CN1990802A - Pressure-sensitive adhesive for polarizing plates, polarizing plate with pressure-sensitive adhesive and production process for the same - Google Patents
Pressure-sensitive adhesive for polarizing plates, polarizing plate with pressure-sensitive adhesive and production process for the same Download PDFInfo
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- CN1990802A CN1990802A CN 200610161799 CN200610161799A CN1990802A CN 1990802 A CN1990802 A CN 1990802A CN 200610161799 CN200610161799 CN 200610161799 CN 200610161799 A CN200610161799 A CN 200610161799A CN 1990802 A CN1990802 A CN 1990802A
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Abstract
A pressure-sensitive adhesive of polarizing plate can apply the polarizing plate bonded well to the polarizing plate of liquid crystal element, the polarizing plate of the pressure-sensitive adhesive and prepared method thereof are provided, the pressure-sensitive adhesive characterized in liquid crystal display can not generate leak light even in high temperature and wet environment easily and removable. The polarizing plate is made by pressure-sensitive adhesive via irradtion of activation energy beam containing (A) monomeric acrylic acid polymer with carboxylic group contains 0.5 wt% or less of monomer component ratio and (B) pressure-sensitive adhesive material with activated energy beam solided compound, which storage elastic modulus (G') is 0.3 MPa or more at 23 DEG C.
Description
Technical field
The present invention relates to pressure-sensitive adhesive for polarizing plates, have polaroid of described pressure sensitive adhesive and preparation method thereof, and relate to optical thin film that uses above-mentioned polaroid with pressure sensitive adhesive and preparation method thereof.More specifically, the present invention relates to be applicable to the pressure-sensitive adhesive for polarizing plates of polaroid, particularly with visual angle film spreading bonded polaroid or comprise the polaroid of lamination retardation film (retardation film) thereon, and above-mentioned polaroid can be applied on the liquid crystal cell with good tackiness, and thus obtained liquid crystal display is characterised in that, even also be not easy to produce light leak and can peel off easily when wrong when using at liquid crystal display described in high temperature and the high humidity environment, also relate to polaroid that has by above-mentioned pressure sensitive adhesive and preparation method thereof, and relate to optical thin film and preparation method thereof.
Background technology
Up to now, when the sheet material that will contain organic substance by pressure sensitive adhesive applications on such as the adherend of glass, pottery and metal the time, As time goes on, the unfavorable situation that can take place usually that the sheet material end is peeled off or be started.
In order to overcome above-mentioned unfavorable situation, use the molecular weight of the component of bond properties by improve forming pressure sensitive adhesive usually or raise its cross-linking density and enhanced is suppressed the sensitive adhesive material.Yet, above-mentioned when suppressing the sensitive adhesive material and making confinement capabilities obtain improveing when using, pressure sensitive adhesive can not change with the sheet material shrinkage that contains organic substance or the caused change of shape that expands in high temperature and high humidity environment, and this can cause producing multiple trouble.
On the other hand, wherein polaroid is applied to its lip-deep those adherends and is classified as optical element, its representative example comprises the have liquid crystal display liquid crystal cell of (LCD).Be described with reference to figure 1 hereinafter.
This liquid crystal cell 13 has following structure usually: wherein two the transparency electrode matrix with oriented layer that form are thereon arranged with the oriented layer that inwardly turns to, thereby obtain sealing by spacer formation appointed interval and its periphery, thereby liquid crystal material is placed in the above-mentioned interval, and wherein polaroid 11 is arranged on aforesaid two transparency electrode matrix by pressure sensitive adhesive 12 respectively.Usually; aforesaid polaroid comprises the light polarizing film (polarizing film) with three-decker; in this light polarizing film; optical isotropy film (optically isotropic film) for example tri acetyl cellulose (TAC) film is bonded on two surfaces of PVA-based polarizer; and on its another surface, further provide pressure sensitive adhesive layer, so that it is applied on optical element such as the liquid crystal cell.
In addition, shown in the synoptic diagram of Fig. 2, in some cases, in order to improve viewing angle characteristic, retardation film 24 is disposed between polaroid 21 and the liquid crystal cell 23 through pressure sensitive adhesive 22 and 25.
