together.
Specific examples of the nonionic surfactant include an alkylphenol ethylene oxide adduct, a higher alcohol ethylene oxide adduct, and a block binary copolymer of ethylene oxide and propylene oxide.
The content of the surfactant in the present invention is preferably 0.01 to 15% by mass, and 0.1 to 10% by mass with respect to the total mass of the fluoropolymer from the viewpoint of dispersibility in water of the present particles. More preferred.
本発明における硬化剤は、含フッ素重合体を架橋させる、水酸基と反応しうる基を２以上有する化合物である。硬化剤によって、含フッ素重合体間の架橋が密に進行し、耐候性、耐水性、耐薬品性、耐熱性等に優れる硬化塗膜を形成できる。 The curing agent in the present invention is a compound having two or more groups capable of reacting with a hydroxyl group to crosslink the fluoropolymer. By the curing agent, cross-linking between the fluoropolymers proceeds densely, and a cured coating film having excellent weather resistance, water resistance, chemical resistance, heat resistance, and the like can be formed.
水酸基と反応しうる基は、イソシアネート基またはブロック化イソシアネート基が好ましい。また、硬化剤の１分子が有する該基の数は、２〜３０が好ましい。
硬化剤の具体例としては、ブロック化ポリイソシアネート化合物またはその乳化分散体、β−ヒドロキシアルキルアミン、メチロールメラミン、ブチルエーテル化メチロールメラミン等のメラミン樹脂、メチロール尿素、ブチルエーテル化メチロール尿素等の尿素樹脂が挙げられる。
本発明における硬化剤の含有量は、水性分散液全質量に対して、０．１〜５０質量％が好ましい。The group capable of reacting with a hydroxyl group is preferably an isocyanate group or a blocked isocyanate group. Moreover, as for the number of this group which 1 molecule of a hardening | curing agent has, 2-30 are preferable.
Specific examples of the curing agent include blocked polyisocyanate compounds or emulsion dispersions thereof, β-hydroxyalkylamine, methylol melamine, melamine resins such as butyl etherified methylol melamine, and urea resins such as methylol urea and butyl etherified methylol urea. It is done.
As for content of the hardening | curing agent in this invention, 0.1-50 mass% is preferable with respect to the aqueous dispersion total mass.
本発明における水は、塗料成分の含フッ素重合体を分散させる分散媒である。なお、分散媒は、水のみからなるか、水と水溶性有機溶媒とからなる混合溶媒からなる。後者の場合、水溶性有機溶媒の含有量は、水の全質量に対して、５質量％以下が好ましく、１質量％以下がより好ましく、０．５質量％以下が特に好ましい。水溶性有機溶媒の具体例としては、メタノール、エタノール、ブタノール、アセトン、メチルエチルケトンが挙げられる。 Water in the present invention is a dispersion medium for dispersing the fluorine-containing polymer of the paint component. The dispersion medium is composed of water alone or a mixed solvent composed of water and a water-soluble organic solvent. In the latter case, the content of the water-soluble organic solvent is preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less with respect to the total mass of water. Specific examples of the water-soluble organic solvent include methanol, ethanol, butanol, acetone, and methyl ethyl ketone.
本発明の水性塗料は、必要に応じて、含フッ素重合体、界面活性剤、硬化剤および水以外の添加剤を含んでもよい。添加剤の具体例としては、顔料、分散剤、消泡剤、造膜助剤、レベリング剤、増粘剤、硬化助剤、光安定剤、表面調整剤が挙げられる。 The water-based paint of the present invention may contain an additive other than a fluorine-containing polymer, a surfactant, a curing agent, and water as necessary. Specific examples of the additive include pigments, dispersants, antifoaming agents, film forming aids, leveling agents, thickeners, curing aids, light stabilizers, and surface conditioners.
