CN102639663A

CN102639663A - Adhesive agent, adhesive agent for optical member, optical member having adhesive layer attached thereto, image display device, active-energy-ray- and/or heat-curable adhesive agent composition, and adhesive agent composition

Info

Publication number: CN102639663A
Application number: CN2011800047727A
Authority: CN
Inventors: 铃木秀昭; 高木圣子; 三谷直也; 堀家浩史
Original assignee: Nippon Synthetic Chemical Industry Co Ltd
Current assignee: Mitsubishi Kasei Corp
Priority date: 2010-01-21
Filing date: 2011-01-20
Publication date: 2012-08-15
Anticipated expiration: 2031-01-20
Also published as: TW201134905A; TWI494403B; KR101766934B1; KR20120124394A; CN104046281A; CN104046281B; CN102639663B; WO2011090090A1

Abstract

Disclosed is an adhesive agent produced by curing an adhesive agent composition [I] with an active energy ray and/or heat, wherein the adhesive agent composition [I] comprises an acrylic resin (A), an aromatic compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated compound (C) having at least two ethylenically unsaturated groups, and wherein the adhesive agent is characterized in that the content of the component (B) is 3 to 300 parts by weight relative to 100 parts by weight of the component (A) and the ratio (mol%) of the content of the component (B) to the total content of the components (B) and (C) is more than 50 mol%. The adhesive agent enables the production of a liquid crystal display device in which an adhesive layer produced by curing the adhesive agent with an active energy ray and/or heat can have excellent handling properties (tack) and optical properties (haze), an optical laminate (particularly an optical member such as a polarizing plate) can be adhered to a glass substrate satisfactorily under high-temperature high-humidity environments, no foaming or detachment occurs between the adhesive agent layer and the glass substrate, and unevenness in color or leakage of light does not occur.

Description

Tackiness agent, used for optical part tackiness agent, the optics that has binder layer, image display device, active energy beam and/or Thermocurable binder compsn, binder compsn

Technical field

The present invention relates to tackiness agent (pressure adhesive), and the used for optical part tackiness agent, use it and the optics that has binder layer, image display device, active energy ray-curable and/or the Thermocurable binder compsn that obtain.In detail; Relate to optical thin film of being suitable for liquid crystal indicator, organic EL display, PDP image display devices such as (plasma display panel) (polarizing film, phase-contrast film, optical compensating film, film etc. adds lustre to) etc.; More specifically; The used for optical part tackiness agent that relates to the glass substrate that is used for bonding optical laminate that forms through protective films such as triacetate fiber prime system film linings polarizing film and liquid crystal cells; And be formed with the optics that has binder layer of the binder layer that constitutes by this used for optical part tackiness agent, especially have the Polarizer of binder layer.

Background technology

Up to now; On the surface with the liquid crystal cells of the range upon range of liquid crystal composition that is the orientation of clamping between two sheet glass of Polarizer; Thereby formation LCD panel; Said Polarizer is given the polyvinyl alcohol film of polarity etc. with the lining of cellulose-based film, for example cellulose triacetate film two sides forms, the lip-deep range upon range of binder layer through will being arranged at the Polarizer surface usually of this liquid crystal cells with the surperficial butt of above-mentioned liquid crystal cells, push and carry out.

It is the 3-tier architecture that protective membrane is clipped in the two sides of polyethenol series polaroid that this Polarizer has with tri acetyl cellulose, but owing to these properties of materials lack dimensional stability.In addition because the polyethenol series polaroid is shaped through extension, therefore cause easily through the time dimensional change.If can't the internal stress that produce owing to such dimensional change absorbed, relax, the residual stress distribution that then acts on Polarizer can become inhomogeneous, and especially stress is concentrated in the circumference of Polarizer.Its result, the circumference that liquid crystal indicator takes place in liquid crystal indicator is than the more bright perhaps irregular colour light leakage phenomena of more dim grade of central authorities.

So about various optical applications, especially Polarizer is pasted and use tackiness agent, for the excellent in te pins of durability of not only bubbling, peeling off etc., and the optical characteristics that is difficult to take place light leak etc. also excellence tackiness agent and study.

For example; Thereby put down in writing a kind of use tackiness agent that the acrylic resin optical characteristics of aromatic monomer copolymerization is excellent in the patent documentation 1; Thereby put down in writing a kind of low-molecular weight compound that will contain aromatic nucleus in the patent documentation 2 and be compounded in the excellent tackiness agent of optical characteristics in the acrylic resin, put down in writing in the patent documentation 3 a kind of will make up the ethylene unsaturated monomer (UV curing monomer) that uses acrylic resin thus make the tackiness agent of the balance excellence of its crosslinking polymerization weather resistance and optical characteristics with the active energy beam irradiation.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2005-53976 communique

Patent documentation 2:WO2007/072799 communique

Patent documentation 3: TOHKEMY 2009-132909 communique

Summary of the invention

The problem that invention will solve

Yet,,, must make a large amount of copolymerization of aromatic monomer in order to satisfy in recent years for the requirements at the higher level of optical characteristics with this technology though disclosed technology has shown certain optical characteristics in the above-mentioned patent documentation 1.

But when using a large amount of aromatic monomers to carry out polymerization, the viscosity in the reaction solution can rise; Therefore (for example be difficult to be manufactured in the tackiness agent of optical applications normally used HMW; Weight-average molecular weight is more than 1,000,000) acrylic resin, in addition, common aromatic monomer; Because the diacrylate body of the impurity that when it is made, produces is difficult to remove through distillation etc.; Therefore the diacrylate body of impurity is contained in regular meeting, because the influence of this impurity, is difficult to make the high-molecular weight acrylic resin equally with above-mentioned.

And then, in polymerization, using when being easier to carry out low-molecular-weight aromatic monomer such as polymeric benzyl acrylate, vinylformic acid phenoxy ethyl, the remaining monomer during polymerization may be still residual after binder layer forms, and its stink also can become problem.

Above-mentioned patent documentation 2 disclosed technology can obtain being difficult for taking place the result of irregular colour, light leak really; But low-molecular weight compound crystallinity height or hydrophobic group with 2 above phenyl ring that patent documentation 2 uses are few, and be therefore poor to the consistency of acrylic resin; And be low molecular weight compositions; Because force of cohesion is low, therefore the force of cohesion as acrylic adhesive can't improve, and the problem of the weather resistance variation of liquid crystal indicator is arranged.

In the above-mentioned patent documentation 3 disclosed technology; The balance of weather resistance and optical characteristics is excellent really; But because the main ethylene unsaturated monomer with 2 above olefinic unsaturated groups that uses is as the UV curing monomer; Therefore cross-linking density, the Young's modulus of the postradiation binder layer of UV are compared with common tackiness agent and are become very high, the problem of exist the viscosity of tackiness agent to reduce, tackiness agent being adhered the sense difference when adherend is pasted.

Therefore; Under such background; The objective of the invention is to; The excellent tackiness agent of operability (viscosity), optical characteristics (mist degree (Haze)) of binder layer is provided, even and under the situation that optics such as Polarizer and glass substrate are fitted also tackiness agent, especially the used for optical part tackiness agent of excellence of endurance quality and optical characteristics (anti-light leak performance).

The scheme that is used to deal with problems

The inventor etc. have carried out deep repeatedly research to above-mentioned situation; The result finds: in the tackiness agent of active energy ray curable and/or thermohardening type; Through being the mode of the main body monofunctional monomer that contains 1 olefinic unsaturated group with specified proportion with the monofunctional monomer and contain the ethylene unsaturated monomer of the polyfunctional monomer of the olefinic unsaturated group more than 2 as solidified nature; And then use monofunctional monomer as monofunctional monomer with aromatic nucleus; Operability (viscosity), optical characteristics (mist degree) excellence, and the balance of endurance quality and anti-light leak property is excellent, thus accomplished the present invention.

Promptly; Main idea of the present invention relates to a kind of tackiness agent; It is characterized in that; It is for being cured the tackiness agent that forms with binder compsn [I] through active energy beam and/or heat; Said binder compsn [I] contains acrylic resin (A), contain the aromatics (B) of 1 olefinic unsaturated group and contain the alefinically unsaturated compounds (C) of 2 above olefinic unsaturated groups, and wherein the content of aromatics (B) is that resin (A) is 3 ~ 300 weight parts with respect to 100 parts by weight of acrylic acid, and aromatics (B) contains ratio (mol%) greater than 50mol% with respect to the total amount of aromatics (B) and alefinically unsaturated compounds (C).

In addition; Main idea of the present invention relates to the used for optical part tackiness agent that uses above-mentioned tackiness agent to form, and the image display device that comprises the optics that has binder layer of the stepped construction of the binder layer that contains this used for optical part tackiness agent and optics, is made up of this optics.

In addition, main idea of the present invention relates to a kind of tackiness agent, it is characterized in that, it contains acrylic resin (A), contain the polymkeric substance of the aromatics (B) of 1 olefinic unsaturated group, contain the aromatics (B) of 1 olefinic unsaturated group, and organic solvent.

And then; Main idea of the present invention relates to a kind of binder compsn; It is characterized in that, its contain acrylic resin (A) and contain the aromatics (B) of 1 olefinic unsaturated group, the alefinically unsaturated compounds (C) that contains 2 above olefinic unsaturated groups forms, wherein; The photoelastic coefficient of acrylic resin (A) is for negative, and the photoelastic coefficient of aromatics (B) and the cured article of alefinically unsaturated compounds (C) is for just.

In addition, the excellent performance of anti-light leak of tackiness agent of the present invention is inferred as follows about the reason that light leak can not take place.

Generally speaking; The major cause that light leak takes place is inferred: because Polarizer is exposed to the contraction in following time of heat-resisting condition; Stress is to concentrate and generation double refraction (having positive photoelastic coefficient) on the protective film at the tri acetyl cellulose (TAC) of Polarizer; Or the XPA of tackiness agent is followed the contraction of Polarizer equally and is orientated generation double refraction (generally speaking having negative photoelastic coefficient).

If the XPA with negative photoelastic coefficient in the past is that the double refraction that protective film is originated compares with the TAC with positive photoelastic coefficient, infer that then the double refraction in XPA source is bigger.That is, when Polarizer shrinks and when producing tensile stress (direction that produces stress is decided to be the x direction of principal axis), it is that protective film reduces effect in the axial specific refractory power of y that the specific refractory power of the XPA that increases at the y direction of principal axis can't be offset TAC.In order to eliminate (counteracting) this double refraction, must strengthen positive photoelastic coefficient somewhere.

Therefore in the present invention; Through the birefringent acrylic resin of bearing with respect to generation in the past (A); Uniform mixing produces the positive birefringent aromatics (B) and the cured article of alefinically unsaturated compounds (C); Can utilize the aromatics (B) and the cured article of alefinically unsaturated compounds (C) to offset the double refraction of acrylic resin (A) and/or the birefringent generation that tri acetyl cellulose is film, thereby obtain the excellent Polarizer that is provided with adhering agent layer of anti-light leak property.

On the other hand; For the foregoing reasons; Simple function and to produce positive birefringent aromatics (B) more than alefinically unsaturated compounds (C) importantly, the cured article performance degree of freedom of aromatics (B) and alefinically unsaturated compounds (C) thus is when acrylic resin (A) is orientated; Aromatics (B) also and then is orientated with the cured article of alefinically unsaturated compounds (C), infers and can reach effect of the present invention therefrom.

Otherwise, if the magnitude relation of aromatics (B) and alefinically unsaturated compounds (C) is conversely, infer that then the branched structure of its cured article can become very many and lose its structural degree of freedom, becoming is difficult to orientation, thereby can't reach effect of the present invention.

The effect of invention

Tackiness agent of the present invention especially can be applicable to the optics purposes; Operability (viscosity), optical characteristics (mist degree) excellence through the binder layer behind active energy beam and/or hot the curing; Even under the environment of high temperature, high humidity, the cementability of optics such as optical laminate, especially Polarizer and glass substrate is also excellent; Do not bubble, peel off between binder layer and the glass substrate, can not produced the liquid crystal indicator of irregular colour, light leak.

Embodiment

Below the present invention is elaborated, but an example of ideal embodiment only is shown here.

In addition, among the present invention, (methyl) vinylformic acid is meant acrylic or methacrylic acid, and (methyl) acryl is meant acryl or methacryloyl, and (methyl) propenoate is meant propenoate or methacrylic ester.

At first, binder compsn of the present invention [I] is described.

Binder compsn of the present invention [I] is for containing acrylic resin (A), contain the aromatics (B) of 1 olefinic unsaturated group and containing the compsn that the alefinically unsaturated compounds (C) of 2 above olefinic unsaturated groups forms.

Acrylic resin used in the present invention (A) is for being that monomer (a1) is a principal constituent with (methyl) alkyl acrylate; To contain the monomer (a2) of functional group as required copolymerization will form as copolymer composition, but and then also can be with the monomer (a3) of other copolymerization as copolymer composition.Acrylic resin among the present invention (A) uses the monomer (a2) that contains functional group as copolymer composition, from becoming the cross-linking set of acrylic resin (A), makes the further viewpoint that rises of adaptation of base material, adherend consider it is preferred.

As this (methyl) alkyl acrylate is monomer (a1); The carbonatoms of alkyl is preferably 1 ~ 20 usually; Be preferably 1 ~ 12 especially; Further be preferably 1 ~ 8; Especially be preferably 4 ~ 8, particularly can enumerate out (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-propyl, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) IBOA etc.They can use a kind of separately or two or more combinations are used.

Should (methyl) alkyl acrylate be in the monomer (a1); Obtain the viewpoint of easy property considers from copolymerization property, bonding rerum natura, processing ease property and raw material; Preferred (methyl) n-butyl acrylate, (methyl) 2-EHA of using more preferably considers to use (methyl) n-butyl acrylate from the viewpoint of excellent in te pins of durability.

