Embodiment
Illustrated below for embodiments of the present invention.
[adherence composition]
The adherence composition (hereinafter referred to as " adherence composition P ") of present embodiment contains active energy ray-curableAdhesion composition and organic fine particles.Active energy ray-curable adhesion composition contains (methyl) acrylate polymer, active-energyLine curability compound and crosslinking agent.In addition, the refractive index of organic fine particles is 1.50~2.00, active energy ray-curable gluesThe poor absolute value for the refractive index of composition and the refractive index of organic fine particles is 0.02~0.50.
In the adherence composition P of present embodiment, the refractive index of organic fine particles is larger, in addition, active energy line curingProperty adhesion composition refractive index and organic fine particles refractive index absolute value it is poor larger.Therefore, by adherence composition P,High light diffusivity can be achieved.Particularly, in the case of adhering agent layer of the utilization adherence composition p-shaped into thickness of thin,Also high light diffusivity can fully be realized.Further, since the required organic fine particles for realizing desired light diffusivity can be reducedAmount, so can suppress because add organic fine particles cause the problem of durability is reduced.In addition, adherence composition P is solidifiedFormed by sticker, pass through by active energy ray irradiation formed active energy ray-curable compound stereoscopic graticuleIn structure, capture by the way that (methyl) acrylate polymer of cross-linked structure is reacted and be formed with crosslinking agent, and show heightCoagulability.Reduction and high coagulability by the usage amount of such a organic fine particles, can be achieved excellent durability.In addition,Possess the optical module for the adhering agent layer that this utilization adherence composition P is formed, particularly polarizer, with sufficiently resistance toLong property, and light diffusivity is excellent.
The composition 1. active energy ray-curable is adhered
Adherence composition P contains active energy ray-curable adhesion composition, active energy ray-curable adhesion compositionContain (methyl) acrylate polymer (A), active energy ray-curable compound (B) and crosslinking agent (C).In addition, this theoryIn bright book, (methyl) acrylate refers to acrylate and (methyl) both acrylate, and other similar terms are also identical.In addition, also including the concept of " copolymer " in " polymer ".
As previously described, when the sticker containing organic fine particles being used for into the optical modules such as polarizer, can often occur durabilityThe problems such as.But in the present embodiment, by making adherence composition P contain above-mentioned active energy ray-curable adhesion composition,Making the durability of obtained sticker becomes excellent.In addition, the usual coagulability reduction of sticker containing organic fine particles, from adhesionWhen oxidant layer peels off stripping film, the situation that adhering agent layer sticks at stripping film side occurs sometimes.But it is above-mentioned containing active energy ray by makingThe adherence composition P solidifications of curability adhesion composition, are not susceptible to above mentioned problem, the operability change of the adhering agent layer obtainedObtain excellent.
(1) (methyl) acrylate polymer
(methyl) acrylate polymer (A), the carbon number for preferably comprising alkyl is 1~20 (methyl) alkyl acrylateBase ester is used as the monomer for constituting the polymer.Thus, the sticker of acquisition can embody excellent adherence.In addition, (methyl) thirdOlefine acid ester polymer (A) is preferably (methyl) alkyl acrylate of the carbon number 1~20 of alkyl, with reactive functional groupsMonomer (monomer containing reactive functional groups) and the copolymer according to required used other monomers.By making (methyl)Acrylate polymer (A) contains the monomer containing reactive functional groups as the monomer for constituting the polymer, can improve and liquid crystalThe adaptation of the glass surfaces such as unit, in addition, also cross-linked structure can be formed with crosslinking agent described later (C) reaction.
(methyl) alkyl acrylate for being 1~20 as the carbon number of alkyl, can include (methyl) acrylic acid firstEster, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester,(methyl) the just own ester of acrylic acid, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid positive last of the ten Heavenly stemsEster, positive ten diester of (methyl) acrylic acid, (methyl) myristyl ester, (methyl) acrylic acid palm ester, (methyl) acrylic acidOctadecyl ester etc..Wherein, from the angle for improving adherence, preferably the carbon number of alkyl is 1~8 (methyl) alkyl acrylateBase ester, more preferably (methyl) n-butyl acrylate or (methyl) 2-EHA.In addition, these (methyl) acrylic acidArrcostab can be used alone a kind, and two or more also can be combined and uses.
(methyl) acrylate polymer (A) preferably comprises 50~99 mass %, further preferably 65~97 mass %, spyThe carbon number for not preferably comprising 80~95 mass % alkyl gathers for 1~20 (methyl) alkyl acrylate as this is constitutedThe monomeric unit of compound.