When the polaroid that will have as mentioned above structure is applied to optical element such as liquid crystal cell or polaroid is applied to retardation film, this can cause adopting the multilayered structure that contains multiple material and can lack dimensional stability, and particularly in high temperature and high humidity environment, can strengthen by the shrinkage and the dimensional change that is caused that expands.Usually with the aforesaid pressure sensitive adhesive of suppressing sensitive adhesive as above-mentioned polaroid, thus, mentioning and peeling off of causing can be inhibited by the polaroid dimensional change.Yet the stress that is produced by above-mentioned polaroid dimensional change can not be absorbed by pressure-sensitive adhesive layer, thereby can make that the unrelieved stress in the polaroid is inhomogeneous.This can cause producing some problems, may produce so-called " light leak " and " uneven color " takes place in stn liquid crystal in the TN liquid crystal cell.
In order to solve aforesaid problem, a kind of technology is disclosed in the prior art, wherein pressure sensitive adhesive has been carried out suitably softening, and by low molecular weight substance is joined in the pressure sensitive adhesive such as softening agent, make it have stress and relax performance (reference, for example patent documentation 1).Yet adherend was painted when the adding of low molecular weight substance had caused peeling off polaroid, in addition, had also reduced holding force, and was easy to as time goes by mention or peel off.
On the other hand, disclose in the prior art that to contain weight ratio by radiation-initiated crosslinking be 100: 1-100: 100 AP-52 (A) and in side chain, have the pressure-sensitive adhesive sheets (reference, for example patent documentation 2) that the mixture of the acrylic acid based polymer (B) of radiation polymerizable group obtains.
In above-mentioned patent documentation, described polaroid among the embodiment, but the sample size of measuring the light leak performance does not describe all in any embodiment.The inventor has measured the light leak performance of the polaroid of 15 inches sizes using pressure sensitive adhesive described in the above-mentioned patent documentation, and its result does not allow the people very satisfied.
As mentioned above, be used for the pressure sensitive adhesive of polaroid, be difficult to make bonding persistence and its leakproof optical property to be consistent, target of the present invention makes them be consistent exactly.
In the manufacturing step of liquid crystal display or the like, polaroid is applied to optical element such as liquid crystal cell on the time, when applying position deviation, in some cases, for the liquid crystal cell to costliness utilizes again, after applying, will have to soon polaroid is stripped down.In view of the above, even just need coated pressure sensitive adhesive on polaroid that it was applied to after liquid crystal cell the preceding paragraph time, all make the pressure sensitive adhesive that polaroid can strip down from liquid crystal cell relatively easily.
This be a kind of and enhancing adhesive strength to provide bonding persistent performance opposite performance, target of the present invention makes them be met simultaneously exactly.
Patent documentation 1: Japanese Patent JP3272921
Patent documentation 2: Japanese Patent Application Publication 107005/2001
Summary of the invention
According to as mentioned above, purpose of the present invention just provides the pressure-sensitive adhesive for polarizing plates that is applicable to polaroid, particularly be combined with the polaroid of visual angle film spreading or comprise the polaroid of lamination retardation film thereon, and can above-mentioned polaroid be applied on the liquid crystal cell with good binding property, in high temperature and high humidity environment, all be not easy to produce light leak even it is characterized in that the liquid-crystal display that obtains thus, even and described polaroid can remove (being called for short " removing " hereinafter) and the polaroid with above-mentioned pressure sensitive adhesive is provided from described liquid crystal cell easily after using for some time.
Has the polaroid pressure sensitive adhesive of characteristic as mentioned above in order to develop, the present inventor has carried out research repeatedly, find that above-mentioned purpose can be accomplished by following pressure-sensitive adhesive for polarizing plates, but described pressure sensitive adhesive can obtain by the pressure sensitive adhesive material that contains specific AP-52 and active-energy beam curing compound with activation evergy beam irradiation.
In addition, the present inventor finds to have as mentioned above the polaroid of pressure sensitive adhesive can effectively make by the following method: polaroid is applied on the pressure sensitive adhesive material layer that is arranged on the releasing sheet release layer and with active-energy beam irradiation releasing sheet side.
Finished the present invention based on above-mentioned cognition.