Content when making (methyl) alkyl acrylate be monomer (a1) copolymerization; Overall with respect to copolymer composition; Be preferably 10 ~ 100 weight %, be preferably 50 ~ 99 weight % especially, more preferably 80 ~ 98 weight %; When the content of (methyl) acrylic ester monomer (a1) was very few, then adhesiveproperties had the tendency of reduction.

As the monomer that contains functional group (a2); Can enumerate out contain can through with after state the monomer that linking agent (E) reaction becomes the functional group of cross-linking set; For example can enumerate out the hydroxyl monomer, contain carboxylic monomer, contain amino monomers, contain the acetoacetyl monomer, contain the NCO monomer, contain glycidyl monomer etc.; In these,, preferably use the hydroxyl monomer, contain carboxylic monomer from carrying out the viewpoint of crosslinking reaction effectively.

As the hydroxyl monomer; Can enumerate out for example alkylidene oxide (oxyalkylene) modified monomers such as caprolactone modification monomer, (methyl) vinylformic acid binaryglycol ester, (methyl) polyalkylene glycol acrylate ester such as vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 5-hydroxyl pentyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, caprolactone modification (methyl) vinylformic acid 2-hydroxy methacrylate, for example can enumerating out in addition, 2-acrylyl oxy-ethyl 2-hydroxyethyl phthalic acid, N-methylol (methyl) acrylic amide etc. contain the monomer of primary hydroxyl; (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-chloro-2-hydroxy propyl ester etc. contain the monomer of secondary hydroxyl; (methyl) vinylformic acid 2,2-dimethyl--2 hydroxy methacrylate etc. contains the monomer of tert-hydroxyl.

In the above-mentioned hydroxyl monomer; From considering with the reactive excellent viewpoint of linking agent (E); The monomer that preferably contains primary hydroxyl, and then preferred use is the hydroxyl monomer below 0.5% as the ratio that contains of impurity two (methyl) propenoate; More preferably use below 0.2%, particularly the hydroxyl monomer below 0.1%.Particularly, preferred vinylformic acid 2-hydroxy methacrylate, vinylformic acid 4-hydroxyl butyl ester.

As containing carboxylic monomer; For example can enumerate out (methyl) vinylformic acid, acrylic acid dimer, Ba Dousuan, toxilic acid, maleic anhydride, fumaric acid, citraconic acid, propene dicarboxylic acid, methylene-succinic acid, acrylic amide N-glycolic acid, TRANSCINNAMIC ACID etc., wherein preferably use (methyl) vinylformic acid.

As containing amino monomers, for example can enumerate out (methyl) vinylformic acid tertiary butyl amino ethyl ester, (methyl) vinylformic acid ethylamino ethyl ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester etc.

As containing the acetoacetyl monomer, for example can enumerate out (methyl) vinylformic acid 2-(acetoacetoxy groups) ethyl ester, acetoacetic acid allyl ester etc.

As containing the NCO monomer, for example can enumerate out 2-acrylyl oxy-ethyl isocyanic ester, 2-methylacryoyloxyethyl isocyanic ester, their alkylidene oxide affixture etc.

As containing the glycidyl monomer, for example can enumerate out (methyl) glycidyl acrylate, (methyl) vinylformic acid allyl glycidyl etc.

The monomer (a2) that these contain functional group, can use separately also can make up use two or more.

Content when making monomer (a2) copolymerization that contains functional group; Overall with respect to copolymer composition, be preferably 0 ~ 30 weight %, be preferably 0.1 ~ 10 weight % especially; 0.2 ~ 3 weight % more preferably; Contain the content of monomer (a2) of functional group when too much, viscosity uprises, and the stability of resin has the tendency of reduction.

As other co-polymerized monomer (a3), for example can enumerate out the monomer that (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy binaryglycol ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy propyl ester, vinylbenzene, alpha-methyl styrene etc. contain 1 aromatic nucleus; Biphenyl propenoate, (methyl) vinylformic acid biphenylyloxy ethyl ester, (methyl) vinylformic acid biphenyl oxyalkyl ester etc. contain the monomer of xenyl; (methyl) vinylformic acid 2-methoxyl group ethyl ester; (methyl) vinylformic acid 2-ethoxy ethyl ester; (methyl) vinylformic acid 3-methoxyl group butyl ester; (methyl) vinylformic acid 2-butoxy ethyl ester; (methyl) vinylformic acid 2-butoxy binaryglycol ester; (methyl) vinylformic acid methoxyl group binaryglycol ester; (methyl) vinylformic acid methoxyl group triglycol ester; (methyl) vinylformic acid oxyethyl group binaryglycol ester; (methyl) vinylformic acid methoxyl group dipropylene glycol ester; (methyl) vinylformic acid methoxy poly (ethylene glycol) ester etc. contains the monomer of alkoxyl group and alkylidene oxide; Alkoxyalkyl (methyl) acrylamide monomers such as methoxymethyl (methyl) acrylic amide, ethoxyl methyl (methyl) acrylic amide, propoxy-methyl (methyl) acrylic amide, n-butoxy methyl (methyl) acrylic amide, isobutoxy methyl (methyl) acrylic amide; (methyl) acrylamide monomers such as (methyl) acryloyl morpholine, dimethyl-(methyl) acrylic amide, diethylammonium (methyl) acrylic amide, (methyl) acrylic amide N-methylol (methyl) acrylic amide; Vinyl cyanide, methacrylonitrile, vinyl acetate etc.

Content during as the co-polymerized monomer that makes other (a3) copolymerization, overall with respect to copolymer composition, be preferably 0 ~ 30 weight %; Be preferably 1 ~ 20 weight % especially; More preferably 2 ~ 10 weight % when the content of other co-polymerized monomer (a3) is too much, have to obtain the tendency that effect of the present invention becomes difficulty.

In addition; When turning to purpose, can make up and use two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) vinylformic acid propylene glycol ester, Vinylstyrene etc. to have the compound etc. of 2 above olefinic unsaturated groups with HMW.

Through acrylic resin (A) is made in the monomer component polymerization of above-mentioned (a1) ~ (a3), this polymerization can be carried out through existing known method such as solution free radical polymerization, suspension polymerization, mass polymerization, letex polymerizations.For example mixing or dropping (methyl) alkyl acrylate are monomer (a1), contain the monomer (a2) of functional group, other co-polymerized monomer polymerization single polymerization monomer, polymerization starters such as (a3) in organic solvent, and with reflux state or 50 ~ 90 ℃ of following polymerizations 2 ~ 20 hours.

As being used for this polymeric organic solvent, for example can enumerate out ketones such as aliphatics alcohols, acetone, methylethylketone, mibk, pimelinketone such as ester class, n-propyl alcohol, Virahols such as toluene, YLENE etc. are aromatic hydrocarbon based, methyl acetate, ETHYLE ACETATE, butylacetate etc.

As the polymerization starter that in this is free-radical polymerized, uses, the azos such as azobis isobutyronitrile, the two methyl pentane nitriles of azo that can enumerate out the radical polymerization initiator that belongs to common as concrete example are peroxo-system polymerization starters such as polymerization starter, Lucidol, lauroyl peroxide, di-t-butyl peroxide, isopropyl benzene hydroperoxide etc.

The weight-average molecular weight of acrylic resin (A) is generally 100,000 ~ 3,000,000, is preferably 300,000 ~ 2,500,000, is preferably 600,000 ~ 2,000,000 especially, especially is preferably 1,000,000 ~ 1,800,000.When weight-average molecular weight was too small, endurance quality had the tendency of reduction, needed the Macrodilution solvent when excessive, considered to have not preferably tendency from coating, cost aspect.

In addition, the dispersity (weight-average molecular weight/number-average molecular weight) of acrylic resin (A) is preferably below 20, is preferably especially below 10, more preferably below 7, especially is preferably below 4.When this dispersity was too high, the endurance quality of binder layer reduced, and easy blistered tendency is arranged.Wherein, the lower limit of dispersity is considered from the viewpoint of manufacturing limit, is generally 2.

And then the second-order transition temperature of acrylic resin (A) is preferably-80 ~-20 ℃, is preferably-75 ~-30 ℃ especially; More preferably-60 ~-40 ℃; When second-order transition temperature is too high, bonding force rising over-drastic tendency is arranged, cross the tendency that has thermotolerance to reduce when hanging down.

In addition; Above-mentioned weight-average molecular weight is the weight-average molecular weight that converts based on the polystyrene standard molecular weight, is at performance liquid chromatography (placed in-line 3 root chromatogram columns of use in Japanese Waters manufactured " Waters2695 (body) " and " Waters 2414 (detector) ": Shodex GPC KF-806L (exclusion limit molecular weight: 2 * 10 ⁷, separating ranges: 100 ~ 2 * 10 ⁷, theoretical plate number: 10000 sections/, filler material: styrene diethylene benzene copoly mer, packing material size: 10 μ m) measure and the value that obtains, number-average molecular weight also can make and use the same method.Dispersity can be tried to achieve by weight-average molecular weight and number-average molecular weight in addition.In addition, second-order transition temperature is calculated through the Fox formula.

[mathematical expression 1]

\frac{1}{Tg} = \frac{Wa}{Tga} + \frac{Wb}{Tgb} + \cdot \cdot \cdot + \frac{Wn}{Tgn}

Tg: the second-order transition temperature of multipolymer (K)

Tga: the second-order transition temperature of the homopolymer of monomer A (K) Wa: the weight fraction of monomer A

Tgb: the second-order transition temperature of the homopolymer of monomers B (K) Wb: the weight fraction of monomers B

Tgn: the second-order transition temperature of the homopolymer of monomer N (K) Wn: the weight fraction of monomer N

(Wa+Wb+…+Wn＝1)

In addition, among the present invention, by can balance satisfying weather resistance and the viewpoint that suppresses light leak well, preferably combination uses side chain to contain the acrylic resin (A1) of hydroxyl and acrylic resin (A2) that side chain contains carboxyl as acrylic resin (A).

On be set forth in the acrylic resin (A1) that side chain contains hydroxyl (following be called for short sometimes " acrylic resin (A1) "); So long as the acrylic resin that contains hydroxyl at side chain gets final product, the functional group that for example can enumerate out method through making the hydroxyl monomer copolymerization, makes the vinyl resin that contains functional group with have the material that can make with the method for the compound reaction (post-modification) of the functional group of this functional group reactions and hydroxyl etc. concurrently.

In the middle of them;, industry can obtain the viewpoint of the acrylic resin (A1) that side chain contains hydroxyl when making easily; Use will contain the monomeric copolymer composition of hydroxyl and other copolymer composition copolymerization and the resin that obtains is preferred; This acrylic resin (A1) can obtain as follows: as constitute aforesaid propylene acid be resin (A) contain monomer (a2), use the hydroxyl monomer as neccessary composition.

In addition, acrylic resin (A1) does not preferably contain carboxylic monomer in fact as the copolymer composition beyond the hydroxyl monomer, does not more preferably in fact contain the monomer of other functional group beyond the carboxyl yet." do not contain in fact " and be meant that the above-mentioned monomeric ratio that contains is below the 1 weight %, be preferably below the 0.1 weight %, be preferably especially and do not contain.

Above-mentioned side chain contains the acrylic resin (A2) (following abbreviate as sometimes " acrylic resin (A2) ") of carboxyl; Get final product so long as side chain contains the acrylic resin of carboxyl, for example can enumerate out through making the method that contains the carboxylic monomer copolymerization, make the functional group of the acrylic resin that contains functional group and having the material that to make with the method for the compound reaction (post-modification) of the functional group of this functional group reactions and carboxyl etc. simultaneously.

In the middle of them; Use will contain the copolymer composition of carboxylic monomer and the material of other copolymer composition copolymerization; The viewpoint that when industry is made, can obtain the acrylic resin (A2) that side chain contains carboxyl easily is preferred; This acrylic resin (A2) can obtain as follows: as constituting aforesaid propylene acid is the monomer that contains functional group (a2) of resin (A), uses to contain carboxylic monomer as neccessary composition.

In addition, acrylic resin (A2) does not preferably contain the hydroxyl monomer in fact as the copolymer composition beyond the hydroxyl monomer, does not more preferably in fact contain the monomer of other functional group beyond the hydroxyl yet." do not contain in fact " and be meant that the above-mentioned monomeric ratio that contains is below the 1 weight %, be preferably below the 0.1 weight %, be preferably especially and do not contain.

When acrylic resin (A1) and acrylic resin (A2) are used in combination; The difference of the weight-average molecular weight of acrylic resin (A1) and acrylic resin (A2) after a little while; Can improve the force of cohesion of the polymer network after crosslinked and improve weather resistance; So preferred, particularly, acrylic resin (A1) is preferably (A1)/(A2)=0.5 ~ 1.5 with the ratio ((A1)/(A2)) of the weight-average molecular weight of acrylic resin (A2); More preferably (A1)/(A2)=0.8 ~ 1.2 further is preferably (A1)/(A2)=0.9 ~ 1.1.

Acrylic resin (A 1) is preferably (A1) with the compounding ratio (weight ratio) of acrylic resin (A2): (A2)=50: 50 ~ 99: 1, be preferably (A1) especially: (A2)=60: 40 ~ 95: 5, more preferably (A1): (A2)=70: 30 ~ 90: 10.

Acrylic resin (A1) is proportional when too much with respect to containing of acrylic resin (A2), exists with ... the linking agent addition, has the gel fraction of generation significantly to rise, and the tendency of weather resistance, anti-light leak property reduction has bonding force rising over-drastic tendency when very few.

, be preferably hydroxyl/carboxyl=0.15 ~ 20 the containing of hydroxyl that is contained in the binder compsn [I] and carboxyl proportional (mol ratio) here, be preferably hydroxyl/carboxyl=0.5 ~ 10 especially, more preferably hydroxyl/carboxyl=1.5 ~ 2.5.Hydroxyl is proportional when too much to containing of carboxyl, exists with ... the linking agent addition, has the gel fraction of generation significantly to rise, and causes the tendency of weather resistance, anti-light leak property reduction, and bonding force rising over-drastic tendency is arranged when very few.