As the above-mentioned monomer containing reactive functional groups, preferably including intramolecular has the monomer (hydroxyl of hydroxylMonomer), the intramolecular monomer (carboxyl group-containing monomer) and intramolecular with carboxyl there is monomer (emulsion stability) of amino etc..These monomers containing reactive functional groups can be used alone a kind, and two or more also can be combined and uses.
As hydroxyl monomer, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (first can be includedBase) acrylic acid 3- hydroxypropyl acrylates, (methyl) acrylic acid 2- hydroxy butyl esters, (methyl) acrylic acid 3- hydroxy butyl esters, (methyl) acrylic acid 4- hydroxylsButyl ester etc. (methyl) acrylic acid hydroxy alkyl ester.Wherein, from the hydroxyl in (methyl) acrylate polymer (A) obtained and friendshipConnection agent (C) reactivity and set out with the angle of the copolymerizable of other monomers, preferably (methyl) acrylic acid 2- hydroxyl ethyl esters or(methyl) acrylic acid 4- hydroxy butyl esters.These hydroxyl monomers can be used alone a kind, and two or more also can be combined and uses.
As carboxyl group-containing monomer, acrylic acid, methacrylic acid, crotonic acid, maleic acid, Yi Kang acid, burnt lemon can be includedThe ethylenically unsaturated carboxylic acids such as acid.Wherein, from the carboxyl in (methyl) acrylate polymer (A) obtained and crosslinking agent (C)Reactivity, and set out with the angle of the copolymerizable of other monomers, preferably acrylic acid.These carboxyl group-containing monomers can be used alone1 kind, two or more also can be combined and uses.
As emulsion stability, (methyl) acrylate, (methyl) acrylic acid n-butyl amine base ethyl ester can be includedDeng.These emulsion stabilities can be used alone a kind, and two or more also can be combined and uses.
As the monomer containing reactive functional groups, hydroxyl monomer and carboxyl group-containing monomer are preferably used simultaneously, particularly preferablyUse acrylic acid simultaneously.In this case, as crosslinking agent described later (C), isocyanates crosslinking agent is preferably used.Due to containingThe reactivity of carboxylic monomer and isocyanates crosslinking agent is high, can turn into the crosslinking points of (methyl) acrylate polymer (A).SeparatelyOn the one hand, carboxyl group-containing monomer, particularly acrylic acid, while the bonding force of the sticker obtained is improved, can also improve glassChange transition temperature to improve coagulability.In addition, carboxyl group-containing monomer, particularly acrylic acid also have and promoted from hydroxyl monomerThe effect of cross-linking reaction between hydroxyl and isocyanates crosslinking agent.
(methyl) acrylate polymer (A) preferably comprises 1~25 mass %, particularly preferably contains 2~15 mass %, entersOne step preferably comprises 3~10 mass % monomer containing reactive functional groups as the monomeric unit for constituting the polymer.SameWhen using in the case of hydroxyl monomer and carboxyl group-containing monomer, preferably comprise 0.05~20 mass %, particularly preferably containing 0.1~10 mass %, further preferably 0.2~2 mass % hydroxyl monomer.Furthermore it is preferred that containing 0.5~20 mass %, spy1~10 mass %, further preferably 2~8 mass % carboxyl group-containing monomer is not preferably comprised.
As above-mentioned other monomers, (methyl) acrylic acid methoxy ethyl ester, (methyl) acrylic acid ethoxy ethyl ester etc. can be included(methyl) alkoxyalkyl acrylate, (methyl) cyclohexyl acrylate etc. has (methyl) acrylate of aliphatic ring, thirdThe acrylamide of the non-crosslinked property such as acrylamide, Methacrylamide, (methyl) acrylic acid N, N- dimethylaminoethyl, (methyl) thirdOlefin(e) acid N, N- dimethylamino propyl ester etc. has (methyl) acrylate of the tertiary amino of non-crosslinked property, vinyl acetate, styreneDeng.These monomers can be used alone a kind, and two or more also can be combined and uses.
The polymerization state of (methyl) acrylate polymer (A) can be random copolymer, or block copolymer.ThisOutside, due to (methyl) acrylate polymer (A) to assign the composition of adherence, therefore preferably do not have active energy line curingProperty.
The weight average molecular weight of (methyl) acrylate polymer (A) is preferably 400,000~2,500,000, particularly preferably 1,000,000~220 ten thousand, more preferably 1,400,000~2,000,000.By make the weight average molecular weight of (methyl) acrylate polymer (A) compared withHeight, can make durability more excellent.In addition, the weight average molecular weight in this specification, to be surveyed by gel permeation chromatography (GPC) methodFixed polystyrene scaled value.