本発明の水性塗料の製造方法としては、フルオロオレフィンと単量体１を含む単量体混合物を、界面活性剤、水および重合開始剤の存在下にて重合させ、含フッ素重合体の粒子を含む水性分散液（以下、単に「水性分散液」ともいう。）を得て、該水性分散液に硬化剤を添加する方法が挙げられる。本発明の水性塗料は、硬化剤を含まない水性塗料と、硬化剤とを別途調製する二液型の水性塗料とし、使用直前に両者を混合して使用されるのが好ましい。
なお、水性分散液は、上記単量体混合物を、有機溶媒と重合開始剤の存在下にて重合させた後、該有機溶媒を除去し、水に分散させても得られる。As a method for producing the water-based paint of the present invention, a monomer mixture containing a fluoroolefin and a monomer 1 is polymerized in the presence of a surfactant, water and a polymerization initiator, and the fluorine-containing polymer particles are obtained. Examples thereof include a method of obtaining an aqueous dispersion containing (hereinafter, also simply referred to as “aqueous dispersion”) and adding a curing agent to the aqueous dispersion. The water-based paint of the present invention is preferably a two-pack type water-based paint in which a water-based paint not containing a curing agent and a curing agent are separately prepared, and both are used immediately before use.
The aqueous dispersion can also be obtained by polymerizing the monomer mixture in the presence of an organic solvent and a polymerization initiator, then removing the organic solvent and dispersing in water.
本発明の水性塗料は、基材の表面に直接塗布してもよく、表面処理（下地処理等）された基材の表面に塗布してもよい。本塗膜の基材密着性と耐候性および耐久性の観点から、本発明のフッ素水性系塗料は、表面処理された基材の表面に塗布するのが好ましい。表面処理された基材は、本塗膜の基材密着性の観点から、エポキシ樹脂またはウレタン樹脂の塗膜を有する基材が好ましい。エポキシ樹脂またはウレタン樹脂の塗膜は、本発明の水性塗料を表面に塗布する前にあらかじめ硬化してもよく、本発明の水性塗料と同時に硬化してもよい。本発明の水性塗料は、エポキシ樹脂またはウレタン樹脂のような柔軟性に富む樹脂に塗布され、該樹脂が変形する場合でも、割れや剥がれの生じにくく、任意の膜厚の硬化塗膜を形成できる。 The water-based paint of the present invention may be applied directly to the surface of the substrate, or may be applied to the surface of the substrate that has been surface-treated (such as a base treatment). From the viewpoints of substrate adhesion, weather resistance and durability of the coating film, it is preferable that the fluorinated aqueous coating material of the present invention is applied to the surface of the surface-treated substrate. The surface-treated substrate is preferably a substrate having a coating film of epoxy resin or urethane resin from the viewpoint of substrate adhesion of the coating film. The coating film of the epoxy resin or the urethane resin may be cured in advance before the aqueous paint of the present invention is applied to the surface, or may be cured simultaneously with the aqueous paint of the present invention. The water-based paint of the present invention is applied to a flexible resin such as an epoxy resin or a urethane resin, and even when the resin is deformed, it is difficult to cause cracking or peeling, and a cured coating film having an arbitrary film thickness can be formed. .
本塗膜の膜厚は、２５〜２００μｍが好ましく、本塗膜の耐久性の観点から、３０〜１００μｍがより好ましく、３０〜８０μｍ特に好ましい。
橋梁、高速道路、送電鉄塔といった屋外構造物に使用される重防食用塗料の塗膜には、厚膜が求められる場合がある。本発明の水性塗料は、割れや剥がれが生じにくいため、厚膜の形成にも充分対応できる。The film thickness of the coating film is preferably 25 to 200 μm, more preferably 30 to 100 μm, and particularly preferably 30 to 80 μm from the viewpoint of durability of the coating film.
A thick film may be required for a coating film of heavy anticorrosion paint used for outdoor structures such as bridges, highways and power transmission towers. Since the water-based paint of the present invention is not easily cracked or peeled off, it can sufficiently cope with the formation of a thick film.
基材の具体例としては、非金属材料（樹脂、ゴム、木材等の有機質材料、コンクリート、ガラス、セラミックス、石材等の無機質材料）および金属材料（鉄、鉄合金、アルミニウム、アルミニウム合金等）が挙げられる。 Specific examples of the substrate include non-metallic materials (organic materials such as resin, rubber, and wood, inorganic materials such as concrete, glass, ceramics, and stone) and metal materials (iron, iron alloy, aluminum, aluminum alloy, etc.). Can be mentioned.