In addition; Hydroxyl, carboxyl in the above-mentioned binder compsn [I]; Be preferably the functional group that comes from acrylic resin (A1) and acrylic resin (A2) in fact; But also can be the hydroxyl, the carboxyl that come from other constituent, as long as in binder compsn [I], be in the above-mentioned scope.

As employed aromatics (B) (following abbreviate as sometimes " simple function property aromatics (B) " that contains 1 olefinic unsaturated group among the present invention; So long as having the compound of aromatic nucleus and 1 olefinic unsaturated group, intramolecularly gets final product; As this functional group of containing the olefinic unsaturated group, can enumerate out (methyl) acryl, crotonyl, vinyl, allyl group etc.

As simple function property aromatics (B); In its structure; For containing the compound of (methyl) acryl, during promptly single (methyl) propenoate based compound, the viewpoint of reacting easily from through active energy beam and/or thermofixation the time considers it is preferred among the above-mentioned functional group.

The number of the aromatic nucleus that contains as simple function property aromatics (B); Can contain 1 also can contain a plurality of; Consider from the equilibrated viewpoint that can obtain sticky object property; Be preferably the compound that contains 1 aromatic nucleus,, the specific refractory power of may command adhesive linkage good from efficient, birefringent viewpoint are considered, are preferably the compound that contains 2 aromatic nucleus.

As above-mentioned simple function property aromatics (B); Particularly; Can enumerate out ether is that simple function property aromatics (b1), ester are simple function property aromatics (b2) etc., is simple function property aromatics (b1) as ether, and for example can enumerate out phenol is dihydroxy benzene derivatives such as verivate, pyrocatechol, Resorcinol, quinhydrones etc.; As the simple function property aromatics (b2) of ester system, for example can enumerate out benzoic acid derivative, phthalic acid derivatives etc.

As phenol derivatives; The Wasserstoffatoms of the hydroxyl of preferred phenol is contained the verivate (b1-1) of the substituted structure of structure position of (methyl) acryl; As dihydroxy benzene derivatives, one of them of 2 hydroxyls that preferred Resorcinol has or two Wasserstoffatomss are contained the substituted verivate of structure position (b1-2) of (methyl) acryl.

Contain the structure position of (methyl) acryl as this, preferably also contain the material with following general formula (1) expression of alkylidene oxide structure.

[Chemical formula 1]

(in the formula, R is Wasserstoffatoms or methyl, and X is an alkylidene group, and n is the integer more than 1.）

X in the above-mentioned general formula (1) is an alkylidene group, wherein is preferably the alkylidene group of carbonatoms 1 ~ 10, is preferably the alkylidene group of carbonatomss 1 ~ 4 such as ethylidene, propylidene, tetramethylene especially, especially is preferably ethylidene.

When n is the polyoxyalkylene chain position more than 2, can be the homopolymer of same alkylidene oxide chain, also can be the multipolymer of different oxidation alkylidene chain with random or block-wise.

In addition, above-mentioned alkylidene group also can have substituting group, as substituting group, can enumerate out halogen atom, hydroxyl, alkoxyl group, amino, sulfane base (sulfanyl), aryl, heteroaryl etc. usually, wherein is preferably hydroxyl.

N in the above-mentioned general formula (1) is the integer more than 1, is preferably 1 ~ 10, is preferably 1 ~ 2 especially, more preferably 2.When this n value was excessive, the humidity resistance of acrylic resin had the tendency of reduction, and in addition, in order to control specific refractory power, double refraction, alkylidene group, alkylidene oxide structure are advisable with the shorter one, and n is preferred for a short time.

Concrete example as above-mentioned (b1-1); The repeat number that for example can enumerate out terepthaloyl moietie structures such as (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid diethylamino phenyl diol ester, (methyl) vinylformic acid phenyl triglycol ester, (methyl) vinylformic acid phenyl TEG ester, (methyl) vinylformic acid phenyl eight glycol esters is that the repeat number of terepthaloyl moietie structures such as (methyl) vinylformic acid phenyl macrogol ester of 2 ~ 8 (being preferably 2 ~ 4), (methyl) vinylformic acid phenoxy propyl ester, (methyl) vinylformic acid phenyl dipropylene glycol ester, (methyl) vinylformic acid phenyl W 166 ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy propyl ester, (methyl) vinylformic acid ethoxyquin phenyl phenyl ester, (methyl) vinylformic acid Nonylphenoxy ethyl ester, (methyl) vinylformic acid nonyl phenyl binaryglycol ester is that the repeat number of Ucar 35 structures such as (methyl) vinylformic acid nonyl phenyl macrogol ester, (methyl) vinylformic acid Nonylphenoxy propyl ester, (methyl) vinylformic acid nonyl phenyl dipropylene glycol ester of 2 ~ 8 (being preferably 2 ~ 4) is (methyl) vinylformic acid nonyl phenyl W 166 ester of 2 ~ 8 (being preferably 2 ~ 4) etc.; (OSAKA ORGANIC CHEMICALINDUSTRY LTD. makes can to enumerate out vinylformic acid phenoxy macrogol ester as commercially available article; Trade(brand)name " viscoat#193 "), (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. makes vinylformic acid 2-hydroxyl-3-phenoxy propyl ester; Trade(brand)name " viscoat#220 ", vinylformic acid phenoxy binaryglycol ester (kyoeisha Chemical Co.; Ltd. make; (Hitachi Chemical Co., Ltd. makes for trade(brand)name " Light acrylate P2HA ", vinylformic acid phenyl triglycol ester; Trade(brand)name " phenoxy triethyleneglycol acrylate "), (Hitachi Chemical Co., Ltd. makes vinylformic acid phenyl TEG ester; Trade(brand)name " phenoxy tetraethyleneglycol acrylate "), (Hitachi Chemical Co., Ltd. makes vinylformic acid nonyl phenyl chlorocarbonate; Trade(brand)name " nonyl phenoxy ethyl acrylate "), (Hitachi Chemical Co., Ltd. makes vinylformic acid nonyl phenyl binaryglycol ester; Trade(brand)name " nonyl phenoxy diethylene glycol acrylate "), (Hitachi Chemical Co., Ltd. makes vinylformic acid nonyl phenyl TEG ester; Trade(brand)name " nonyl phenoxy tetraethylene glycol acrylate "), (Hitachi Chemical Co., Ltd. makes vinylformic acid nonyl phenyl eight glycol esters; Trade(brand)name " nonyl phenoxy octaethylene glycol acrylate "), (Hitachi Chemical Co., Ltd. makes (methyl) vinylformic acid nonyl phenyl W 166 ester; Trade(brand)name " nonyl phenoxy plypropylene glycol (meta) acrylate "), the adjacent phenyl phenyl ester of vinylformic acid ethoxyquin (Shin Nakamura Chemical Co.; Ltd. make trade(brand)name " NK ester A-LEN-10 ") etc.

As benzoic acid derivative; The Wasserstoffatoms that is preferably benzoic carboxyl is contained the verivate (b2-1) of the substituted structure of structure position of (methyl) acryl; As phthalic acid derivatives, be preferably one of them of 2 carboxyls that phthalic acid has or the verivate (b2-2) that two Wasserstoffatomss are contained the substituted structure of structure position of (methyl) acryl.

As this structure position that contains (methyl) acryl, be preferably the material of aforementioned formula (1) expression.

Can enumerate out phthalic acid 2-acrylyl oxy-ethyl-2-hydroxy propyl ester (OSAKA ORGANICCHEMICAL INDUSTRY LTD. manufacturing as the concrete example of said derivative (b2-2) as commercially available article; Trade(brand)name " viscoat#2311HP "), (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. makes 2-acrylyl oxy-ethyl hydrogen phthalic ester; Trade(brand)name " viscoat#2000 "), (OSAKA ORGANIC CHEMICAL INDUSTRY LTD. makes 2-acryloyl-oxy propyl group hydrogen phthalic ester; Trade(brand)name " viscoat#2100 "), 2-methylacryoyloxyethyl phthalic acid (Shin Nakamura Chemical Co.; Ltd. make trade(brand)name " CB-1 ") etc.

Simple function property aromatics (B) used in the present invention; As previously mentioned; Just have no particular limits so long as intramolecularly has the compound of aromatic nucleus and 1 olefinic unsaturated group, but be preferably the material that intramolecularly contains 2 above aromatic nucleus, sulphur atom or bromine atoms especially.

Aromatic nucleus, sulphur atom, bromine atoms are known as the high structure of specific refractory power and import the structure of Acrylic Acid Monomer easily; Side chain through these structures being imported acrylic resins (being preferably on the side chain position away from main chain), the double refraction composition that produces in the time of can making the whole stress application of acrylic adhesive layer rises in the specific refractory power efficient of draw direction one side (x axle one side) very well.

The result; Through containing in the tackiness agent that makes vinyl resin, constitutes with the total of the polymkeric substance of above-mentioned simple function property compound (B) with respect to (methyl) alkyl acrylate main body that rises perpendicular to the specific refractory power of draw direction (y axle side); The double refraction of binder layer is cancelled, and can become to be difficult for taking place birefringent binder layer and to suppress light leak with good efficiencies.

The structure position that satisfies " containing 2 above aromatic nucleus, sulphur atom or bromine atoms " condition that contains as simple function property aromatics (B); Can enumerate out biphenyl structural, naphthalene structure, anthracene structure, benzene sulphur structure, bromobenzene structure etc., wherein biphenyl structural, benzene sulphur structure consider it is preferred from the viewpoint that effectively provides positive double refraction to improve effect.

For above-mentioned simple function property aromatics (B), (methyl) propenoate based compound that particularly can enumerate out (methyl) propenoate based compound that contains biphenyl structural, (methyl) propenoate based compound that contains benzene sulphur structure, (methyl) propenoate based compound that contains naphthalene structure, contains the bromobenzene structure etc.

As this (methyl) propenoate based compound that contains biphenyl structural, can enumerate out (methyl) biphenyl acrylate, (methyl) vinylformic acid biphenyl oxyalkyl ester, (methyl) vinylformic acid biphenyl and gather and stretch the alkyl diol ester.

As this (methyl) vinylformic acid biphenyl oxyalkyl ester; The carbonatoms that can enumerate out alkyl is (methyl) vinylformic acid biphenyl oxyalkyl ester of 1 ~ 8, particularly can enumerate out (methyl) vinylformic acid biphenyl oxygen methyl esters, (methyl) vinylformic acid biphenyl 2-ethoxyethyl acetate, (methyl) vinylformic acid biphenyl oxygen propyl ester etc.

As this (methyl) vinylformic acid biphenyl polyalkylene glycol ester; The carbonatoms that can enumerate out alkylidene group is 1 ~ 8; The number of repeat unit of alkylene glycol chain is (methyl) vinylformic acid biphenyl polyalkylene glycol of 2 ~ 10, particularly can enumerate out (methyl) vinylformic acid biphenyl binaryglycol ester, (methyl) vinylformic acid biphenyl triglycol ester, (methyl) vinylformic acid biphenyl TEG ester, (methyl) vinylformic acid biphenyl dipropylene glycol ester, (methyl) vinylformic acid biphenyl macrogol ester, (methyl) vinylformic acid biphenyl W 166 ester etc.

In the middle of them; Preferred (methyl) vinylformic acid biphenyl polyalkylene glycol ester; (methyl) vinylformic acid biphenyl macrogol ester of especially preferably considering from the viewpoint that positive photoelasticity effect can be provided efficiently, more preferably the number of repeat unit of glycol chain is (methyl) vinylformic acid biphenyl polyoxyethylene glycol of 1 ~ 4.

Contain (methyl) propenoate based compound of benzene sulphur structure as this; Can enumerate out (methyl) vinylformic acid benzene thioesters, (methyl) vinylformic acid benzene sulphur alkyl ester etc.; As this (methyl) vinylformic acid phenyl sulphur alkyl ester; The carbonatoms that can enumerate out alkyl is (methyl) vinylformic acid phenyl sulphur alkyl ester of 1 ~ 12, particularly can enumerate out (methyl) vinylformic acid benzene sulphur methyl esters, (methyl) vinylformic acid benzene sulphur ethyl ester, (methyl) vinylformic acid benzene sulphur propyl ester, (methyl) vinylformic acid benzene sulphur butyl ester, (methyl) vinylformic acid benzene sulphur pentyl ester, the own ester of (methyl) vinylformic acid benzene sulphur, (methyl) vinylformic acid benzene sulphur heptyl ester, (methyl) vinylformic acid benzene sulphur monooctyl ester, (methyl) vinylformic acid benzene sulphur ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid benzene sulphur ester in the last of the ten Heavenly stems etc.

In the middle of them, preferred (methyl) vinylformic acid benzene sulphur alkyl ester, (methyl) vinylformic acid benzene sulphur ethyl ester of especially preferably considering, more preferably vinylformic acid benzene sulphur ethyl ester from the viewpoint that positive photoelasticity effect can be provided effectively.

As this (methyl) acryliccompound that contains naphthalene structure, can enumerate out (methyl) vinylformic acid naphthyloxy ester, (methyl) vinylformic acid naphthyloxy methyl esters, (methyl) vinylformic acid naphthyloxy ethyl ester, (methyl) vinylformic acid naphthyloxy propyl ester etc.