That is to say, the invention provides:
(1) pressure-sensitive adhesive for polarizing plates, described pressure sensitive adhesive is by containing (A) with activation evergy beam irradiation and pressure sensitive adhesive material (B) makes, described (A) accounts for monomer ratio 0.5 weight % or the lower monomeric acrylic acid based polymer with carboxyl (acrylic base polymer) for containing, described (B) but be active-energy beam solidified compound, and the storage modulus of elasticity of described pressure sensitive adhesive in the time of 23 ℃ (G ') is 0.3 MPa or higher.
(2) as above (1) described pressure-sensitive adhesive for polarizing plates, wherein, the storage modulus of elasticity of described pressure sensitive adhesive in the time of 23 ℃ (G ') be the 0.3-15 MPa,
(3) as above (1) or (2) described pressure-sensitive adhesive for polarizing plates, wherein, the storage modulus of elasticity of described pressure sensitive adhesive in the time of 80 ℃ (G ') be 0.3 MPa or higher,
(4) as above (3) described pressure-sensitive adhesive for polarizing plates, wherein, the storage modulus of elasticity of described pressure sensitive adhesive in the time of 80 ℃ (G ') be the 0.3-10 MPa,
(5) as above each described pressure-sensitive adhesive for polarizing plates in (1)-(4), wherein, described pressure sensitive adhesive is used for polaroid is applied to the liquid-crystalline glasses element,
(6) as above each described pressure-sensitive adhesive for polarizing plates in (1)-(5), wherein, described component (B) but active-energy beam solidified compound be molecular weight less than multifunctional (methyl) acrylate-based monomer of 1000,
(7) as above (6) described pressure-sensitive adhesive for polarizing plates, wherein, described multifunctional (methyl) acrylate-based monomer has ring texture,
(8) as above each described pressure-sensitive adhesive for polarizing plates in (1)-(7), wherein, described component (A) is mass ratio 100: 1-100 with the content ratio of component (B): 100,
(9) as above each described pressure-sensitive adhesive for polarizing plates in (1)-(8), wherein, described pressure sensitive adhesive material also comprises (C) linking agent,
(10) as above each described pressure-sensitive adhesive for polarizing plates in (1)-(9), wherein, described pressure sensitive adhesive material also comprises (D) silane coupling agent,
(11) as above each described pressure-sensitive adhesive for polarizing plates in (1)-(10), wherein, described pressure sensitive adhesive is 0.2-20 ox/25 millimeter to the bond strength of non-alkali glass,
(12) as above (11) described pressure-sensitive adhesive for polarizing plates, wherein, based on initial value, after using 168 hours, described pressure sensitive adhesive is 20% or lower to the rising percentage ratio of the bond strength of non-alkali glass,
(13) as above each described pressure-sensitive adhesive for polarizing plates in (1)-(12), wherein, with polaroid with 100 millimeters
2The area that applies of (10 millimeters * 10 millimeters) is applied on the non-alkali glass and measures under the shearing rate of 0.1 mm/min in the shear-type load, when distortion is 4000% or when lower, maximum shear load is 70 Ns or lower,
(1 4) are each described pressure-sensitive adhesive for polarizing plates in (1)-(13) as above, and wherein, the gel ratio is 85% or higher,
(15) have the polaroid of pressure sensitive adhesive, it is characterized in that, on polaroid, have the layer that contains each described pressure sensitive adhesive in above (1)-(14),
(16) as above (15) described preparation method with polaroid of pressure sensitive adhesive, this method comprises polaroid is administered on the pressure sensitive adhesive material layer that is arranged on the releasing sheet release layer, use subsequently activation evergy beam irradiation releasing sheet side and
(17) a kind of by being placed between two releasing sheets as each described pressure-sensitive adhesive for polarizing plates in above (1)-(14), make pressure sensitive adhesive contact and the pressure-sensitive adhesive sheets that makes with the release layer side of releasing sheet.
According to the present invention, the pressure-sensitive adhesive for polarizing plates that is applicable to polaroid can be provided, particularly be combined with the polaroid of visual angle film spreading or comprise the polaroid of lamination retardation film thereon, and described pressure sensitive adhesive can be applied to above-mentioned polaroid on the liquid crystal cell with good binding property, in high temperature and high humidity environment, all be not easy to produce light leak even it is characterized in that the liquid-crystal display that obtains thus, even and after using for some time, can peel off and provide polaroid from described liquid crystal cell easily with above-mentioned pressure sensitive adhesive.