In addition, in adherence composition P, (methyl) acrylate polymer (A) can be used alone a kind, 2 kinds are also can be combinedIt is used above.
(2) active energy ray-curable compound
The active energy ray-curable compound contained by active energy ray-curable adhesion composition in present embodiment(B), as long as active energy ray-curable adhesion composition and organic fine particles containing the active energy ray-curable compound (B)The absolute value of refringence can be any of monomer, oligomer or polymer in the scope, orThe mixture of these materials.The molecular weight excellent with the intermiscibility of (methyl) acrylate polymer (A) etc. can wherein be includedFor less than 1000 polyfunctional acrylic ester class monomer.
In adherence composition P in present embodiment, pass through the irradiation of active energy ray, active energy ray-curableCompound (B) forms mutually chemical bond, and then generates space network.In addition, in the structure, by capturing (methyl) acrylic acidEster polymer (A), can improve coagulability, as a result, durability becomes excellent.
As the polyfunctional acrylic ester class monomer that molecular weight is less than 1000, BDO two (methyl) can be includedAcrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl)Acrylate, neopentyl glycol adipic acid two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylic acidIt is ester, bicyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modifiedDi(2-ethylhexyl)phosphate (methyl) acrylate, two (acryloyl-oxyethyl) isocyanuric acid esters, allylation cyclohexyl two (methyl) propyleneThe functional-type of acid esters etc. two；Trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid changeProperty dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trihydroxy methyl thirdAlkane three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters, 6-caprolactone are modified 33 (2- (methyl) propyleneTrimethylammonium) the trifunctional type such as isocyanuric acid ester；Two glycerine four (methyl) acrylate, new penta tetrol four (methyl) acrylic acidThe tetrafunctional type such as ester；Propionic acid is modified five functional-types such as dipentaerythritol five (methyl) acrylate；Dipentaerythritol six (methyl)Six functional-types such as acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..These polyfunctional acrylic estersClass monomer can be used alone a kind, and two or more also can be combined and uses.
The content of active energy ray-curable compound (B) is relative to the mass of (methyl) acrylate polymer (A) 100Part, preferably 1~50 mass parts, particularly preferably 5~30 mass parts, more preferably 10~20 mass parts.By making workWithin the above range, the durability of the sticker obtained becomes more excellent to the content of property energy ray-curable compound (B),And the operability of the adhering agent layer obtained becomes more excellent.In addition, can also maintain (methyl) acrylic ester polymerization wellThe adherence that thing (A) is brought.
(3) crosslinking agent
In adherence composition P in present embodiment, active energy ray-curable adhesion composition contains crosslinking agent (C).Included in adherence composition P adhesion composition：Contain the monomer containing reactive functional groups as the monomer list for constituting polymerIn the case of (methyl) acrylate polymer (A) and crosslinking agent (C) of member, if adherence composition P is heated etc., hand overThe reactive functional groups for joining monomer containing reactive functional groups of agent (C) meeting with constituting (methyl) acrylate polymer (A) are anti-Should.Thus, by the structure of crosslinking agent (C) (methyl) acrylate polymer (A) formation crosslinking, obtained sticker is improvedCoagulability.
In addition, in adherence composition P in present embodiment, passing through above-mentioned active energy ray-curable compound(B) it can expect that the coagulability of the sticker obtained is improved, durability is improved.In addition, by using crosslinking agent (C), can tie up simultaneouslyThe appropriate bonding force of sticker is held, while further improving coagulability, durability is become more excellent.
As crosslinking agent (C), as long as the reactive functional groups reaction having with (methyl) acrylate polymer (A) is i.e.Can, it can such as enumerate：Isocyanates crosslinking agent, epoxies crosslinking agent, amine cross-linking agent, melamine class crosslinking agent, nitrogen thirdPyridine class crosslinking agent, hydrazine class crosslinking agent, aldehyde crosslinking agent, oxazoline class crosslinking agent, metal alkoxide class crosslinking agent, metallo-chelateClass crosslinking agent, metallic salt crosslinking agent, ammonium salt class crosslinking agent etc..There is hydroxyl conduct in (methyl) acrylate polymer (A)In the case of reactive functional groups, in above-mentioned crosslinking agent, the isocyanates crosslinking agent excellent with hydroxyl reactive is preferably used.In addition, crosslinking agent (C) can be used alone a kind, two or more also can be combined and uses.