As this (methyl) propenoate that contains the bromobenzene structure, can enumerate out phenyl ring such as (methyl) vinylformic acid bromine phenoxy methyl esters, (methyl) vinylformic acid dibromo-phenoxy base methyl esters, (methyl) vinylformic acid tribromophenoxy methyl esters, (methyl) vinylformic acid tetrabromo phenoxy methyl esters, (methyl) vinylformic acid pentabromo-phenoxy methyl esters, (methyl) vinylformic acid bromine phenoxy ethyl, (methyl) vinylformic acid dibromo-phenoxy base ethyl ester, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid tetrabromo phenoxy ethyl, (methyl) vinylformic acid pentabromo-phenoxy ethyl, (methyl) vinylformic acid bromine phenoxy propyl ester, (methyl) vinylformic acid dibromo-phenoxy base propyl ester, (methyl) vinylformic acid tribromophenoxy propyl ester, (methyl) vinylformic acid tetrabromo phenoxy propyl ester, (methyl) vinylformic acid pentabromo-phenoxy propyl ester through 1 ~ 5 bromine atoms substituted (methyl) vinylformic acid phenoxyalkyl ester.

Wherein, the carbonatoms of alkyl is generally 1 ~ 12.

In addition; As simple function property aromatics (B); When not containing easily the functional group of reacting with acrylic resin (A), linking agent (E); From through containing the cross-linked network of acrylic resin (A), thus the few viewpoint of possibility that causes simple function property aromatics (B) and the degree of freedom forfeiture of the cured article of alefinically unsaturated compounds (C), anti-light leak property improved effect to reduce consider, be preferred.

In the above-mentioned simple function property aromatics (B), be preferably vinylformic acid phenyl macrogol ester (number of repeat unit of polyoxyethylene glycol is 2 ~ 4), vinylformic acid Nonylphenoxy ethyl ester, vinylformic acid nonyl phenyl macrogol ester (number of repeat unit of polyoxyethylene glycol is 2 ~ 4), vinylformic acid Nonylphenoxy propylene glycol ester, vinylformic acid nonyl phenyl W 166 ester (number of repeat unit of W 166 is 2 ~ 4), vinylformic acid biphenyl 2-ethoxyethyl acetate, (methyl) vinylformic acid biphenyl macrogol ester (number of repeat unit of polyoxyethylene glycol is 2 ~ 4) especially.

This functional group particularly, in NCO, hydroxyl, the carboxyl any or two or more.

As the weight-average molecular weight of simple function property aromatics (B), be generally 200 ~ 10000, be preferably 210 ~ 1000, be preferably 220 ~ 500 especially.This weight-average molecular weight has the minimizing owing to aromatic nucleus concentration to become to be difficult for the birefringent tendency of adjustment, to volatilize easily when having tackiness agent dry when too small, be difficult to obtain inventing the tendency of effect when excessive.

As simple function property aromatics (B), preferably its flash-point is preferably 145 ~ 500 ℃ especially more than 120 ℃, more preferably 150 ~ 400 ℃, especially is preferably 160 ~ 300 ℃.When this flash-point is too high, the tendency that the double refraction adjustment capability reduces because molecular weight increases is arranged, have when too small, volatilization and be difficult to obtain to invent the tendency of effect easily when tackiness agent is dry because volatility rises.

As the simple function property aromatics (B) that satisfies this flash-point, for example can enumerate out vinylformic acid diethylamino phenyl diol ester (flash-point: 165 ℃), ethoxyquin orthoxenol propenoate (flash-point: 170 ~ 199 ℃) etc.[< reference value >, vinylformic acid phenoxy ethyl (flash-point: 139 ~ 141 ℃), benzyl acrylate (flash-point: 107 ℃)].

The content of simple function property aromatics (B) is resin (A) with respect to 100 parts by weight of acrylic acid, is required to be 3 ~ 300 weight parts, is preferably 5 ~ 100 weight parts, and more preferably 8 ~ 60 weight parts especially are preferably 25 ~ 45 weight parts.When the content of simple function property aromatics (B) was too much, the tendency that has weather resistance to worsen with anti-light leak property had the tendency of anti-light leak property reduction when very few.

As the spendable ethene property unsaturates (C) (following abbreviate as sometimes " multi-functional unsaturated compound (C) ") that contains 2 above olefinic unsaturated groups of the present invention; It for example is the ethylene unsaturated monomer that 1 intramolecularly contains 2 above olefinic unsaturated groups; For example can use 2 functional monomers, 3 officials can above monomer, or (methyl) propenoic methyl carbamate based compound, epoxy (methyl) propenoate based compound, polyester (methyl) propenoate based compound.Among these, use ethylene unsaturated monomer, (methyl) propenoic methyl carbamate based compound, consider it is preferred from the viewpoint of curing speed, arrival physical properties stable property excellence.

As above-mentioned 2 functional monomers; Get final product so long as contain the monomer of 2 olefinic unsaturated groups; For example can enumerate out two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid TEG ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) vinylformic acid propylene glycol ester, two (methyl) vinylformic acid dipropylene glycol ester, two (methyl) vinylformic acid W 166 ester, two (methyl) vinylformic acid butanediol ester, two (methyl) vinylformic acid DOPCP, oxyethane modified bisphenol A type two (methyl) propenoate, epoxy pronane modification bisphenol A-type two (methyl) propenoate, 1; 6-pinakon two (methyl) propenoate, 1,6-pinakon oxyethane modification two (methyl) propenoate, two (methyl) vinylformic acid glyceryl ester, two (methyl) vinylformic acid pentaerythritol ester, ethylene glycol diglycidylether two (methyl) propenoate, Diethylene Glycol diglycidylether two (methyl) propenoate, o-phthalic acid diglycidyl ester two (methyl) propenoate, hydroxyl trimethylacetic acid modification two (methyl) vinylformic acid DOPCP, isocyanuric acid oxyethane modification diacrylate, 2-(methyl) acryl oxygen ethyl phosphate ester acid etc.

As the above monomer of above-mentioned 3 officials ability; Get final product so long as contain the monomer of 3 above olefinic unsaturated groups, for example can enumerate out three (methyl) vinylformic acid TriMethylolPropane(TMP), three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, three (methyl) vinylformic acid dipentaerythritol ester, four (methyl) vinylformic acid dipentaerythritol ester, five (methyl) vinylformic acid dipentaerythritol ester, six (methyl) vinylformic acid dipentaerythritol ester, three (methyl) acryloyl-oxy oxyethyl group TriMethylolPropane(TMP), glycerine and gather the dehydration glyceryl ether and gather (methyl) propenoate, isocyanuric acid oxyethane modification three (methyl) propenoate, oxyethane modification five (methyl) vinylformic acid dipentaerythritol ester, oxyethane modification six (methyl) vinylformic acid dipentaerythritol ester, oxyethane modification three (methyl) vinylformic acid pentaerythritol ester, oxyethane modification four (methyl) vinylformic acid pentaerythritol ester, succsinic acid modification three (methyl) vinylformic acid pentaerythritol ester etc.

As above-mentioned (methyl) propenoic methyl carbamate based compound; (methyl) propenoate based compound that has amino-formate bond for intramolecularly; Use will contain hydroxyl (methyl) acrylic acid series compound and multicomponent isocyanate based compound (as required; The polyvalent alcohol based compound) material through known general method reaction gained gets final product, and as its weight-average molecular weight, uses 300 ~ 4000 material to get final product usually.

The content of multi-functional unsaturated compound (C) is resin (A) with respect to 100 parts by weight of acrylic acid, and it is desirable to is 0.01 ~ 30 weight part, is preferably 0.5 ~ 10 weight part, more preferably 1 ~ 5 weight part.When the content of multi-functional unsaturated compound (C) was too much, the tendency that has weather resistance, anti-light leak property all to reduce had the insufficient tendency of anti-light leak property when very few.

Among the present invention, from can suitably adjusting cross-linking density, suitably adjustment adhesion sense, and then the equilibrated viewpoint that can obtain weather resistance is considered; With respect to the total amount of above-mentioned simple function property aromatics (B) with multi-functional unsaturated compound (C); The ratio (mol%) that contains of simple function property aromatics (B) needs to be preferably more than 50mol% and less than 100mol%, to be preferably 55 ~ 99mol% especially greater than 50mol%; More preferably 60 ~ 98mol% especially is preferably 65 ~ 97mol%.

With respect to the total amount of simple function property aromatics (B) with multi-functional unsaturated compound (C); Containing of simple function property aromatics (B) is proportional when too small; Because the content of multi-functional unsaturated compound (C) becomes many with respect to simple function property aromatics (B); There is cross-linking density to rise excessively, the tendency of shortcoming adhesion sense.In addition; Simple function property aromatics (B) is proportional when excessive with respect to containing of the total amount of simple function property aromatics (B) and multifunctional unsaturated compound (C); Because the content of multi-functional unsaturated compound (C) tails off with respect to simple function property aromatics (B); There have cross-linking density to rise to be few, the tendency of poor durability.

In addition; To (A) ~ (C) of the present invention composition; About through after state the photoelastic coefficient that method is measured; The photoelastic coefficient of acrylic resin (A) is for negative, and the photoelastic coefficient of the aromatics (B) that contains 1 olefinic unsaturated group and the cured article of the alefinically unsaturated compounds (C) that contains 2 above olefinic unsaturated groups is correct time, considers it is preferred from eliminating birefringent viewpoint effectively.

It is resin (A), simple function property aromatics (B) and multi-functional unsaturated compound (C) binder compsn [I] as neccessary composition that the present invention provides containing aforesaid propylene acid, the tackiness agent that is solidified into through active energy beam and/or heat (active energy beam irradiation and/or heating).Saidly be cured as the polymerization (high molecular) of simple function property aromatics (B) and multi-functional unsaturated compound (C), thereby solidify through active energy beam and/or heat.

In addition; Acrylic resin (A) is when relating to reaction; Be not limited to through active energy beam and/or the simple function property aromatics (B) of heat and the high molecular of multi-functional unsaturated compound (C); Also can be along with acrylic resin (A) and simple function property aromatics (B), and solidify with the high molecular of multi-functional unsaturated compound (C) etc.

Above-mentioned when being cured through active energy beam and/or heat, the viewpoint of the stable reactionization from can make the active energy beam irradiation time and/or during heating considers that preferred adhesive compsn [I] also contains polymerization starter (D).

In addition; Among the present invention; As with above-mentioned binder compsn [I] solidified method; Also can enumerate out above-mentioned (A) ~ (C) composition except that containing or (D) the composition, the material that also contains linking agent (E) is as binder compsn [I], and with its method that is cured through active energy beam and/or heat and is cured through linking agent.Wherein, when using linking agent (E), acrylic resin (A) preferably has functional group, can be cured (crosslinked) through this functional group and linking agent reaction.

Among the present invention; Above-mentioned curing through active energy beam and/or heat (active energy beam irradiation and/or heating); It is preferred from the active energy beam irradiation of ultraviolet ray that can be through the utmost point short period of time etc. its solidified viewpoint being considered; And then it also is preferred that the curing (crosslinked) through linking agent is used in combination, can obtain to improve tackiness agent cross-linking density, improve force of cohesion and make the more excellent material of weather resistance.

As above-mentioned polymerization starter (D); For example can use Photoepolymerizationinitiater initiater (d1), thermal polymerization various polymerization starters such as (d2); Particularly use Photoepolymerizationinitiater initiater (d1), it is preferred from the irradiation of ultraviolet isoreactivity energy-ray that can be through the utmost point short period of time its solidified viewpoint being considered.

In addition, when using above-mentioned Photoepolymerizationinitiater initiater (d1), binder compsn [I] is solidified, when using thermal polymerization (d2), through heating binder compsn [I] is solidified, but also preferably both are made up use as required through the active energy beam irradiation.

As this Photoepolymerizationinitiater initiater (d1), so long as the material that produces radical owing to light action gets final product, have no particular limits, can use the Photoepolymerizationinitiater initiater (d1-1) of intramolecularly autothermic cracking type, the Photoepolymerizationinitiater initiater (d1-2) of hydrogen-abstraction.

The Photoepolymerizationinitiater initiater (d1-1) of intramolecularly autothermic cracking type; For example can enumerate out 4-phenoxy dichloroacetophenone, 4-tertiary butyl dichloroacetophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropylidene phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl propane-1-ketone, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin ethyl isobutyl ether, benzyl dimethyl ketal, alpha-acyloxy oxime ester, acylphosphine oxide, aminomethyl phenyl glyoxylic ester, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 4-benzoyl--4 '-methyldiphenyl sulphur etc., wherein preferred 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone.

In addition, as the Photoepolymerizationinitiater initiater (d1-2) of hydrogen-abstraction, for example can enumerate out UVNUL MS-40, benzoyl-phenylformic acid, benzoyl-oil of Niobe, 4-phenyl benzophenone, dihydroxy benaophenonel, 3; 3 '-dimethyl--4-methoxy benzophenone, 2,4,6-tri-methyl benzophenone, 4-methyldiphenyl ketone, thioxanthone (thioxanthone), 2-clopenthixal ketone, 2-methyl thioxanthone, 2; 4-dimethyl-thioxanthone, isopropyl thioxanthone, camphorquinone, dibenzosuberone (Dibenzosuberone), 2-ethyl-anthraquinone, 3; 3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) UVNUL MS-40, benzyl, 9; 10-phenanthrenequione etc.; Wherein preferred UVNUL MS-40, methyldiphenyl ketone, 2,4, the 6-tri-methyl benzophenone.

The present invention preferably uses the Photoepolymerizationinitiater initiater (d1-2) of hydrogen-abstraction from the viewpoint of excellent in te pins of durability,, good from the photo-crosslinking of the surface portion that can make binder layer with the balance of inner photo-crosslinking, and the viewpoint that overall performance improves is considered.Especially preferably both make up use with the Photoepolymerizationinitiater initiater (d1-2) of the Photoepolymerizationinitiater initiater (d1-1) of intramolecularly autothermic cracking type and hydrogen-abstraction

Combination as the Photoepolymerizationinitiater initiater of the Photoepolymerizationinitiater initiater of autothermic cracking type and hydrogen-abstraction; Be preferably the 1-hydroxycyclohexylphenylketone of autothermic cracking type or UVNUL MS-40, the methyldiphenyl ketone or 2 of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone and hydrogen-abstraction; 4, the combination of 6-tri-methyl benzophenone.