本発明の水性塗料の、塗布方法の具体例としては、刷毛、ローラー、ディッピング、スプレー、ロールコーター、ダイコーター、アプリケーター、スピンコーター等の塗布装置を使用する方法が挙げられる。 Specific examples of the coating method of the water-based paint of the present invention include a method using a coating device such as a brush, a roller, dipping, spraying, a roll coater, a die coater, an applicator, and a spin coater.
本塗膜は、本発明の水性塗料を塗布して形成された塗膜を、乾燥させ、硬化させて形成するのが好ましい。塗布後の乾燥温度と硬化温度は、それぞれ２５℃〜３００℃が好ましい。
つまり、本発明によれば、エポキシ樹脂またはウレタン樹脂の塗膜を有する基材の、該塗膜の表面に、本発明の水性塗料を塗布して塗膜を形成し、該塗膜を硬化させて膜厚が２５〜２００μｍの硬化塗膜を形成する、硬化塗膜付き基材の製造方法が提供される。
上述の通り、本塗膜付き基材は、割れや剥がれが生じにくく、耐候性に極めて優れるため、橋梁、高速道路、送電鉄塔といった、厳しい環境に長期に渡って曝される屋外構造物の保護に使用される重防食用塗料として、好適に使用できる。The coating film is preferably formed by drying and curing a coating film formed by applying the aqueous paint of the present invention. The drying temperature and the curing temperature after application are preferably 25 ° C to 300 ° C, respectively.
That is, according to the present invention, the water-based paint of the present invention is applied to the surface of the substrate having an epoxy resin or urethane resin coating to form a coating, and the coating is cured. The manufacturing method of the base material with a cured coating film which forms a cured coating film with a film thickness of 25-200 micrometers is provided.
As mentioned above, this coated substrate is not easily cracked or peeled off and has excellent weather resistance. Therefore, it protects outdoor structures such as bridges, highways, and power transmission towers that are exposed to harsh environments for a long time. It can be suitably used as a heavy anticorrosion paint used in the above.
以下、例を挙げて本発明を詳細に説明する。ただし本発明はこれらの例に限定されない。なお、後述する表中における各成分の配合量は、質量基準を示す。 Hereinafter, the present invention will be described in detail with examples. However, the present invention is not limited to these examples. In addition, the compounding quantity of each component in the table | surface mentioned later shows a mass reference | standard.
〔水性塗料の製造に使用した成分〕
（含フッ素重合体）
以下の単量体を用い、後述する例により得られる含フッ素重合体を使用した。
単量体Ｆ：ＣＦ２＝ＣＦＣｌ（ＣＴＦＥ）
単量体１：シクロヘキサンジメタノールモノビニルエーテル（ＣＨＭＶＥ）、ヒドロキシブチルビニルエーテル（ＨＢＶＥ）、ＣＨ２＝ＣＨＯＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１Ｈ（ｎ１＝１５）（ＣＭ−１５ＥＯＶＥ）
単量体２：エチルビニルエーテル（ＥＶＥ）、シクロヘキシルビニルエーテル（ＣＨＶＥ）、２−エチルヘキシルビニルエーテル（２−ＥＨＶＥ）
（界面活性剤）
ＤＫＳ ＮＬ−１００：ポリオキシエチレンアルキルエーテル（ＨＬＢ値が１３．８であるノニオン性界面活性剤、第一工業製薬社製）
Ｎｅｗｃｏｌ Ｎ−２３２０：（ＨＬＢ値が１６．４であるノニオン性界面活性剤、日本乳化剤社製）
ＳＬＳ：ラウリル硫酸ナトリウム
（硬化剤）
Ｂａｙｈｙｄｕｒ３１００（２以上のイソシアネート基を有する化合物、Ｂａｙｅｒ社製）
（その他添加剤）
顔料：Ｄ９１８（堺化学工業社製）
分散剤：ＢＹＫ−１９０（ＢＹＫ−Ｃｈｅｍｉｅ社製）
消泡剤：デヒドラン １６２０（ＢＡＳＦ社製）
造膜助剤：ＣＳ−１２（Ａｌｄｒｉｃｈ社製）
レベリング剤：ＢＹＫ−３４８（ＢＹＫ−Ｃｈｅｍｉｅ社製）
増粘剤：Ｒｈｅｏｌａｔｅ ２８８（Ｅｌｅｍｅｎｔｉｓ社製）[Ingredients used in the manufacture of water-based paints]
(Fluoropolymer)
The following monomers were used and the fluoropolymer obtained by the example mentioned later was used.