Isocyanates crosslinking agent comprises at least polyisocyanate compounds.As polyisocyanate compounds, it can enumerateGo out the aromatic poly-isocyanates such as toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, eylylene diisocyanate；SixThe aliphatic polymeric isocyanates such as the aliphatic such as methylene diisocyanate；IPDI, hydrogenated methylene diphenyld twoEster ring type PIC such as isocyanates etc., and the biuret bodies of these materials, isocyanuric acid ester body or with ethylene glycol,Addition product of reactant of the active dydrogen compounds containing low molecule such as propane diols, neopentyl glycol, trimethylolpropane, castor oil etc..Wherein, from the reactive angle with hydroxyl, preferably trimethylolpropane modified aromatic adoption isocyanates, particularly preferred threeHydroxymethyl-propane modified toluene diisocyanate.
The content of crosslinking agent (C) is relative to the mass parts of (methyl) acrylate polymer (A) 100, preferably 0.01~10Mass parts, particularly preferably 0.05~5 mass parts, more preferably 0.1~1 mass parts.
(4) various additives
Active energy ray-curable adhesion composition can contain various additives according to demand, for example：Light trigger, silane are evenJoin agent, refractive index adjusters, antistatic additive, tackifier, antioxidant, ultra-violet absorber, light stabilizer, softening agent, fillingAgent etc..
In the case of using ultraviolet as the active energy ray for solidifying adherence composition P, active energy ray is solidIt is preferable that the property changed adhesion composition preferably comprises light trigger.By containing light trigger, active energy ray-curable can be allowed to adhere intoDivide and efficiently solidify, in addition, can also reduce the exposure of polymerizing curable time and active energy ray.
As light trigger, styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, styrax can be includedN-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethylsEpoxide -2- phenyl acetophenones, 2- hydroxy-2-methyl -1- phenylpropyl alcohol alkane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- methyl isophthalic acids-[4-(methyl mercapto) benzene] -2- morpholines-propane -1- ketone, 4- (2- hydroxyls ethoxy) phenyl -2- (hydroxyl -2- propyl group) ketone, benzophenone, to benzeneBase benzophenone, 4,4 '-lignocaine benzophenone, dichloro benzophenone, 2- first anthraquinone, 2- second anthraquinone, the tertiary fourth anthraquinones of 2-, 2-Ammonia anthraquinone, 2- methyl mercaptos xanthone, 2- ethylmercapto groups xanthone, 2- chlorine sulfenyls xanthone, 2,4- dimethyl sulphur-baseds xanthone, 2,4- bis-Ethylmercapto group xanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, to dimethylamino benzoin ester, widow [2- hydroxyls -2-Methyl isophthalic acid [4- (1- methyl ethylenes) benzene] acetone], 2,4,6- trimethylbenzoy-diphenies-phosphine oxide etc..These lightInitiator can be used alone a kind, and two or more also can be combined and uses.
Relative to the mass parts of active energy ray-curable compound (B) 100 in active energy ray-curable adhesion composition,It is preferred that using light trigger with the amount of the scope of 0.1~20 mass parts, particularly preferably used with the amount of the scope of 1~12 mass partsLight trigger.
In addition, from angle of the obtained sticker for the bonding force of glass surface etc. is improved, active energy ray is solidThe property changed adhesion composition preferably comprises silane coupler.As silane coupler, it is that intramolecular has at least one alcoxyl silicon substrateOrgano-silicon compound, preferably with adhere composition intermiscibility it is good and have excellent translucency silane coupler.
As this silane coupler, vinyltrimethoxy silane, VTES, methyl can be includedThe silicon compound containing polymerism unsaturated group such as acryloxypropyl trimethoxy silane；3- glycidoxypropyl group front threesThe silicon compounds containing epoxy construction such as TMOS, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane；3- sulfydryls thirdBase trimethoxy silane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi dimethoxymethylsilanes etc. contain sulfydrylSilicon compound；3- TSL 8330s, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- ammoniaBase ethyl) silicon compound containing amino such as -3- amino propyl methyl dimethoxysilanes；3- r-chloropropyl trimethoxyl silanes,3- isocyanates propyl-triethoxysilicanes, or it is at least one of above-mentioned with MTES, ethyl triethoxy silicaneCondensation product of the silicon compounds containing alkyl such as alkane, MTMS, ethyl trimethoxy silane etc..These silane couplersIt can be used alone a kind, two or more also can be combined and uses.
The content of silane coupler is relative to the mass parts of (methyl) acrylate polymer (A) 100, preferably 0.01~10Mass parts, particularly preferably 0.05~5 mass parts, more preferably 0.1~1 mass parts.