In addition; Auxiliary agent as as required Photoepolymerizationinitiater initiater; Also can make up and use trolamine, tri-isopropanolamine, 4; 4 '-dimethylamino UVNUL MS-40 (Michler's keton), 2-dimethyl aminoethyl phenylformic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone etc.These can use a kind of or combination is used two or more.

In addition, as above-mentioned thermal polymerization (d2), for example can enumerate out methylethyl ketone peroxide, cyclohexanone peroxide, peroxo-methylcyclohexanone, methyl acetoacetate superoxide, diacetone peroxide, 1; Two (the uncle's hexyl peroxides)-3,3 of 1-, 5-trimethyl-cyclohexane, 1; Two (uncle's hexyl peroxide)-hexanaphthenes, 1 of 1-, two (t-butyl peroxy)-3,3 of 1-; 5-trimethyl-cyclohexane, 1, two (the t-butyl peroxy)-2-methylcyclohexanes, 1 of 1-, two (the t-butyl peroxy)-hexanaphthenes, 1 of 1-; Two (t-butyl peroxy) cyclododecanes, 1 of 1-, two (t-butyl peroxy) butane, 2 of 1-, 2-two (4; 4-di-t-butyl peroxide cyclohexyl) propane, to menthane hydrogen peroxide, di-isopropylbenzene hydroperoxide, 1,1,3; 3-tetramethyl butyl hydroperoxide, hydrogen phosphide cumene, uncle's hexyl hydrogen peroxide, tertbutyl peroxide, α, α '-two (t-butyl peroxy) diisopropylbenzene(DIPB), Di Cumyl Peroxide 99,2,5-dimethyl--2; Two (t-butyl peroxy) hexanes of 5-, tert-butyl peroxide isopropyl benzene, ditertiary butyl peroxide, 2,5-dimethyl--2, two (the t-butyl peroxy)-3-hexins of 5-, peroxo-isobutyryl, peroxo-3; 5,5-trimethyl acetyl, peroxo-decoyl, lauroyl peroxide, stearoyl, peroxysuccinic acid, m-toluyl peroxide benzoyl, Lucidol, peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, two (4-tert-butylcyclohexyl) esters of peroxy dicarbonate, peroxy dicarbonate two-2-ethoxy ethyl ester, the own ester of peroxy dicarbonate two-2-oxyethyl group, peroxy dicarbonate two-3-methoxyl group butyl ester, peroxide-butyl carbonate, peroxy dicarbonate two (3-methyl-3-methoxyl group butyl) ester, α, α '-two (new decanoyl peroxide) diisopropylbenzene(DIPB), peroxo-neodecanoic acid isopropyl benzene ester, peroxo-neodecanoic acid 1; 1,3,3-tetramethyl-butyl ester, peroxo-neodecanoic acid 1-cyclohexyl-1-methyl ethyl ester, the own ester of peroxo-neodecanoic acid uncle, new peroxide tert-butyl caprate, the own ester of peroxo-PIVALIC ACID CRUDE (25) uncle, the peroxo-PIVALIC ACID CRUDE (25) tert-butyl ester, peroxo--2 ethyl hexanoic acid 1; 1; 3,3-tetramethyl-butyl ester, 2,5-dimethyl--2; Two (the 2-ethyl hexanoyl base peroxide) capronates of 5-, peroxo--2 ethyl hexanoic acid 1-cyclohexyl-1-methyl ethyl ester, the peroxo--own ester of 2 ethyl hexanoic acid uncle, peroxide-2-ethyl hexanoic acid tert-butyl, the own ester of peroxo-sec.-propyl list carbonic acid uncle, peroxo-tert-butyl isobutyrate, the peroxo-toxilic acid tert-butyl ester, peroxo--3; 5, the 5-tri-methyl hexanoic acid tert-butyl ester, the peroxo-LAURIC ACID 99 MIN tert-butyl ester, the peroxo-sec.-propyl list carbonic acid tert-butyl ester, the peroxo--2-ethylhexyl list carbonic acid tert-butyl ester, peroxide acetic acid butyl ester, peroxo--toluoyl t-butyl perbenzoate, peroxidized t-butyl perbenzoate, two (t-butyl peroxy) isophthalic acid ester, 2,5-dimethyl--2; Two (toluoyl peroxide) hexanes of 5-, the own ester of peroxo-phenylformic acid uncle, 2; 5-dimethyl--2, two (benzoyl-peroxide) hexanes of 5-, the peroxo-alkylene propyl group list carbonic acid tert-butyl ester, tertiary butyl trimethyl silyl superoxide, 3,3 '; 4; 4 '-four (t-butyl peroxy carbonyl) UVNUL MS-40,2,3-dimethyl--2, organo-peroxide series initiators such as 3-diphenyl butane; 2-phenylazo-4-methoxyl group-2,4-methyl pentane nitrile, 1-[(1-cyanic acid-1-methylethyl) azo] methane amide, 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two (2-methylbutyronitrile), 2; 2 '-azobis isobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2, two (the 2-methyl-prop amidine) dihydrochlorides, 2 of 2 '-azo; Two (2-methyl-N-phenyl third amidine) dihydrochlorides, 2 of 2 '-azo, two [N-(4-the chloro-phenyl-)-2-methyl-prop amidine] dihydrochlorides, 2 of 2 '-azo, two [N-(4-hydrogen the phenyl)-2-methyl-prop amidine] dihydrochlorides, 2 of 2 '-azo, two [2-methyl-N-(phenyl methyl) third amidine] dihydrochlorides, 2 of 2 '-azo; Two [2-methyl-N-(2-propenyl) third amidine] dihydrochlorides, 2 of 2 '-azo, two [N-(2-the hydroxyethyl)-2-methyl-prop amidine] dihydrochlorides, 2 of 2 '-azo, two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides, 2 of 2 '-azo, two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides, 2 of 2 '-azo; 2 '-azo two [2-(and 4,5,6,7-tetrahydrochysene-1H-1; 3-diazepine-2-yl) propane] dihydrochloride, 2,2 '-azo is two, and [2-(3,4; 5,6-tetrahydropyrimidine-2-yl) propane] dihydrochloride, 2, two [2-(the 5-hydroxyls-3 of 2 '-azo; 4,5,6-tetrahydropyrimidine-2-yl) propane] dihydrochloride, 2; Two [2-[1-(2-the hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] propane] dihydrochlorides, 2 of 2 '-azo, 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2, the two [2-methyl-N-[1 of 2 '-azo; Two (the methylol)-2-hydroxyethyls of 1-] propionic acid amide], 2,2 '-azo two [2-methyl-N-[1, two (methylol) ethyls of 1-] propionic acid amides], 2; 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 2,2 '-azo two (2-methyl propanamide), 2,2 '-azo two (2; 4,4-trimethylpentane), 2,2 '-azo two (2-methylpropane), dimethyl--2; 2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azo two (4-cyanopentanoic acid), 2, the two azo series initiators such as [2-(methylol) propionitrile] of 2 '-azo; Deng.In addition, these thermal polymerizations can use separately, also can two or more combinations be used.

The content of above-mentioned polymerization starter (D); With respect to the aforementioned acrylic resin of 100 weight parts (A), be preferably 0.01 ~ 20 weight part, be preferably 0.1 ~ 10 weight part especially; 0.3 ~ 5 weight part more preferably; When the content of above-mentioned polymerization starter (D) was very few, the solidified nature that is weak and the rerum natura unsettled tendency that becomes had the tendency that can not get better effect in the time of too much.In addition, with respect to total 100 weight parts of simple function property aromatics (B) with multi-functional unsaturated compound (C), be preferably 0.01 ~ 100 weight part, more preferably 0.1 ~ 20 weight part is preferably 1 ~ 12 weight part especially.

In addition; As Photoepolymerizationinitiater initiater (d1), when the Photoepolymerizationinitiater initiater (d1-1) of combination use intramolecularly autothermic cracking type and the Photoepolymerizationinitiater initiater (d1-2) of hydrogen-abstraction, the ratio of the Photoepolymerizationinitiater initiater (d1-2) of Photoepolymerizationinitiater initiater of autothermic cracking type (d1-1) and hydrogen-abstraction; Be preferably (d1-1): (d1-2)=70: 30 ~ 1: 99 (weight ratio); Be preferably (d1-1) especially: (d1-2)=55: 45 ~ 5: 95 (weight ratio), more preferably (d1-1): (d1-2)=45: 55 ~ 10: 90 (weight ratio), containing (d1-1) is proportional when too much or very few; The tendency that the whole crosslinked balance collapse of binder layer is all arranged has the possibility of bonding rerum natura deterioration.

When above-mentioned active energy beam shines; Can pass through light such as far ultraviolet rays yue, ultraviolet ray, near-ultraviolet ray, infrared rays; Hertzian wave such as X ray, gamma-rays; Can pass through electron beam, proton beam, neutron beam etc. in addition, from considerations such as easy to be acquired, the prices of curing speed, irradiating unit, the curing through uviolizing is favourable.In addition, when carrying out the electron beam irradiation, even do not use above-mentioned Photoepolymerizationinitiater initiater (d1) also can solidify.

And the light source when carrying out above-mentioned uviolizing can use high voltage mercury lamp, electrodeless lamp, ultrahigh pressure mercury lamp, carbon arc lamp, xenon lamp, metal halide lamp, chemical lamp, black lamp etc.Under the situation of above-mentioned high voltage mercury lamp, for example at 5 ~ 3000mJ/cm ², preferred 10 ~ 1000mJ/cm ²Condition under carry out.In addition, under the situation of above-mentioned electrodeless lamp, for example at 2 ~ 1500mJ/cm ², preferred 5 ~ 500mJ/cm ²Condition under carry out.And irradiation time is according to the distance of the kind of light source, light source and coated face, coating thickness, other conditions and different, usually can for the several seconds ~ tens of seconds, according to circumstances, also can be part second.On the other hand, when above-mentioned electron beam shines, for example can use the electron beam of the energy with 50 ~ 1000Kev scope, irradiation dose is 2 ~ 50Mrad.

In addition, as above-mentioned polymerization starter (D), when using thermal polymerization (d2), through adding thermal initiation, carrying out polyreaction.Treatment temp when being heating and curing, treatment time are according to the kind of employed thermal polymerization (d2) and difference; Usually; Transformation period through initiator calculates; Treatment temp is preferably 70 ℃ ~ 170 ℃ usually, and the treatment time is preferably 0.2 ~ 20 minute usually, is preferably 0.5 ~ 10 minute especially.

As above-mentioned linking agent (E), for example can enumerate out the isocyanate-based linking agent, epoxy is that linking agent, Soluol XC 100 are that linking agent, trimeric cyanamide are that linking agent, aldehyde are that linking agent, amine are linking agent, metal-chelating system linking agent.Among these, from can improve with the viewpoint of the adaptation of base material, with reactive viewpoint of base polymer, preferably use the isocyanate-based linking agent.

As above-mentioned isocyanate-based linking agent; For example can enumerate out 2; 4-tolylene diisocyanate, 2; 6-tolylene diisocyanate, HTDI, 1; 3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene diisocyanate, ditan-4,4 '-vulcabond, isophorone diisocyanate, 1; Two (isocyanato-methyl) hexanaphthenes of 3-, tetramethyl-xylylene diisocyanate, 1, the adducts of polyol crosslink agent such as 5-naphthalene diisocyanate, triphenylmethane triisocyanate and these polyisocyanate crosslinkers and TriMethylolPropane(TMP), the biuret body of these polyisocyanate crosslinkers, isocyanuric acid ester body etc.

As above-mentioned epoxy is linking agent; For example can enumerate out epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, the T 55,1 of dihydroxyphenyl propane-Epicholorohydrin type, 6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, sorbyl alcohol polyglycidyl ether, poly-glycerol polyglycidyl ether, tetramethylolmethane polyglycidyl ether, two glycerine polyglycidyl ethers etc.

As above-mentioned Soluol XC 100 is linking agent; For example can enumerate out tetramethylol methane-three--'-aziridino propionic ester, TriMethylolPropane(TMP)-three--'-aziridino propionic ester, N; N '-ditan-4; 4 '-two (1-Soluol XC 100 carboxylic acid amides), N, N '-hexa-methylene-1,6-two (1-Soluol XC 100 carboxylic acid amides) etc.

As above-mentioned trimeric cyanamide is linking agent, for example can enumerate out HMMM, six ethoxyl methyl trimeric cyanamides, six propoxy-methyl melamines, six butoxymethyl trimeric cyanamides, six pentyloxy methyl melamines, six hexyloxy methyl melamines, melamine resin etc.

As above-mentioned aldehyde is linking agent, for example can enumerate out oxalic dialdehyde, mda, suceinic aldehyde, maleic dialdehyde, LUTARALDEHYDE, formaldehyde, acetaldehyde, phenyl aldehyde etc.

As above-mentioned amine is linking agent, for example can enumerate out hexamethylene-diamine, triethyl diamines, polymine, vulkacit H, NSC 446, triethyl tetramine, isophorone diamine, aminoresin, polymeric amide etc.

As above-mentioned metal-chelating system linking agent, can enumerate out methyl ethyl diketone, acetylacetic ester coordination compound of polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium etc.

In addition, these linking agents (E) can use separately, also can two or more combinations be used.

The content of above-mentioned linking agent (E) is resin (A) with respect to 100 parts by weight of acrylic acid usually, is preferably 0.01 ~ 10 weight part, and more preferably 0.05 ~ 5 weight part is preferably 0.1 ~ 2 weight part especially.When linking agent (E) is very few, have force of cohesion not enough, can't obtain the tendency of sufficient weather resistance, have flexibility and bonding force to reduce in the time of too much, weather resistance reduces, and becomes and peels off easily, therefore is difficult to the tendency of using as optics.