In addition, according to the present invention, can provide effective formation to have the method for the polaroid of pressure sensitive adhesive as mentioned above.
Description of drawings
Fig. 1 is the synoptic diagram of expression LCD structure;
Fig. 2 is the synoptic diagram of expression LCD structure;
Fig. 3 is the method explanatory view that expression is used for measuring the light leak performance of the polaroid that is equipped with the pressure sensitive adhesive that is obtained in embodiment and Comparative Examples.
Description of reference numerals
1,2: liquid crystal display
11,21: polaroid
12,22,25: pressure sensitive adhesive
13,23: glass (liquid crystal cell)
24: retardation film
Embodiment
The pressure sensitive adhesive of the present invention that is used for polaroid is a pressure-sensitive adhesive for polarizing plates, described pressure-sensitive adhesive for polarizing plates is by comprising (A) with activation evergy beam irradiation and pressure sensitive adhesive material (B) prepares, wherein (A) but account for monomer component ratio 0.5 weight % or lower monomeric acrylic acid based polymer and (B) be active-energy beam solidified compound for containing with carboxyl.
Can be with the given acrylic acid based polymer of (methyl) acrylic ester polymer as component (A).In the present invention, (methyl) acrylate is meant acrylate and methacrylic ester.This statement also is used for other similar terms.Polymkeric substance is held concurrently and is referred to " homopolymer " and " multipolymer "
In the present invention, component (A) is characterised in that wherein to contain and accounts for monomer component ratio 0.5 weight % or the lower monomer with carboxyl.Usually, has the pressure sensitive adhesive of suppressing quick bond properties in order to provide, make the monomer of cross-linking set and (methyl) acrylate monomer copolymerization that does not have cross-linking set with carboxyl representative, thereby obtain (methyl) acrylate base co-polymer, and with this main agents as pressure sensitive adhesive.In contrast, acrylic acid based polymer (A) comprises that accounting for the monomer component ratio is 0.5 weight % or the lower monomer with carboxyl, and is preferably the polymkeric substance of (methyl) acrylate monomer with carboxyl.
The monomeric content that will have a carboxyl is controlled at 0.5 weight % or lowlyer can guarantees its removable property, this purpose of the present invention just.Monomer with carboxyl comprises (methyl) vinylformic acid, Ba Dousuan, toxilic acid and methylene-succinic acid.
Can be preferably that ester moiety alkyl is wherein had a polymkeric substance of (methyl) acrylate of 1-20 carbon atom is given as above-mentioned (methyl) acrylic ester polymer.Based on above-mentioned, wherein the example of ester moiety alkyl with (methyl) acrylate of 1-20 carbon atom comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid palm ester and (methyl) stearyl acrylate acyl octadecane ester.They can use separately or two or more are used in combination.
In above-claimed cpd, just form and be easy to control the molecular weight aspect in the polymer process, preferred especially (methyl) ethyl propenoate and (methyl) butyl acrylate.
Aforesaid (methyl) but acrylic ester polymer can contain the copolymerization component as constituent, as long as effect of the present invention do not suffer damage.Particularly, it is to have hydroxyl, amino and the amide group monomer as functional group, its specific examples comprises (methyl) vinylformic acid hydroxyalkyl acrylate, such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester and (methyl) vinylformic acid 4-hydroxyl butyl ester; Acrylamide is such as acrylamide, Methacrylamide, N methacrylamide, N-methyl acrylamide, N hydroxymethyl acrylamide and N-methylol methacrylamide; (methyl) vinylformic acid alkyl monosubstituted amino ester is such as (methyl) vinylformic acid monomethyl amino ethyl ester, (methyl) vinylformic acid list ethylamino ethyl ester, the amino propyl ester of (methyl) vinylformic acid monomethyl and (methyl) vinylformic acid list ethylamino propyl ester.Above-mentioned monomer can use separately or two or more are used in combination.