2. organic fine particles
The refractive index of organic fine particles contained by the adherence composition P of present embodiment is 1.50~2.00, is preferably1.52~1.80, particularly preferably 1.54~1.65.By making above-mentioned refractive index be more than 1.50, even if being film sticker,Also sufficient light diffusivity can be assigned in the case where not damaging durability.On the other hand, in above-mentioned refractive index more than 2.00In the case of, because the reflection of particle interface can become too much, there is the possibility for making optical characteristics be deteriorated.
As the organic fine particles for meeting above-mentioned refractive index, acrylic resin, polystyrene resin, polyethylene tree can be includedOrganic translucency particulate such as fat, epoxy resin etc.；As acrylic resin particulate, the equal of methyl methacrylate can be includedPolymers or the monomer such as methyl methacrylate and vinyl acetate, styrene, methacrylate, (methyl) ethyl acrylateThe particulate that copolymer etc. is formed.Wherein, as organic fine particles, preferably acrylic resin particulate, particularly preferably by including firstThe particulate that base methyl acrylate is formed as the polymer of structures alone unit, further preferably by methyl methacrylate and benzeneThe particulate of the copolymer formation of ethene.Because this particulate readily satisfies above-mentioned refractive index, therefore suitably.Above organic fine particles can1 kind is used alone, two or more also can be combined and uses.
It is used as the shape of organic fine particles, the preferably uniform spheroidal particle of light diffusion.Organic fine particles pass through centrifugal sedimentation lightThe average grain diameter that saturating method is obtained is preferably 0.5~10 μm, particularly preferably 1.0~4.0 μm, more preferably 1.2~2.5 μm.It is less than 10 μm by making the average grain diameter of organic fine particles, is being applicable the light with adhering agent layer of the sticker obtainedLearn in component, fineness becomes more excellent.On the other hand, it is more than 0.5 μm by the average grain diameter for making organic fine particles, can obtainsObtain sufficient light diffusivity.
In addition, for the average grain diameter obtained above by centrifugal sedimentation light transmission method, it is by 1.2g particulates and 98.8g isopropylsAlcohol be sufficiently stirred for after material as test sample, using telecentricity decanter type particle size analyzer (Horiba, Ltd. are manufactured,CAPA-700) it is measured.
Organic fine particles content in adherence composition P is relative to the above-mentioned active energy ray-curable adhesion matter of composition 100Measure part, more preferably preferably 1~30 mass parts, particularly preferably 2~15 mass parts, 4~9 mass parts.This embodiment partyIn the adherence composition P of formula, active energy ray-curable adhesion composition refractive index and organic fine particles refractive index it is poorAbsolute value is larger.Therefore, even if the content of organic fine particles is few, sufficient light diffusivity can also be realized.Further, since can reduceContent, therefore can suppress the problem of the durability caused by adding organic fine particles is reduced, and then realize excellent durability.
3. refringence
The poor absolute value of the refractive index of active energy ray-curable adhesion composition and the refractive index of organic fine particles is 0.02~0.50, preferably 0.04~0.20, particularly preferably 0.06~0.10.Adhered into by active energy ray-curable like thisPoint and organic fine particles refringence absolute value it is larger, high light diffusivity can be realized with a small amount of addition.ParticularlyIn the case of adhering agent layer of the use adherence composition p-shaped into thickness of thin, sufficient high light diffusivity can be also realized.Further, since the amount of the required organic fine particles for light diffusivity needed for realizing can be reduced, therefore it can suppress because being added withDurability reduction caused by machine particulate, and then realize excellent durability.
In addition, the refractive index of active energy ray-curable adhesion composition is preferably 1.40~1.55, particularly preferably 1.42~1.50, more preferably 1.44~1.49.
Here, the refractive index of active energy ray-curable adhesion composition is uses Abbe refractometer, using JIS K0062 as baseThe numerical value that standard is determined.Further, since the refractive index of active energy ray-curable adhesion composition is constant before and after its solidification, becauseThis, can use the numerical value determined before its solidification, also can use the numerical value determined after its solidification.On the other hand, the folding of organic fine particlesPenetrate shown in the test example of rate as be described hereinafter, for the numerical value determined using refractive index titer.
4. the preparation method of adherence composition
Adherence composition P can be by by (methyl) acrylate polymer (A), active energy ray-curable compound(B), crosslinking agent (C) and organic fine particles are mixed and prepared.For example, (methyl) acrylate polymer (A) can be first prepared, thenBlended by active energy ray-curable compound (B), crosslinking agent (C) and organic fine particles and according to required additive,Prepare adherence composition P.