Among the present invention, also contain the constituent of silane coupling agent (F), consider it is preferred for the viewpoint of the adaptation of optics from raising as binder compsn [I].

As above-mentioned silane coupling agent (F), for example can enumerate out and contain epoxy silane coupling, contain the acrylic silane coupling agent, contain mercaptosilane coupling agents, the hydroxyl silane coupling agent, contain the carboxyl silane coupling agent, contain amino silicane coupling agent, the amide-containing silane coupling agent, contain isocyanato silanes coupling agent etc.These can use separately, also can two or more combinations be used.Among these, preferred use contains epoxy silane coupling, contains mercaptosilane coupling agents, and from improving damp and hot weather resistance and the viewpoint that does not excessively improve bounding force, also preferably combination is used and contained epoxy silane coupling and contain mercaptosilane coupling agents.

As the above-mentioned object lesson that contains epoxy silane coupling; For example can enumerate out γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, methyl three (glycidyl) silane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane etc.; Wherein, Preferably γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane, β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan.

As the above-mentioned concrete example that contains mercaptosilane coupling agents, for example can enumerate out the silane coupling agent etc. of the oligomeric of γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group dimethoxy-methyl silane or these compounds.

As the content of silane coupling agent (F), be resin (A) with respect to 100 parts by weight of acrylic acid, be generally 0.001 ~ 10 weight part, be preferably 0.01 ~ 1 weight part, be preferably 0.03 ~ 0.8 weight part especially.When the content of this silane coupling agent (F) is very few, the tendency that can not get additive effect is arranged, have the mutual solubility with acrylic resin (A) to reduce in the time of too much, can not get the tendency of bonding force, force of cohesion.

In addition; In the binder compsn [I]; In the scope that does not undermine effect of the present invention, also further compounding static inhibitor, other acrylic adhesive, other tackifiers such as tackiness agent, urethane resin, rosin, rosin ester, hydrogenated wood rosin glycerol ester, resol, aromatic series modified terpene resin, aliphatics through-stone oleo-resinous, alicyclic through-stone oleo-resinous, phenylethylene resin series, diformazan benzene series resin, tinting material, weighting agent, inhibitor, UV light absorber, known in the past additive such as functional pigmented, develop the color or the compound of variable color through ultraviolet ray or radiation exposure.

In addition, beyond the above-mentioned additive, also can contain contained impurity of the manufacturing raw material etc. of constituent of binder compsn [I] etc. on a small quantity.

As above-mentioned static inhibitor, for example can enumerate out an alkali metal salt, alkali earth metal salt, higher alcohols oxidation alkylene affixture, the polyalkylene glycol fatty esters etc. such as anionic antistatic agent, two (fluorosulfonyl) imide potassium, two (three fluorosulfonyls) imide li, lithium chloride such as cationic static inhibitor, aliphatic sulfonate, higher alcohol sulfate salt, higher alcohols oxidation alkylene affixture sulfuric acid, high alcohol phosphate salt, higher alcohols alkylidene oxide affixture phosphate ester salt of quaternary ammonium salts such as imidazole salts, tetra-allkylammonium sulphonate.

Like this, the present invention obtains above-mentioned binder compsn [I] is solidified the tackiness agent that forms.

Here; Adhesive sheet with the tackiness agent that binder compsn of the present invention is solidified and get; When its tackiness agent (layer) is formed by the tackiness agent that contains acrylic resin (A), contains the polymkeric substance of the aromatics (B) of 1 olefinic unsaturated group, the aromatics (B) that contains 1 olefinic unsaturated group and organic solvent, consider it is preferred from the viewpoint of easy performance effect of the present invention.

In this case; The content of the aromatics that contains 1 olefinic unsaturated group (B) that contains as the tackiness agent after solidifying; Being preferably 0.1 ~ 10 weight %, being preferably 1 ~ 5 weight % especially, is 0.5 ppm by weight ~ 5 weight % as the content of organic solvent; Be preferably 1 ~ 1000 ppm by weight, be preferably 10 ~ 100 ppm by weight especially.

And then above-mentioned tackiness agent, preferably containing alkyl acrylate is monomer (a1).For example, be the material of the manufacturing that comes from acrylic resin (A).

When containing alkyl acrylate and being monomer (a1), content is 1ppm ~ 5%, is preferably 10ppm ~ 1000ppm, is preferably 50 ~ 100ppm especially.

And, on optics (optical laminate), can obtain to have the optics of binder layer through the binder layer stratification that will constitute by above-mentioned tackiness agent.

In the above-mentioned optics that has a binder layer, preferably on the one side opposite, stripping film is set also with the optics face of binder layer.

As the above-mentioned method of manufacture that has the optics of binder layer; Binder compsn [I] has following method through active energy beam irradiation and when adding at least a being cured of pining for: [1] with binder compsn [I] on optics, be coated with, after the drying, the applying stripping film; Through active energy beam irradiation with add at least a method of handling of pining for; [2] with binder compsn [I] on stripping film, be coated with, after the drying, the applying optics is through the active energy beam irradiation with add at least a method of handling of pining for; [3] with binder compsn [I] on optics, be coated with, drying; Further through active energy beam irradiation with add after at least a processing of pining for, the method for applying stripping film, [4] with binder compsn [I] on stripping film, be coated with, drying; Further shine and add pine at least a and handle the method for the optics of fitting afterwards etc. through active energy beam.Among these, never damage viewpoint, operability, the stable viewpoint of making of base material, the situation of in the method for [2], carrying out the active energy beam irradiation is preferred.

In addition, when binder compsn [I] uses linking agent (when also the curing of carrying out through linking agent (crosslinked) is used in combination), implement maturation process after preferably stating the optics that the method manufacturing has binder layer in the use.In this maturation process, with the time of carrying out for the balance that obtains bonding rerum natura be the reaction times of the chemically crosslinked of tackiness agent, as the condition of slaking; Temperature is generally room temperature ~ 70 ℃; Time is generally 1 ~ and 30 days, particularly, for example can carry out 1 ~ 20 in 23 ℃; Carried out 3 ~ 10 in 23 ℃, carried out 1 ~ 7 etc. implementing under the condition in 40 ℃.

When being coated with above-mentioned binder compsn [I], preferably with this binder compsn [I] to be coated with behind the solvent cut, to weaker concn, be preferably 5 ~ 60 weight % as heating residue concentration, be preferably 10 ~ 30 weight % especially.In addition; As long as as above-mentioned solvent binder compsn [I] dissolving is just had no particular limits, for example can use pure series solvents such as aromatic series series solvent, methyl alcohol, ethanol, propyl alcohol such as ketone series solvent, toluene, YLENE such as ester series solvent, acetone, methylethylketone, mibk such as methyl acetate, ETHYLE ACETATE, methyl acetoacetate, methyl aceto acetate.Among these, consider, can suit to use ETHYLE ACETATE, methylethylketone from viewpoints such as solvability, drying property, prices.

In addition, about the coating of above-mentioned binder compsn [I], can carry out through customary ways such as rolling method, die head coating method, photogravure coating method, comma coating method, silk screen printings.

The gel fraction of the binder layer of making through aforesaid method is considered from endurance quality and anti-viewpoint of leaking rotary light performance, is preferably 30 ~ 99%, is preferably 60 ~ 90% especially, more preferably 70 ~ 85%.Gel fraction is crossed to be had when low because of the force of cohesion deficiency weather resistance insufficient tendency that becomes.In addition, have the rising owing to force of cohesion to make viscosity become not enough when gel fraction is too high, tackiness agent is for the tendency of the adhesion sense reduction of to-be-adhered object.

The binder layer of making through aforesaid method during with the finger contact, has well attached sense person because actual water vapour permeability when being attached on the to-be-adhered object is good, and the tendency that promotes operation property is arranged, and is preferred.

In addition; When the gel fraction of adjustment used for optical part tackiness agent was above-mentioned scope, kind and the amount etc. that for example can contain compounding amount, the adjustment linking agent of kind and combination usage ratio thereof, the adjustment polymerization starter of kind and amount, the adjustment polymerization starter of the compound of unsaturated group through irradiation dose, exposure intensity, the adjustment of adjustment active energy beam were reached.In addition, the ratio of components of the irradiation dose of above-mentioned active energy beam or exposure intensity, polymerization starter, addition pass through interaction separately, and gel fraction changes, and therefore are necessary to obtain balance separately.

Above-mentioned gel fraction constitutes degree of crosslinking, and (standard of state of cure is for example calculated with following method.Promptly; Being wrapped in the polymer sheet that constitutes base material (for example pet film etc.) with 200 purpose SUS system wire netting goes up and forms the adhesive sheet (barrier film is not set) that binder layer forms; Dipping is 23 ℃ * 24 hours in toluene, is gel fraction with the weight percent of undissolved binder constituents residual in the wire netting.Wherein, deduct the weight of base material in advance.

In addition, the specific refractory power of the binder layer through the aforesaid method manufacturing is preferably 1.470 ~ 1.575, is preferably 1.475 ~ 1.550 especially, and more preferably 1.475 ~ 1.520, especially be preferably 1.480 ~ 1.500.This specific refractory power is crossed has the whole birefringence-compensated tendency that becomes not enough of optical laminate when low, has the refringence with optical thin film to become big when too high, and the tendency of boundary reflection takes place easily.

This specific refractory power is for using ATAGO corporate system " Abbe refractometer 1T ", with the measured value of NaD line under 23 ℃.

In addition, in the optics that has binder layer of acquisition, the thickness of binder layer does not have special qualification, is preferably 5 ~ 300 μ m, is preferably 10 ~ 50 μ m especially, more preferably 12 ~ 30 μ m.The thickness of this binder layer has bonding rerum natura to be difficult for stable tendency when too thin, have the whole thickness of optics to increase the over-drastic tendency when blocked up.

The optics that has binder layer of the present invention directly is fitted in the tackiness agent aspect on the glass substrate, or the optics with stripping film is fitted in the tackiness agent aspect on the glass substrate after stripping film is peeled off, and supplies with for example LCD panel.

The initial of binder layer of the present invention is according to the suitably decisions such as material of adherend.For example, in the time of on fitting in glass substrate, preferably has the bounding force of 0.2N/25mm ~ 20N/25mm, more preferably 0.5N/25mm ~ 10N/25mm.

Above-mentioned initial is calculated as follows.For the Polarizer that has binder layer, be cut into width 25mm, stripping film is peeled off, the binder layer side is pushed on non-alkali glass plate (Corning Incorporated makes, " Corning XG "), Polarizer and sheet glass are fitted.After this, carry out autoclave and handle (50 ℃, 0.5MPa, 20 minutes) afterwards, after 24 hours, carry out 180 ℃ of stripping tests at 23 ℃, 50%RH held.

To the not special restriction of optics of the present invention; Can enumerate out the optical thin film of image display devices such as being applicable to liquid crystal indicator, organic EL display, PDP, for example Polarizer, polarizer, elliptical polarization plate, optical compensating film, brightness enhancement film and their duplexer etc.Wherein, Polarizer is effective especially in the present invention.

Normally laminated has the material as the triacetate fiber prime system film of protective film to the Polarizer that uses among the present invention on the two sides of polarizing film; As above-mentioned polarizing film; The film that use forms with the polyvinyl alcohol resin by mean polymerisation degree 1500 ~ 10000,85 ~ 100 moles of % of saponification deg is as material film, the aqueous solution or the painted single axle drawn membrane of dichroic dye (common 2 ~ 10 times, preferred about 3 ~ 7 times stretching ratio) through IKI.

As above-mentioned polyvinyl alcohol resin; Usually make through the PVA saponification that vinyl acetate is polymerized, also can contain a spot of unsaturated carboxylic acid (comprising salt, ester, acid amides, nitrile etc.), olefines, vinyl ethers, unsaturated sulfonic acid salt etc. can with vinyl acetate copolymerized composition.In addition, can enumerate out Z 150PH in the presence of acid with aldehydes reaction and so-called polyvinyl acetal resin and polyvinyl alcohol derivatives such as the for example bunching butyral resin that obtains, vinyl-formal resins.

In addition; Among the present invention; Also can use the aromatics (B) that contains acrylic resin (A) and contain 1 olefinic unsaturated group; And the alefinically unsaturated compounds (C) that contains 2 above olefinic unsaturated groups forms, and the photoelastic coefficient of acrylic resin (A) is for negative, and the photoelastic coefficient of aromatics (B) and the cured article of alefinically unsaturated compounds (C) is positive binder compsn.

Wherein, among the present invention, photoelastic coefficient positive and negative is as result that following mode is measured.

< the positive and negative condition determination of photoelastic coefficient >

In photoelasticity measurement device (UNIOPT CORPORATION, LTD. system: the test film of film like is set PEL-3A-102R), measures the positive and negative of photoelastic coefficient.

The positive and negative of photoelastic coefficient do, in the face that comprises width and length, with bearing of trend be 0 °, when being 90 ° perpendicular to the direction of bearing of trend, orientations of major just is decided to be when 0 ° of direction, orientations of major is decided to be negative when 90 ° of directions.

The thickness of the test film during about said determination; The positive and negative refringence that depends in arbitrary face of photoelastic coefficient; The positive and negative thickness effect that do not receive of photoelastic coefficient; Therefore the thickness of test film can be any thickness, and maneuverable thickness such as use operation property get final product, usually the test film of used thickness 1 ~ 1000 μ m.

The size of the test film during about said determination so long as in the scope that can be arranged at testing apparatus, get final product, does not have special qualification, uses length 20 ~ 50mm usually, the test film of width 10 ~ 20mm.