Monomer F: CF2 = CFCl (CTFE)
Monomer 1: cyclohexanedimethanol monovinyl ether (CHMVE), hydroxybutyl vinyl ether(HBVE), CH 2 = CHOCH 2 -cycloC 6 H 10 -CH 2 O (CH 2 CH 2 O) n1 H (n1 = 15) ( CM-15EOVE)
Monomer 2: Ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), 2-ethylhexyl vinyl ether (2-EHVE)
(Surfactant)
DKS NL-100: polyoxyethylene alkyl ether (nonionic surfactant having an HLB value of 13.8, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Newcol N-2320: (nonionic surfactant having an HLB value of 16.4, manufactured by Nippon Emulsifier Co., Ltd.)
SLS: Sodium lauryl sulfate (curing agent)
Bayhydrur 3100 (compound having two or more isocyanate groups, manufactured by Bayer)
(Other additives)
Pigment: D918 (manufactured by Sakai Chemical Industry Co., Ltd.)
Dispersant: BYK-190 (manufactured by BYK-Chemie)
Antifoaming agent: Dehydran 1620 (manufactured by BASF)
Film-forming aid: CS-12 (manufactured by Aldrich)
Leveling agent: BYK-348 (manufactured by BYK-Chemie)
Thickener: Rheolate 288 (made by Elementis)
［合成例１］
真空脱気したオートクレーブ内に、ＣＴＦＥ（５２９．５５ｇ）、ＣＨＭＶＥ（７７．４１ｇ）、ＣＭ−１５ＥＯＶＥ（２５．６７ｇ）、ＥＶＥ（２８６．２９ｇ）、ＣＨＶＥ（１１．４８ｇ）、イオン交換水（９３０ｇ）、炭酸カリウム（１．４ｇ）、ＤＫＳ ＮＬ−１００（４６．５２ｇ）、ＳＬＳ（０．９３ｇ）を撹拌下で導入して昇温し、５０℃に保持した。
続いて、オートクレーブ内に、過硫酸アンモニウムの０．４質量％水溶液（５０ｍＬ）を連続的に添加しながら２４時間重合した後、オートクレーブ内溶液をろ過し、含フッ素重合体を含む水性分散液１（固形分濃度５０質量％）を得た。
水性分散液１の水酸基価は２７ｍｇＫＯＨ／ｇであり、最低造膜温度は２１℃であり、含フッ素重合体の粒子の平均粒子径は１８１ｎｍであった。
なお、水性分散液１の、ＣＴＦＥに基づく単位、ＣＨＭＶＥに基づく単位、ＣＭ−ＥＯＶＥに基づく単位、ＥＶＥに基づく単位、ＣＨＶＥに基づく単位の含有量は、この順に５０モル％、７モル％、０．３４モル％、４１．７モル％、１モル％であった。[Synthesis Example 1]
In a vacuum degassed autoclave, CTFE (529.55 g), CHMVE (77.41 g), CM-15EOOVE (25.67 g), EVE (286.29 g), CHVE (11.48 g), ion-exchanged water (930 g) ), Potassium carbonate (1.4 g), DKS NL-100 (46.52 g) and SLS (0.93 g) were introduced with stirring, and the temperature was raised and maintained at 50 ° C.
Subsequently, after polymerizing for 24 hours while continuously adding a 0.4% by mass aqueous solution of ammonium persulfate (50 mL) in the autoclave, the solution in the autoclave was filtered, and the aqueous dispersion 1 containing the fluoropolymer ( Solid content concentration 50 mass%) was obtained.
The hydroxyl value of the aqueous dispersion 1 was 27 mgKOH / g, the minimum film-forming temperature was 21 ° C., and the average particle size of the fluoropolymer particles was 181 nm.
In addition, the content of the unit based on CTFE, the unit based on CHMVE, the unit based on CM-EOVE, the unit based on EVE, and the unit based on CHVE of the aqueous dispersion 1 was 50 mol%, 7 mol%, 0 in this order. .34 mol%, 41.7 mol%, and 1 mol%.