(methyl) acrylate polymer (A) can pass through：Using common radical polymerization, the list to constituting polymerThe mixture of body unit is polymerize and prepared.The polymerization of (methyl) acrylate polymer (A), can be according to demand using polymerizationInitiator, is acted on etc. by polymerisation in solution and carried out.As polymer solvent, ethyl acetate, n-butyl acetate, acetic acid can be included differentButyl ester, toluene, acetone, hexane, MEK etc., two or more can be also used simultaneously.
As polymerization initiator, azo compound, organic peroxide etc. can be included, also can simultaneously using 2 kinds withOn.Azo compound, can include 2,2'- azobis isobutyronitriles, 2,2'- azos double (2- methylbutyronitriles), 1,1'- azos double(hexamethylene 1- formonitrile HCNs), 2,2'- azos double (2,4- methyl pentane nitriles), the double (2,4- dimethyl -4- methoxyl groups penta of 2,2'- azosNitrile), dimethyl 2,2'- azos double (2- methyl propionates), 4,4'- azos double (the positive valeric acids of 4- cyano group), double (the 2- hydroxyls of 2,2'- azosYlmethyl propionitrile), 2,2'- azos double [2- (2- imidazoline -2- bases) propane] etc..
As organic peroxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, hydrogen peroxide isopropyl can be includedBenzene, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxide two carbonic acid two (2- ethoxyethyl groups) ester, mistakeAoxidize the neodecanoic acid tert-butyl ester, tert-Butyl peroxypivalate, peroxidating (3,5,5- front threes hexanoyl), dipropyonyl peroxide, peroxideChange diacetyl etc..
In addition, in above-mentioned polymerization process, obtained polymer can be adjusted by blending the chain-transferring agents such as 2- mercaptoethanolsWeight average molecular weight.
Obtain after (methyl) acrylate polymer (A), by being added to the solution of (methyl) acrylate polymer (A)Active energy ray-curable compound (B), crosslinking agent (C) and organic fine particles and according to required addition additive, it is fully mixedClose, be derived from forming adherence composition P (coating solution) through solvent dilution.
As the retarder thinner that coating solution is prepared for diluting adherence composition P, hexane, heptane, ring can be includedThe aliphatic hydrocarbons such as hexane；The aromatic hydrocarbons such as toluene, dimethylbenzene；The halogenated hydrocarbons such as dichloromethane, dichloroethanes；Methanol, ethanol, thirdThe alcohol such as alcohol, butanol, 1- methoxy-2-propanols；The ketone such as acetone, MEK, 2 pentanone, isophorone, cyclohexanone；Ethyl acetate,The esters such as butyl acetate；Cellosolve type solvents such as ethyl cellosolve etc..
As the concentration and viscosity according to the above-mentioned coating solution being prepared from, as long as in the scope that can be coatedThere is no particular restriction, according to circumstances can suitably select.For example, using adherence composition P concentration as 10~40 mass %'sMode is diluted.In addition, when obtaining coating solution, retarder thinner not necessarily condition is added, if adherence composition P is canThe viscosity being coated, also can be without retarder thinner etc..
[sticker]
The sticker of present embodiment is formed by solidifying adherence composition P, needed for adherence composition P is coated onObject and make its dry after, by the irradiation of active energy ray make adherence composition P solidify, preferable adhesion can be obtainedAgent.
Though adherence composition P drying can be by air-drying progress, generally by heating (preferably heated-air drying)Carry out.In the case where being heated, heating-up temperature is preferably 50~150 DEG C, particularly preferably 70~120 DEG C.In addition,Heat time is preferably 10 seconds~10 minutes, particularly preferably 50 seconds~2 minutes.
As active energy ray, generally using ultraviolet, electron beam etc..Though the exposure of active energy ray is according to energyThe species of line and it is different, but for example using in the case of ultraviolet, light quantity is preferably 50~1000mJ/cm2, particularly preferably100~500mJ/cm2.In addition, in the case of using electron beam, preferably 10~1000krad or so.
In adherence composition P active energy ray-curable adhesion composition, by adherence composition P drying (plusHeat treatment), (methyl) acrylate polymer (A) is crosslinked by crosslinking agent (C) and is formed cross-linked structure.In addition, by rightAdherence composition P irradiates active energy ray, and the formation connected to each other of multiple active energy ray-curable compounds (B) is solid nettedStructure, thus it is speculated that (methyl) acrylate polymer that capture is crosslinked by crosslinking agent (C) in the space network(A)。
[adhesive sheet]
As shown in figure 1, the adhesive sheet 1A of first embodiment since lower successively by stripping film 12, be laminated in stripping film 12Release surface adhering agent layer 11 and be laminated in the base material 13 of adhering agent layer 11 and constitute.