In addition; Photoelasticity is meant material owing to receive stress; Orientation takes place and phenomenon that the double refraction size changes in the molecule of constitute; During uniaxial extension because stress direction is consistent with bearing of trend, so birefringent orientations of major of when the elongation test sheet, representing of mensuration, decidable photoelastic coefficient positive and negative.Therefore; The extension ratio of the test film during about said determination is stable multiplying power as long as set orientations of major, like the soft material of tackiness agent owing to take place easily that orientation relaxes, the stress mitigation; Extension ratio hour can't stably be measured orientations of major sometimes; Therefore 2 ~ 5 times of extensible former approximately test length of a film, if like the hard material of film, about about 1.01 ~ 2 times that then extend former test length of a film get final product.

Embodiment

Below lift embodiment and come more specifically to explain the present invention, as long as but the present invention is no more than its main idea, be not limited to following examples.Wherein, " part " in the example, " % " are not having all to represent weight basis under the situation about specifying.

Prepare various acrylic resins (A) at first, in the following manner.Wherein, about the mensuration of the weight-average molecular weight of acrylic resin (A), dispersity, second-order transition temperature, measure according to preceding method.

Wherein, about the mensuration of the viscosity of acrylic resin (A), measure according to the 4.5.3 rotational viscosimeter method of JIS K5400 (1990).

In addition, the positive and negative mensuration of the photoelastic coefficient of acrylic resin (A) is carried out in such a way.

< the positive and negative mensuration 1 of photoelastic coefficient >

Acrylic resin (A) is coated on the SP-01 (gently peeling off PET), after under 100 ℃ dry 3 minutes, lamination SP-003 (heavily peeling off PET).40 ℃ of following 1 weeks of slaking, the thickness that obtains adhesive linkage is the adhesive sheet of 25 μ m with the sheet material that obtains.After this adhesive sheet was cut into 3cm * 2cm, (Uniopt Corporation, Ltd. made: in " PEL-3A-102R " only binder layer to be arranged at the photoelasticity measurement device.The orientations of major when making it extend 2 times is also measured in the two ends of stretched bonded agent layer, judges the positive and negative of photoelastic coefficient.

Be positioned at 0 ° of direction person for just with main shaft (slow axis) orientation, be positioned at 90 ° of direction persons for negative with main shaft (slow axis) orientation.

[preparation of acrylic resin (A)] (with reference to table 1)

[acrylic resin (A-1)]

Possess that condensation reflux device, whisking appliance, nitrogen are blown into mouthful and the four-hole round-bottomed flask of TM in drop into 98.5 parts of Bing Xisuandingzhis (a1), 1 part of vinylformic acid 2-hydroxy methacrylate (a2), 0.5 part of vinylformic acid (a2) and 75 parts of ETHYLE ACETATE, 45 parts of acetone; After the beginning reflux; Add 0.03 part of azobis isobutyronitrile (AIBN) as polymerization starter; After reacting 3 hours under the ethyl acetate backflow temperature; With ETHYLE ACETATE dilution, obtain acrylic resin (A-1) solution (weight-average molecular weight (Mw) 2,000,000, dispersity (Mw/Mn) 3.1, second-order transition temperature-54 ℃, solids component 16%, viscosity 8000mPas (25 ℃)).

[acrylic resin (A-2)]

Possess that condensation reflux device, whisking appliance, nitrogen are blown into mouthful and the four-hole round-bottomed flask of TM in drop into 97 parts of Bing Xisuandingzhis (a1), 3 parts of vinylformic acid (a2) and 100 parts of ETHYLE ACETATE, 45 parts of acetone; After the beginning reflux; Add 0.03 part of azobis isobutyronitrile (AIBN) as polymerization starter; After reacting 3 hours under the ethyl acetate backflow temperature; With ETHYLE ACETATE dilution, obtain acrylic resin (A-2) solution (weight-average molecular weight (Mw) 1,800,000, dispersity (Mw/Mn) 3.2, second-order transition temperature-53 ℃, solids component 18%, viscosity 8000mPas (25 ℃)).

[acrylic resin (A-3)]

Possess that condensation reflux device, whisking appliance, nitrogen are blown into mouthful and the four-hole round-bottomed flask of TM in drop into 98.5 parts of Bing Xisuandingzhis (a1), 1.5 parts of vinylformic acid 2-hydroxy methacrylates (a2) and 120 parts of ETHYLE ACETATE, 45 parts of acetone; After the beginning reflux; Add 0.03 part of azobis isobutyronitrile (AIBN) as polymerization starter; After reacting 3 hours under the ethyl acetate backflow temperature; With ETHYLE ACETATE dilution, obtain acrylic resin (A-3) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.4, second-order transition temperature-53 ℃, solids component 23%, viscosity 8000mPas (25 ℃)).

[acrylic resin (A-4)]

Be equipped with condensation reflux device, whisking appliance, nitrogen to be blown into mouthful and the four-hole round-bottomed flask of TM in drop into 95 parts of Bing Xisuandingzhis (a1), 5 parts of vinylformic acid (a2) and 120 parts of ETHYLE ACETATE, 45 parts of acetone; After the beginning reflux; Add 0.03 part of azobis isobutyronitrile (AIBN) as polymerization starter; After reacting 3 hours under the ethyl acetate backflow temperature; With ETHYLE ACETATE dilution, obtain acrylic resin (A-4) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.4, second-order transition temperature-51 ℃, solids component 23%, viscosity 8000mPas (25 ℃)).

[acrylic resin (A-5)]

Possess that condensation reflux device, whisking appliance, nitrogen are blown into mouthful and the four-hole round-bottomed flask of TM in; Drop into 95 parts of Bing Xisuandingzhis (a1), 5 parts of vinylformic acid (a2) and 100 parts of ETHYLE ACETATE, 45 parts of acetone; After the beginning reflux; Add 0.03 part of azobis isobutyronitrile (AIBN) as polymerization starter; In reaction under the ethyl acetate backflow temperature after 3 hours,, obtain acrylic resin (A-5) solution (weight-average molecular weight (Mw) 1,700,000, dispersity (Mw/Mn) 3.2, second-order transition temperature-51 ℃, solids component 18%, viscosity 8000mPas (25 ℃)) with ETHYLE ACETATE dilution.

[acrylic resin (A-6)]

Possess that condensation reflux device, whisking appliance, nitrogen are blown into mouthful and the four-hole round-bottomed flask of TM in drop into 61.3 parts of Bing Xisuandingzhis (a1), 35 parts of benzyl acrylates, 3.5 parts of vinylformic acid 2-hydroxy methacrylates (a2), 150 parts in 0.2 part of vinylformic acid (a2) and ETHYLE ACETATE, 45 parts of acetone; After the beginning reflux; Add 0.03 part of azobis isobutyronitrile (AIBN) as polymerization starter; After reacting 3 hours under the ethyl acetate backflow temperature; With ETHYLE ACETATE dilution, obtain acrylic resin (A-6) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.5, second-order transition temperature-36 ℃, solids component 20%, viscosity 8000mPas (25 ℃)).

[acrylic resin (A-7)]

Possess that condensation reflux device, whisking appliance, nitrogen are blown into mouthful and the four-hole round-bottomed flask of TM in; Drop into 94.8 parts of Bing Xisuandingzhis (a1), 0.2 part of vinylformic acid 2-hydroxy methacrylate (a2), 5 parts of vinylformic acid (a2) and 120 parts of ETHYLE ACETATE, 45 parts of acetone; After the beginning reflux; Add 0.03 part of azobis isobutyronitrile (AIBN) as polymerization starter; In reaction under the ethyl acetate backflow temperature after 3 hours,, obtain acrylic resin (A-7) solution (weight-average molecular weight (Mw) 1,500,000, dispersity (Mw/Mn) 3.4, second-order transition temperature-51 ℃, solids component 23%, viscosity 8000mPas (25 ℃)) with ETHYLE ACETATE dilution.

[table 1]

Annotate: BA: Bing Xisuandingzhi

HEA: vinylformic acid 2-hydroxy methacrylate

AAc: vinylformic acid

BzA: benzyl acrylate

[simple function property aromatics (B)]

Prepare following material as simple function property aromatics (B-1).

(kyoeisha Chemical Co., Ltd. makes vinylformic acid diethylamino phenyl diol ester, trade(brand)name " Light acrylate P2HA ": molecular weight 236.3)

Prepare following material as simple function property aromatics (B-2).

Ethoxyquin orthoxenol propenoate (Hitachi Chemical Co., Ltd. makes, trade(brand)name " FA-301A ": molecular weight 268, flash-point 170-199 ℃, the residual part 100% of volatilize)

Prepare following material as simple function property aromatics (B-3).

(Shin Nakamura Chemical Co., Ltd. makes the adjacent biphenyl 2-ethoxyethyl acetate of vinylformic acid, trade(brand)name " A-LEN-10T ": molecular weight 268)

Prepare following material as simple function property aromatics (B-4).

(OSAKA ORGANIC CHEMICAL INDUSTRY LTD. makes vinylformic acid benzene sulphur ethyl ester, trade(brand)name " PhSEA ": molecular weight 207)

[multifunctional unsaturated compound (C)]

Prepare following material as multifunctional unsaturated compound (C-1).

Viscoat 295 (molecular weight 296.3)

[polymerization starter (D)]

Prepare following material as Photoepolymerizationinitiater initiater (D-1).

1: 1 mixture of the mass ratio of UVNUL MS-40 and 1-hydroxycyclohexylphenylketone (Ciba Specialty Chemicals Inc. makes, " Irgacure 500 ")

[linking agent (E)]

Prepare following material as linking agent (E-1).

55% ethyl acetate solution of the tolylene diisocyanate affixture of TriMethylolPropane(TMP) (Nippon Polyurethane Industry Co., Ltd. makes, " Coronate L-55E ")

[silane coupling agent (F)]

Prepare following material as silane-based compound (F-1).

γ-glycidoxypropyltrime,hoxysilane (Shin-Etsu Chemial Co., Ltd makes, " KBM403 ")

Prepare following material as silane-based compound (F-2).

γ-Qiu Jibingjisanjiayangjiguiwan (Shin-Etsu Chemial Co., Ltd makes, " KBM803 ")

Prepare following material as silane-based compound (F-3).

Sulfydryl is silane coupling agent (oligomer type) (Shin-Etsu Chemial Co., Ltd makes, " X-41-1805 ")

[embodiment 1 ~ 13, comparative example 1 ~ 6]

With each the compounding composition for preparing in a manner described, prepares; Through ratio compounding shown in the following table 2; Thereby preparation becomes the binder compsn that the used for optical part tackiness agent forms material, with its dilution (viscosity [500 ~ 10000mPas (25 ℃)]), makes binder compsn solution with ETHYLE ACETATE.

Then; Is on the release sheet with the above-mentioned binder compsn solution coat that obtains at polyester; Make that dried thickness is 25 μ m, at 90 ℃ down after dry 3 minutes, with formed adhesive composition layer transfer printing on polyethylene terephthalate (PET) film (thickness 38 μ m); With the electrodeless lamp [the H bulb of LH6UV lamp] of Fusion manufactured, with peak illumination: 600mW/cm ², cumulative exposure amount: 240mJ/cm ²Carry out uviolizing (120mJ/cm ², 2 subpulses), slaking is 10 under 23 ℃, the condition of 65%R.H., obtains having the PET film of binder layer.

Use the PET film that has binder layer that obtains like this, according to each method evaluation of measuring operability shown in following, anti-smelly property, gel fraction, mist degree, specific refractory power.These results are shown in following table 2 in the lump.

[operability]

After the PET film that gained is had a binder layer is cut into 25mm * 40mm, peel off release sheet, with the finger contact adhesive layer, by its adhesion sense of following benchmark evaluation.

Zero: the good adherence sense is arranged

*: the adhesion sense is not too arranged

[anti-smelly property]

The PET film that gained is had a binder layer after 3 hours, is peeled off release sheet at 23 ℃, the temperature and humidity control condition held of 50%R.H., smells its taste and with following benchmark evaluation.

Zero: imperceptible monomer smell

*: feel to obtain the monomer smell

[gel fraction]

After the PET film that gained is had a binder layer is cut into 40mm * 40mm; Peel off release sheet; And a side of binder layer is fitted on the SUS net sheet (200 order) of 50mm * 100mm, then, with respect to SUS net sheet vertically; From central part is folding wrap into sample after, the weight change determination gel fraction when in the sealed vessel that 250g toluene is housed, flooding 24 hours under 23 ℃.

[mist degree]

The manufacturing of mist degree test sample

Gently peel off release sheet in polyester system above-mentioned binder compsn solution coat; Make that dried thickness is 25 μ m; After under 90 ℃ dry 3 minutes; With polyester is a side of heavily peeling off the adhesive composition layer of release sheet applying formation, with the electrodeless lamp [the H bulb of LH6UV lamp] of Fusion manufactured, with peak illumination: 600mW/cm ², cumulative exposure amount: 240mJ/cm ²Carry out uviolizing (120mJ/cm ², 2 subpulses), slaking 10 days under 23 ℃, the condition of 50%R.H. then obtains the binder layer of no base material.The binder layer of the no base material of gained is cut away 3cm * 4cm, divests and gently peel off release sheet, with a side of binder layer by be pressed in the non-alkali glass plate (Corning Incorporated makes, EagleXG) on, and then peel off and heavily peel off release sheet, obtain the mist degree test sample.

The mensuration of haze value

Use HAZE MATER NDH2000 (Japanese electric look Industrial Co., Ltd make) to measure the diffusion transsmissivity and the full light transmittance of above-mentioned mist degree test sample.Wherein, this machine is according to JIS K7361-1.

With the diffusion transsmissivity that obtains and the value substitution following formula of full light transmittance, calculate haze value.

Haze value (%)=(diffusion transsmissivity/full light transmittance) * 100

[specific refractory power]

Use above-mentioned mist degree test sample, use " the Abbe refractometer 1T " of Atago manufactured, with the value under 23 ℃ of the NaD ray mensuration.

[table 2]

Annotate: (A)～(F), the numerical value in the table is the compounding weight part.

In the table, "-" representes not compounding.