In above-mentioned pressure sensitive adhesive material, based on weight-average molecular weight, the molecular weight that is preferably used as (methyl) acrylic ester polymer of component (A) is 500000 or higher.If its weight-average molecular weight is 500000 or higher, the bonding and tackiness agent persistence of itself and adherend all is gratifying under high temperature and high humidity so, and can not produce and mention and peel off.Consider bonding and the tackiness agent persistence, preferred above-mentioned weight-average molecular weight is 1000000-2200000, preferred especially 1200000-2000000.Preferred expression weight-average molecular weight (Mw) is 20 or lower with the molecular weight distribution (Mw/Mn) of number-average molecular weight (Mn) ratio.If molecular weight distribution is 20 or lower, can obtain gratifying tackiness agent persistence so.
Aforesaid weight-average molecular weight and number-average molecular weight are the values that is converted into the polystyrene of measuring by gel permeation chromatography (GPC).
In above-mentioned pressure sensitive adhesive material, (methyl) acrylic ester polymer of component (A) can use separately or two or more are used in combination.
In pressure sensitive adhesive material of the present invention, preferably can with molecular weight less than multifunctional (methyl) acrylate-based monomer of 1000 given as component (B) but active-energy beam curing compound.
Above-mentioned molecular weight comprises less than multifunctional (methyl) acrylate-based monomer of 1000, for example, the acrylate-based monomer of difunctionality type (methyl), such as two (methyl) vinylformic acid 1,4-fourth diester, two (methyl) vinylformic acid 1, the own diester of 6-, two (methyl) vinylformic acid DOPCP, two (methyl) polyalkylene glycol acrylate ester, neopentyl glycol adipic acid two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, two (methyl) vinylformic acid, two ring pentyl esters, caprolactone modification two cyclopentyl two (methyl) acrylate, oxyethane modified phosphate two (methyl) acrylate, two (methyl) acrylyl oxy-ethyl isocyanuric acid ester, allylation cyclohexyl two (methyl) acrylate, tristane three methyl alcohol (methyl) acrylate, dihydroxymethyl two pentamethylene two (methyl) acrylate, oxyethane modification six hydrogen phthalandione two (methyl) acrylate, neopentyl glycol modification trimethyl propane two (methyl) acrylate, diamantane two (methyl) acrylate and 9,9-two [4-(2-acryloyl-oxy base oxethyl) phenyl] fluorenes; Trifunctional type (methyl) acrylate is such as trimethylolpropane tris (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, propionic acid modification Dipentaerythritol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate and three (methyl) acryloxy ethyl isocyanuric acid ester; Four functional-type (methyl) acrylate is such as four (methyl) vinylformic acid two glyceryl ester and four (methyl) vinylformic acid pentaerythritol ester; Five functional-type (methyl) acrylate is such as propionic acid modification Dipentaerythritol five (methyl) acrylate; With six functional-type (methyl) acrylate, such as Dipentaerythritol six (methyl) acrylate and caprolactone modification Dipentaerythritol six (methyl) acrylate.
In the present invention, only a kind of above-mentioned multifunctional (methyl) acrylate-based monomer can use separately or they can two kinds or more kinds of being used in combination.Among them, preferred those (methyl) acrylate that wherein in skeleton structure, have ring texture.Described ring texture can be carbocyclic ring structure or heterocycle structure, and can be single ring architecture or polynuclear plane.Being applicable to that above-mentioned multifunctional (methyl) is acrylate-based monomericly is, those multifunctional (methyl) acrylate-based monomers that for example have isocyanurate structure are such as two (methyl) acryloxy ethyl isocyanuric acid ester and three (methyl) acryloxy isocyanuric acid ester, dihydroxymethyl two pentamethylene two (methyl) acrylate, oxyethane modification six hydrogen phthalandione two (methyl) acrylate, tristane dimethanol (methyl) acrylate, neopentyl glycol modification TriMethylolPropane(TMP) two (methyl) acrylate and diamantane two (methyl) acrylate.
But the acrylate-based oligopolymer of active-energy beam curing type can be used as component (B).The weight-average molecular weight of preferred aforesaid propylene perester radical oligopolymer is 50000 or lower.The example of aforesaid propylene perester radical oligopolymer comprises polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, PBAA ester and siloxanes acrylate.