［合成例２〜５］
使用する単量体の種類と量を表１に示すように変更した以外は、合成例１と同様にして、水性分散液２、３および５を得た。また、使用する単量体および界面活性剤の種類と量を表１に示すように変更した以外は、合成例１と同様にして、水性分散液４を得た。[Synthesis Examples 2 to 5]
Aqueous dispersions 2, 3 and 5 were obtained in the same manner as in Synthesis Example 1 except that the types and amounts of the monomers used were changed as shown in Table 1. Further, an aqueous dispersion 4 was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of the monomers and surfactants used were changed as shown in Table 1.
［合成例６］
真空脱気したオートクレーブ内に、ＣＴＦＥ（６２０ｇ）、ＨＢＶＥ（１２２ｇ）、ＥＶＥ（７０ｇ）、ＣＨＶＥ（３８５ｇ）、キシレン（５９０ｇ）、炭酸カリウム（１１ｇ）を撹拌下で導入して昇温し、６５℃に保持した。
続いて、オートクレーブ内に、ｔｅｒｔ−ブチルペルオキシピバレートの５質量％キシレン溶液（７０ｇ）を連続的に添加しながら１１時間重合した後、オートクレーブ内溶液をろ過し、含フッ素重合体を含む溶液を得た。
該溶液を、６５℃にて２４時間真空乾燥し、さらに１３０℃にて２０分間真空乾燥して得られるブロック状の含フッ素重合体を粉砕して、粉末状の含フッ素重合体を得た。
得られた粉末状の含フッ素重合体をメチルエチルケトンに溶解させてなるワニス（３００ｇ）に、無水コハク酸の２０質量％アセトン溶液（１６．１ｇ）および触媒としてトリエチルアミン（０．０７２ｇ）を加え、７０℃で６時間反応させた。
続いて、フラスコ内溶液にトリエチルアミン（３．２６ｇ）を加え２５℃にて２０分撹拌し、イオン交換水の１８０ｇを徐々に加えた。さらに、減圧留去し、さらにイオン交換水の９０ｇを加えて、含フッ素重合体を含む水性分散液６（固形分濃度４０質量％）を得た。なお、水に対する、アセトンとメチルエチルケトンの総含有量は０．５質量％以下であった。
水性分散液６の水酸基価は８５ｍｇＫＯＨ／ｇであり、最低造膜温度は３０℃であり、含フッ素重合体の粒子の平均粒子径は７０ｎｍであった。
なお、水性分散液６の、ＣＴＦＥに基づく単位、ＨＢＶＥに基づく単位、ＨＢＶＥに基づく単位のヒドロキシ基に無水コハク酸が付加して形成された単位（側鎖に−Ｏ（ＣＨ２）４ＯＣ（Ｏ）ＣＨ２ＣＨ２ＣＯＯＨを有する単位。以下、「ＨＢＶＥ−ＳＡ」ともいう。）、ＥＶＥに基づく単位、ＣＨＶＥに基づく単位の含有量は、この順に、５０モル％、１７モル％、３モル％、１５モル％、１５モル％であった。
合成例１〜６で得られた水性分散液１〜６の物性をまとめて、表１に示す。[Synthesis Example 6]
In a vacuum degassed autoclave, CTFE (620 g), HBVE (122 g), EVE (70 g), CHVE (385 g), xylene (590 g) and potassium carbonate (11 g) were introduced with stirring, and the temperature was raised. Held at 0C.
Subsequently, after continuously polymerizing for 11 hours while continuously adding a 5% by mass xylene solution (70 g) of tert-butylperoxypivalate into the autoclave, the solution in the autoclave was filtered to obtain a solution containing the fluoropolymer. Obtained.
The solution was vacuum-dried at 65 ° C. for 24 hours, and further vacuum-dried at 130 ° C. for 20 minutes to pulverize the block-like fluoropolymer to obtain a powdery fluoropolymer.
To a varnish (300 g) obtained by dissolving the obtained powdery fluoropolymer in methyl ethyl ketone, a 20% by mass acetone solution (16.1 g) of succinic anhydride and triethylamine (0.072 g) as a catalyst were added. The reaction was carried out at 6 ° C for 6 hours.