In the comparative example 5,15 parts of fluorenes of compounding, in the comparative example 6,30 parts of fluorenes of compounding.

In addition; Among the embodiment 13; Use the above-mentioned PET film that has binder layer to measure remaining simple function property aromatics (B) and ethyl acetate concentration in the tackiness agent (layer), the concentration of simple function property aromatics (B) is 4 weight % as a result, and ethyl acetate concentration is 25 ppm by weight.

Wherein, measuring method is following.

[measuring method of the concentration of simple function property aromatics (B)]

After the above-mentioned PET film that has binder layer is cut into 40mm * 40mm, divest release sheet, a side of binder layer is fitted on the SUS net sheet (200 order) of 50mm * 100mm; Afterwards; With respect to SUS net sheet vertically, folding from central part, wrap into sample after; After soaking 24 hours in the sealed vessel that 250g acetone is being housed under 23 ℃; The acetone soln of gained is injected 1 μ L (Injector:Agilent Technologies manufactured 7683B series) with the liquid automatic sampler, use gas chromatograph/mass fragments detector (GC:Agilent Technologies manufactured, 6890NNetwork GCsystem; MSD:Agilent Technologies manufactured 5973inert), measure the concentration of the simple function property aromatics (B) in the solution.The chromatographic column of using is the DB-17MS (30m * 250 μ m φ * 0.25 μ m) of Agilent manufactured, and current-carrying gas is He, and flow is 1.0ml/min, and pressure is 7.0psi (40 ℃ time).In addition, splitting ratio is 30: 1, and injector temperature is 220 ℃.The temperature condition of post case is 40 ℃ after following 5 minutes, heats up with 10 ℃/min, arrive 220 ℃ after, kept 10 minutes.Transmission line temperature to MSD is 220 ℃, and scan pattern (mass range: 10 ~ 600, scanning times: 2.52/sec).In addition, the weight of the PET film of the weight of the PET film that has binder layer of the concentration of the simple function property aromatics (B) in the acetone soln that obtains through said determination of the concentration of simple function property aromatics (B), above-mentioned 40mm * 40mm, 40mm * 40mm is calculated and is tried to achieve.

[measuring method of ethyl acetate concentration]

The PET film that has binder layer of gained is cut into 25mm * 25mm, weighs after divesting demoulding PET.Sample vial and the lid of this sample being put into capacity 20mL are tight.Should heat 30 minutes down at 120 ℃ with head-space sampler (Agilent Technologies manufactured headspace sampler G1888) by bottle; The gas of heated condition is taken out with the condition of (15psi * 4 minute); And use gas chromatograph/mass fragments detector (GC:Agilent Technologies manufactured; 6890N Network GC system, MSD:Agilent Technologies manufactured 5973inert) measures ethyl acetate concentration contained in this gas.The chromatographic column of using is the DB-17MS (30m * 250 μ m φ * 0.25 μ m) of Agilent manufactured, and current-carrying gas is He, and flow is 1.0ml/min, and pressure is 7.0psi (40 ℃ time).In addition, splitting ratio is 30: 1, and injector temperature is 220 ℃.The temperature condition of post case be 40 ℃ following 5 minutes, heat up with 10 ℃/min then, arrive 220 ℃ after, placed 10 minutes.To 220 ℃ of the transmission line temperature of MSD, and scan pattern (mass range: 10 ~ 600, scanning times: 2.52/sec).

In addition, this only measures ETHYLE ACETATE is general, and the ETHYLE ACETATE that uses with representative among this embodiment is measured as representative.

< the positive and negative mensuration 2 of photoelastic coefficient >

In addition, measure the simple function property aromatics (photoelastic coefficient of B-1 ~ B-4) positive and negative.Cured article can be not crosslinked under the situation of independent simple function property aromatics; Therefore operational difficulty, a spot of multi-functional unsaturated compound of compounding is also judged positive and negative photoelastic coefficient as simple function property aromatics positive and negative of the photoelastic coefficient of its cured article.Promptly; 100 parts of simple function property aromatics of compounding (B-1 ~ B-4), 10 parts of multi-functional unsaturated compounds (C-1) and 10 parts of Photoepolymerizationinitiater initiaters (D-1); It is coated on the sheet glass that is provided with spacer of thick 400 μ m; From the upper layers laminated glass, with the electrodeless lamp [the H bulb of LH6UV lamp] of Fusion manufactured, with peak illumination: 600mW/cm ², cumulative exposure amount: 240mJ/cm ²Carry out uviolizing (120mJ/cm ², 2 subpulses) make its curing.The thickness of the cured article that obtains is about 300 μ m.This cured article is cut into 3cm * 2cm, (longitudinal end is with the anchor clamps clamping) is set on photoelasticity measurement device (Uniopt Corporation, Ltd. makes: " PEL-3A-102R ").The two ends of stretching cured article are measured and to be made its orientations of major of being out of shape at 2% o'clock, likewise judge the positive and negative of photoelastic coefficient with aforementioned.

Its result, (photoelastic coefficient of each cured article of B-1 ~ B-4) just is simple function property aromatics.

Then; Is on the stripping film with the binder compsn solution coat of embodiment 1 ~ 13, comparative example 1 ~ 6 at polyester; Making dried thickness is 25 μ m, after under 90 ℃ dry 3 minutes, formed adhesive composition layer (thickness 190 μ m) is transferred on the Polarizer; With the electrodeless lamp [the H bulb of LH6UV lamp] of Fusion manufactured, with peak illumination: 600mW/cm ², cumulative exposure amount: 240mJ/cm ²Carry out uviolizing (120mJ/cm ², 2 subpulses), slaking is 10 under 23 ℃, the condition of 65%R.H., obtains to have the Polarizer of binder layer.

Wherein, above-mentioned Polarizer " MLP38U " that make with MeCan Imaging Inc is that 45 ° mode is cut use with relative outrigger shaft.

Use the Polarizer that has binder layer that obtains in this way, according to each method evaluation of measuring weather resistance (hot resistance test, thermal cycling test, oven test) shown in following, bonding force.These results state table 3 after being shown in the lump.

[weather resistance]

Peel off the release sheet of the Polarizer that has binder layer of gained; (Corning Incorporated makes by being pressed in the non-alkali glass plate with a side of binder layer; Eagle XG) on, behind applying Polarizer and the sheet glass, carries out autoclave and handle (50 ℃, 0.5MPa, 20 minutes); The evaluation of afterwards, in the long duration test (hot resistance test, thermal cycling test, oven test) of following (1) ~ (4), bubbling, peeling off.And then; In the oven test of following (4); Except above-mentioned foaming, the evaluation of peeling off, also make so that Polarizer is the mode of crossed nicols (crossed Nicol) observes with the light leak of two sides, back side applying same sample on the surface and use sample, carry out the evaluation of light leakage phenomena.

In addition, the size of employed test film is punched to 20cm * 15cm use.

[long duration test]

(1) hot resistance test

The long duration test of 60 ℃, 90%R.H.150 hour

(2) thermal cycling test

To as 1 circulation, carry out 75 round-robin long duration tests 70 ℃ of operations of placing 60 minutes-35 ℃ of held after 60 minutes

(3) oven test (A)

90 ℃, 150 hours long duration test

(4) oven test (B)

80 ℃, 150 hours long duration test and light leak

[metewand]

(foaming)

Zero ... Almost do not observe foaming

△ ... Observe slightly and bubble

* ... Observe a lot of foamings

(peeling off)

Zero ... Appearance is peeled off less than 0.5mm's, or less than the vestige that floats of 0.5mm

△ ... It is above and less than the peeling off of 10mm 0.5mm to occur, or 0.5mm is above and less than the vestige that floats of 10mm

* ... Above the peeling off of 10mm appears, or 10mm above float vestige

(light leak)

◎ ... Basically there is not light leak

Zero ... Light leak slightly takes place

△ ... A small amount of light leak takes place

* ... A large amount of light leaks take place in four limits

[bonding force]

The Polarizer that has binder layer of preparation is cut into width 25mm, divests mould release film, with a side of binder layer by being pressed in non-alkali glass plate (Corning Incorporated makes, " Corning 1737 "), and applying Polarizer and sheet glass.Afterwards, carry out autoclave and handle (50 ℃, 0.5MPa, 20 minutes), after 24 hours, carry out 180 ℃ of stripping tests at 23 ℃, the condition held of 50%R.H..About separability, bonding force is ideal for a short time, and target is that bonding force is below the 10N/25mm after 1 day.

[table 3]

※: the tackiness agent of comparative example 6, the fluorenes that uses as non-solidified nature aromatic series based compound and the consistency of acrylic resin are poor, and fluorenes oozes out and albefaction, and then also can't fit to sheet glass, can't carry out above-mentioned endurance test.

The tackiness agent of embodiment, the weather resistance when applying Polarizer and sheet glass, anti-light leak property, bonding force are that very high level and balance are very excellent, and adhesion sense, mist degree, anti-smelly property when processing binder layer are also excellent.Relative therewith, comparative example 1 ~ 6 is failed the performance that meets the demands in the following areas.

Not in the comparative example 1 of compounding simple function property aromatics (B-1); Though the rerum natura of binder layer itself is excellent; But the poor performance when applying Polarizer and sheet glass; Compounding simple function property aromatics (B-1) and increasing in the comparative example 2 of compounding amount of multi-functional unsaturated compound (C-1) not, though the performance when applying Polarizer and sheet glass is excellent, the poor properties of binder layer itself.

With respect to (B-1) and (C-1) total amount, only in the comparative example 3 of compounding simple function property aromatics (B-1) 15.7mol%, though the performance excellence when applying Polarizer and sheet glass, the poor properties of binder layer itself (operability is poor).

The comparative example 4 of the acrylic resin that use forms the aromatic monomer copolymerization; The result has taken place that aromatic monomer by not copolymerization causes lets the uncomfortable monomer smell of people; And because remaining monomeric influence, foaming has slightly taken place in the result in oven test.

Be mixed with in the comparative example 5,6 of the fluorenes that contains the aromatic nucleus low molecular compound that belongs to non-solidified nature; The stink that not only comes from fluorenes; And poor with the consistency of acrylic resin when increasing combined amount, so the mist degree of filming significantly worsens, and then; The low molecular compound seepage has not been given play to the function as adhesive linkage fully.

In addition, embodiment of the present invention has been shown in the foregoing description, but the foregoing description is merely illustration, does not do the explanation of qualification.In addition, belong to the change of the impartial scope of claim, all within the scope of the invention.

Utilizability on the industry

Tackiness agent of the present invention; Through the binder layer after active energy beam and/or hot being cured; Its operability (viscosity), optical characteristics (mist degree) excellence, even under the environment of high temperature, high humidity, the cementability of optics such as optical laminate, especially Polarizer and glass substrate is still excellent; Can obtain between binder layer and glass substrate, not bubble, peel off, the liquid crystal indicator of irregular colour or light leak does not take place.Therefore, be effectively especially, and then the optics that has binder layer that obtains as being used to obtain to use them and the tackiness agent of image display device are very useful for the used for optical part tackiness agent.

Claims

1. tackiness agent; It is characterized in that; It is that binder compsn [I] is cured the tackiness agent that forms through active energy beam and/or heat; Said binder compsn [I] contains acrylic resin (A), contain the aromatics (B) of 1 olefinic unsaturated group and contain the alefinically unsaturated compounds (C) of 2 above olefinic unsaturated groups; Wherein, the content of aromatics (B) is that resin (A) is 3 ~ 300 weight parts with respect to 100 parts by weight of acrylic acid, and aromatics (B) contains ratio (mol%) greater than 50mol% with respect to the total amount of aromatics (B) and alefinically unsaturated compounds (C).

2. tackiness agent according to claim 1 is characterized in that, acrylic resin (A) contains the acrylic resin (A1) and the carboxylic acrylic resin of side chain (A2) of side chain hydroxyl.

3. tackiness agent according to claim 1 and 2 is characterized in that, aromatics (B) contains 2 above aromatic nucleus, sulphur atom or bromine atoms.

4. according to each the described tackiness agent in the claim 1 ~ 3, it is characterized in that binder compsn [I] contains polymerization starter (D).

5. according to each the described tackiness agent in the claim 1 ~ 4, it is characterized in that binder compsn [I] contains linking agent (E), and form through linking agent is crosslinked.

6. a used for optical part tackiness agent is characterized in that, it is to use each described tackiness agent in the claim 1 ~ 5 to form.

7. used for optical part tackiness agent according to claim 6 is characterized in that, optics is a Polarizer.

8. optics that has binder layer, it comprises the stepped construction of binder layer and optics, and said binder layer contains claim 6 or 7 described used for optical part tackiness agents.

9. a kind of image display device of gel fraction is characterized in that, it uses the described optics that has binder layer of claim 8.

10. active energy ray-curable and/or Thermocurable binder compsn; It is characterized in that; The alefinically unsaturated compounds (C) that it contains acrylic resin (A), contains the aromatics (B) of 1 olefinic unsaturated group and contain 2 above olefinic unsaturated groups; Wherein, The content of aromatics (B) is that resin (A) is 3 ~ 300 weight parts with respect to 100 parts by weight of acrylic acid, and aromatics (B) contains ratio (mol%) greater than 50mol% with respect to the total amount of aromatics (B) and alefinically unsaturated compounds (C).

11. a tackiness agent is characterized in that, it contains acrylic resin (A), contain the polymkeric substance of the aromatics (B) of 1 olefinic unsaturated group, contain the aromatics (B) and the organic solvent of 1 olefinic unsaturated group.

12. binder compsn; It is characterized in that; It is contain acrylic resin (A) and contain the aromatics (B) of 1 olefinic unsaturated group, the alefinically unsaturated compounds (C) that contains 2 above olefinic unsaturated groups forms; Wherein, the photoelastic coefficient of acrylic resin (A) is for negative, and the photoelastic coefficient of aromatics (B) and the cured article of alefinically unsaturated compounds (C) is for just.