In addition, as shown in Fig. 2 the adhesive sheet 1B of second embodiment is by 2 stripping film 12a, 12b and adhering agent layer11 are constituted, and the adhering agent layer 11 is held in the way of the release surface with this 2 stripping film 12a, 12b is contacted this 2Between stripping film 12a, 12b.In addition, the release surface of the stripping film in this specification refers to, the face in stripping film with fissility,Even if including implementing the face of lift-off processing and lift-off processing is not carried out but showing any of the face of fissility.
In any adhesive sheet 1A, 1B, adhering agent layer 11 is by above-mentioned by the way that adherence composition P solidifiedSticker is formed.
The thickness of adhering agent layer 11 can suitably determine according to adhesive sheet 1A, 1B application target, but from realizing adhesive sheetThe angle of 1A, 1B filming and excellent durability and light diffusivity is set out, preferably 1~50 μm, more preferably 3~20μm, in addition, along with the angle from fineness, particularly preferably 5~15 μm.As described earlier, present embodimentBy the way that the adherence composition P stickers solidified are contained into organic fine particles, while showing high coagulability.Therefore, adhereEven if the thickness of oxidant layer 11 is thin, excellent durability can be also realized.That is, by the adherence composition P of present embodiment, it can obtainThere must be the adhering agent layer of the film of excellent light diffusivity and durability.
As base material 13, there is no particular restriction, and the base material used generally as the substrate sheets of adhesive sheet can be used.ExampleSuch as, in addition to required optical module, the spinning cloth or non-woven fabrics of the fibers such as artificial silk, acrylic acid, polyester are used；Glazed printing paper,The stationeries such as glassine paper, dipping paper, coating paper；The metal foils such as aluminium, copper；The foaming bodies such as polyurethane foaming body, foam polyethylene；It is poly-The polyester films such as PETP film, polybutylene terephthalate film, PEN film；Polyethylene film,The polyolefin films such as polypropylene screen；The cellulose membranes such as cellulose triacetate；Polychloroethylene film, polyvinylidene chloride film, polyvinyl alcoholFilm, vinyl-vinyl acetate copolymer film, polyurethane film, polystyrene film, polycarbonate membrane, acrylic resin film, norborneolThe plastic foils such as vinyl resin film, cycloolefin resin film, layered product of two or more these film etc..Plastic foil can pass through uniaxial tension,It may also pass through biaxial stretch-formed.
As optical module, polarizer (polarizing coating), polarizer, polarizer (phase retardation film), visual angle benefit can be includedRepay film, brightness and improve film, contrast raising film, liquid crystalline polymer film, diffusion barrier, Transflective film etc..Wherein, due to polarizer(polarizing coating) shrinks easily and change in size is big, from the angle of durability, is suitable as being formed the adhesion of present embodimentThe object of agent (above-mentioned adhering agent layer 11).
Although the thickness of base material 13 is different according to species, such as in the case of optical module, usually 10~500 μM, particularly preferably preferably 50~300 μm, 80~150 μm.
As stripping film 12,12a, 12b, polyethylene film can be included, polypropylene screen, polybutene film, polybutadiene film, poly-Methylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, PEN film,Polybutylene terephthalate film, polyurethane film, ethane-acetic acid ethyenyl ester film, ionomer resin film, ethene-(methyl) propyleneAcid copolymer film, ethene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyimide film, fluorine treeAdipose membrane etc..In addition, it is also possible to use the cross linking membrane of these films.The stacked film of further or these films.
It is preferred that implementing lift-off processing in the release surface (face particularly contacted with adhering agent layer 11) of above-mentioned stripping film.MakeFor the remover used in lift-off processing, can include alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, TPO,The remover of wax class.Peeled off furthermore it is preferred that a stripping film in stripping film 12a, 12b is set into the big re-release type of peeling forcePiece, another stripping film is set to the small light exfoliated stripping film of peeling force.
Though it is not particularly limited for stripping film 12,12a, 12b thickness, usually 20~150 μm or so.
It is coated and dried molten comprising adherence composition P in the release surface of stripping film 12 when manufacturing above-mentioned adhesive sheet 1AAfter liquid (coating solution), the film layer for forming adhesion agent composition P, the laminated substrate 13 on the film layer.Also, by acrossStripping film 12 solidifies it above-mentioned film layer irradiation active energy ray, is consequently formed adhering agent layer 11.In addition, active energy rayIrradiation condition is as hereinbefore.