Subsequently, triethylamine (3.26 g) was added to the solution in the flask and stirred at 25 ° C. for 20 minutes, and 180 g of ion-exchanged water was gradually added. Further, the solvent was distilled off under reduced pressure, and 90 g of ion-exchanged water was further added to obtain an aqueous dispersion 6 (solid content concentration: 40% by mass) containing a fluoropolymer. The total content of acetone and methyl ethyl ketone with respect to water was 0.5% by mass or less.
The hydroxyl value of the aqueous dispersion 6 was 85 mgKOH / g, the minimum film-forming temperature was 30 ° C., and the average particle size of the fluoropolymer particles was 70 nm.
In addition, units formed by adding succinic anhydride to the hydroxy group of units based on CTFE, units based on HBVE, and units based on HBVE in the aqueous dispersion 6 (-O (CH2 )4 OC ( O) a unit having CH2 CH2 COOH. Hereinafter also referred to as “HBVE-SA”), the content of the unit based on EVE, and the unit based on CHVE are 50 mol%, 17 mol%, 3 mol in this order. %, 15 mol%, and 15 mol%.
The physical properties of the aqueous dispersions 1 to 6 obtained in Synthesis Examples 1 to 6 are summarized in Table 1.
［例１］
顔料（７２ｇ）、分散剤（５ｇ）、消泡剤（０．５ｇ）、およびイオン交換水（２２．５ｇ）を加えて混合し、ミルベースを得た。
次に、水性分散液１、硬化剤、造膜助剤、レベリング剤、増粘剤、および該ミルベースを、表２にしたがって混合し、水性塗料１を得た。
縦１２０ｍｍ、横６０ｍｍ、厚さ１５ｍｍのスレート板の表面に、水性セラタイトプライマー（エスケー化研社製）を、アプリケーターにて、乾燥膜厚が１０μｍになるように塗布し、８０℃で２１０秒間乾燥させて下塗り膜を形成した。
続いて、下塗り膜の表面に、水性デュフロン１００中塗り塗料（日本ペイント社製。）を、アプリケーターにて、乾燥膜厚が３０μｍになるように塗布し、８０℃で２１０秒間乾燥させて、エポキシ樹脂の塗膜を基材の表面に形成した。
最後に、該塗膜の表面に、水性塗料１を、アプリケーターにて塗布し、２５℃で６０分養生した後、８０℃で２０分乾燥させ、硬化させて、水性塗料１を硬化してなる硬化塗膜（膜厚５０μｍ）を有する硬化塗膜付き基材を得た。該硬化塗膜付き基材を試験片１として、後述の評価に供した。[Example 1]
A pigment (72 g), a dispersant (5 g), an antifoaming agent (0.5 g), and ion-exchanged water (22.5 g) were added and mixed to obtain a mill base.
Next, the aqueous dispersion 1, the curing agent, the film-forming aid, the leveling agent, the thickener, and the mill base were mixed according to Table 2 to obtain an aqueous paint 1.
An aqueous seratite primer (manufactured by SK Kaken Co., Ltd.) was applied to the surface of a slate plate having a length of 120 mm, a width of 60 mm, and a thickness of 15 mm with an applicator so that the dry film thickness was 10 μm, and at 80 ° C. for 210 seconds. An undercoat film was formed by drying.
Subsequently, an aqueous duflon 100 intermediate coating (manufactured by Nippon Paint Co., Ltd.) was applied to the surface of the undercoat film with an applicator so that the dry film thickness was 30 μm, and dried at 80 ° C. for 210 seconds to obtain an epoxy. A resin coating was formed on the surface of the substrate.
Finally, the aqueous paint 1 is applied to the surface of the coating film with an applicator, cured at 25 ° C. for 60 minutes, dried at 80 ° C. for 20 minutes, and cured to cure the aqueous paint 1. A substrate with a cured coating film having a cured coating film (film thickness 50 μm) was obtained. The substrate with a cured coating film was used as a test piece 1 for the evaluation described later.
［例２〜６］
水性分散液１を水性分散液２〜６に変更する以外は例１と同様にして、水性塗料２〜６および試験片２〜６を得、後述の評価に供した。[Examples 2 to 6]
Except having changed the aqueous dispersion 1 into the aqueous dispersions 2-6, it carried out similarly to Example 1, and obtained the aqueous coating materials 2-6 and the test pieces 2-6, and used for evaluation mentioned later.
試験片の評価方法を、以下に示す。
（硬化塗膜の基材密着性）
クロスカット法（ＪＩＳ Ｋ ５６００−５−６）によって判定した。試験板の硬化塗膜を１ｍｍ間隔１００マスの碁盤目状にカットし、その上に粘着テープを貼付し、続けてその粘着テープを剥離したときに、１００マスのうち、粘着テープによって剥離しなかったマス目の数（マス数／１００）から、以下の基準で密着性を評価した。
○：マス数が９０超である。
△：マス数が５０以上９０以下である。
×：マス数が５０未満である。The test piece evaluation method is shown below.
(Substrate adhesion of cured coating)
Determination was made by the cross-cut method (JIS K 5600-5-6). When the cured coating on the test plate is cut into a grid of 100 squares with an interval of 1 mm, an adhesive tape is pasted on it, and when the adhesive tape is subsequently peeled off, the adhesive tape does not peel off of the 100 squares. From the number of squares (number of squares / 100), the adhesion was evaluated according to the following criteria.
○: The number of cells is more than 90.
Δ: The number of cells is 50 or more and 90 or less.
X: The number of cells is less than 50.
（硬化塗膜の耐候性）
サンシャインウェザオメータ方式（ＪＩＳ Ｂ ７７５３：２００７）に準拠した促進耐候性試験機を用い、試験時間を３０００時間として促進耐候性試験をした。試験前の硬化塗膜の６０度鏡面光沢値を１００％として、試験後の硬化塗膜の６０度鏡面光沢値の保持率（光沢保持率）（％）を求め、以下の基準で評価した。なお、６０度鏡面光沢値は、光沢計（製品名「ｍｉｃｒｏ−ＴＲＩ−ｇｒｏｓｓ」、入反射角６０度、ＢＹＫ社製。）にて測定した。また、光沢保持率が高いほど、耐候性が良好である。
○：３０００時間における光沢保持率が８０％超である。
×：３０００時間における光沢保持率が８０％未満である。
評価結果を表２に示す。(Weather resistance of cured coating)
An accelerated weather resistance test was conducted using an accelerated weather resistance tester based on the sunshine weatherometer method (JIS B 7753: 2007) with a test time of 3000 hours. Taking the 60-degree specular gloss value of the cured coating film before the test as 100%, the retention rate (gloss retention ratio) (%) of the 60-degree specular gloss value of the cured coating film after the test was determined and evaluated according to the following criteria. The 60-degree specular gloss value was measured with a gloss meter (product name “micro-TRI-gross”, incident reflection angle 60 degrees, manufactured by BYK). Further, the higher the gloss retention, the better the weather resistance.
A: The gloss retention at 3000 hours is more than 80%.
X: Gloss retention at 3000 hours is less than 80%.
The evaluation results are shown in Table 2.
表１および表２に示すように、例１および例２で使用した、水酸基価が１５〜５０ｍｇＫＯＨ／ｇ、最低造膜温度が５〜４０℃である含フッ素重合体の粒子を含む水性塗料の硬化塗膜は、割れや剥がれが生じにくく、耐候性に優れる硬化塗膜を形成することが示された。 As shown in Tables 1 and 2, the water-based paint containing fluoropolymer particles having a hydroxyl value of 15 to 50 mg KOH / g and a minimum film-forming temperature of 5 to 40 ° C. used in Examples 1 and 2. It was shown that the cured coating film forms a cured coating film that hardly breaks or peels off and has excellent weather resistance.
| Application Number | Priority Date | Filing Date | Title |
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| JP2017045016AJP2018145375A (en) | 2017-03-09 | 2017-03-09 | Fluorine-based aqueous coating |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017045016AJP2018145375A (en) | 2017-03-09 | 2017-03-09 | Fluorine-based aqueous coating |
| Publication Number | Publication Date |
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| JP2018145375Atrue JP2018145375A (en) | 2018-09-20 |
| Application Number | Title | Priority Date | Filing Date |
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| JP2017045016APendingJP2018145375A (en) | 2017-03-09 | 2017-03-09 | Fluorine-based aqueous coating |
| Country | Link |
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| JP (1) | JP2018145375A (en) |
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