In addition, when manufacturing above-mentioned adhesive sheet 1B, it is coated and dried in the stripping film 12a (or 12b) of side release surfaceAbove-mentioned adherence composition P coating solution is included, after the film layer for forming adherence composition P, is laminated on the film layerThe stripping film 12b (or 12a) of the opposing party.Also, by irradiating active energy to above-mentioned film layer across stripping film 12a (or 12b)Amount line solidifies it, is consequently formed adhering agent layer 11.
In addition, can be substituted with following methods as described above across stripping film irradiation active energy ray formation adhering agent layer11：Adherence composition P film layer is formed on stripping film, in the film layer to irradiate active-energy in the state of exposedLine, is formed after adhering agent layer 11, laminated substrate or stripping film on the adhering agent layer 11.Further, can also be straight on base materialThe film layer to form adherence composition P is connect, active energy ray is irradiated to the film layer, adhering agent layer 11 is formed.
As the method for being coated with above-mentioned coating solution, it can include using scraper rubbing method, scraper for coating method (knifeCoating method), rolling method, scraping blade rubbing method (blade coating method), die coating methods (dieCoating method), gravure coating process etc..
The bonding force of the adhesive sheet of present embodiment, the bonding force preferably for alkali-free glass is 0.5~20N/25mm, specialYou Xuanwei not 1~15N/25mm, more preferably 3~more than 10N/25mm.In addition, herein so-called bonding force refer toJIS Z0237:180 ° of peel adhesions (peeling rate 300mm/min) on the basis of 2009, are pasted on adherend,0.5MPa, at 50 DEG C after pressurization 20 minutes, it is measured after standing 24 hours under conditions of 23 DEG C, 50%RH.By making bondingPower within the above range, can be prevented from floating or peeled off when suitable for optical modules such as polarizers.
The transmission definition (image definition) of adhering agent layer in the adhesive sheet of present embodiment, by 0.125mm,In the case that the transmission definition total value of the light comb of 0.25mm, 0.5mm, 1.0mm and 2.0mm comb width is represented, preferably 200~500%, particularly preferably 290~490%, more preferably 400~480%.Adhering agent layer thickness now, be, for example,5~15 μm.In addition, transmission definition herein refers to JIS K7374:Measured transmission is clear on the basis of 2007 transmission beam methodDegree.
The haze value of adhering agent layer in the adhesive sheet of present embodiment is (with JIS K7136:Determined on the basis of 2000Numerical value) it is preferably 20~95%, particularly preferably 40~90%, more preferably 50~85%.By making haze value upperIn the range of stating, the sticker of present embodiment can take into account light diffusivity and fineness.Adhering agent layer thickness now, be, for example,5~15 μm.
Herein, for example, manufacture be made up of liquid crystal cells and polarizer liquid crystal display device when, using polarizer as viscousPiece 1A base material 13, adhesive sheet 1A stripping film 12 is peeled off, exposed adhering agent layer 11 and liquid crystal cells of fitting.
In addition, for example, being used as the liquid crystal display device for manufacturing the poor plate of the configuration phase between liquid crystal cells and polarizerOne example, first, the stripping film 12a (or 12b) of an adhesive sheet 1B side is peeled off, by adhesive sheet 1B exposed stickerLayer 11 is fitted with polarizer.Then, the stripping film 12 for having used polarizer as the adhesive sheet 1A of base material 13 is peeled off, will be viscousThe exposed adhering agent layer 11 for piece 1A is fitted with above-mentioned polarizer.Further, from above-mentioned adhesive sheet B adhering agent layer 11The stripping film 12b (or 12a) of the opposing party is peeled off, adhesive sheet B exposed adhering agent layer 11 is fitted with liquid crystal cells.
Adhesive sheet 1A, 1B more than, can obtain can play the optics group of excellent light diffusivity by adhering agent layer 11Part.Further, since the morphological stability of adhering agent layer 11 is very excellent, such as, thus it is speculated that even in the bonding suitable for polarizerIn the case of, the deformation that adhering agent layer 11 suppresses polarizer can also be used, and then play high-durability.Thus, even in byUnder the environment for accumulating heat, the excellent light diffusivity of optical module and excellent ageing stability can be also assigned.
Embodiments described above, is to be recorded for the ease of understanding the present invention, is not intended to limit implementation of the present inventionScope.Therefore, all design alterations or equivalent belonged in the technical scope of each element described in above-mentioned embodimentThing, is belonged in the range of patent of the present invention covers.
For example, adhesive sheet 1A stripping film 12 can be omitted, appointing in stripping film 12a, 12b in adhesive sheet 1B can be also omittedOne.