About in this respect, described polyester acrylic ester group oligopolymer can obtain by the following method, for example, by obtaining by the hydroxyl that has the polyester oligomer of hydroxyl at two ends that condensation between polycarboxylic acid and the polyvalent alcohol obtains with (methyl) acroleic acid esterification, perhaps obtain by the hydroxyl of usefulness (methyl) acroleic acid esterification by the oligomer end that alkylene oxide is added to polycarboxylic acid and obtains.Described epoxy acrylic ester group oligopolymer can obtain by the following method, for example, makes the oxyethane ring and the reaction of (methyl) vinylformic acid of low-molecular-weight relatively bisphenol A type epoxy resin or novolac-type Resins, epoxy, and it is carried out esterification.In addition, also can use epoxy acrylate oligomer by the carboxy-modified type that obtains with the partially modified above-mentioned epoxy acrylic ester group oligopolymer of dicarboxylic acid anhydride.Described urethane acrylate base oligopolymer can obtain by the following method, for example, can obtain by the hydroxyl of usefulness (methyl) acroleic acid esterification polyether glycol by making polyether glycol or polyester polyol and the polymeric polyisocyanate urethane oligomer that obtains of reaction and polyalcohol acrylate base oligopolymer with (methyl) acroleic acid esterification.
Based on the value that is converted into the standard polymethylmethacrylate, the weight-average molecular weight of preferred aforesaid acrylate-based oligopolymer is 50000 or lower, 500-50000 more preferably, and 3000-40000 more preferably.
Aforesaid propylene perester radical oligopolymer can use separately or two or more are used in combination.
In the present invention, adducts (adduct) the acrylate based polyalcohol that the group that wherein has (methyl) acryl is introduced in side chain also can be used as component (B).Above-mentioned adducts acrylate based polyalcohol can be by using the monomeric multipolymer that has functional group in (methyl) acrylate and the molecule as (methyl) acrylic ester polymer of component (A) described in, makes the part functional group of above-mentioned multipolymer and have (methyl) acryl and react with the compound of the group of above-mentioned functional group reactions and obtain.Based on the value that is converted into polystyrene, the weight-average molecular weight of above-mentioned adducts acrylate based polyalcohol is generally 500000-2000000.
In the present invention, can be with a kind of material that suitably is selected from aforesaid separately polyfunctional acrylic ester base monomer, acrylate-based oligopolymer and adducts acrylate based polyalcohol as component (B), perhaps can or more kinds ofly be selected from above-mentioned combinations of substances and use two kinds.
In the present invention, angle based on the performance of the pressure sensitive adhesive that obtains, the acrylate copolymer of preferred ingredient (A) and component (B) but the content ratio of active-energy beam curing compound be mass ratio 100: 1-100: 100, more preferably 100: 5-100: 50, and more preferably 100: 10-100: 40.
If necessary, the photopolymerization initiator can be joined in the pressure sensitive adhesive material of the present invention.Above-mentioned photopolymerization initiator comprises; for example; st-yrax; benzoin methyl ether; Benzoin ethyl ether; benzoin isopropyl ether; the st-yrax n-butyl ether; benzoin isobutyl butyl ether; methyl phenyl ketone; the dimethylamino benzoylformaldoxime; 2; 2-dimethoxy-2-phenyl methyl phenyl ketone; 2; 2-diethoxy-2-phenyl methyl phenyl ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-hydroxy-cyclohexyl benzophenone; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholine propane-1-ketone; 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone; benzophenone; to phenyl benzophenone; 4; 4 '-diethylamino benzophenone; dichloro benzophenone; 2-methylanthraquinone; 2-ethyl-anthraquinone; 2-tertiary butyl anthraquinone; the 2-aminoanthraquinone; 2-methyl thioxanthone; 2-ethyl thioxanthone; the 2-clopenthixal ketone; 2; 4-dimethyl thioxanthone; 2; the 4-diethyl thioxanthone; benzyl dimethyl ketal; the methyl phenyl ketone dimethyl ketal; the ESCAROL 507 ester; oligomeric [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone] and 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide.They can use separately or two or more are used in combination.Its combined amount is generally with respect to 100 parts of aforesaid components of every weight (B) and is the 0.2-20 weight part.
If necessary, the linking agent as component (C) can be joined in the pressure sensitive adhesive material of the present invention.Above-mentioned linking agent is clearly limited, can use and suitably be selected from any linking agent that is used as the linking agent of acrylic pressure sensitive adhesive usually up to now.Above-mentioned linking agent comprises, for example, polyisocyanate compounds, Resins, epoxy, melamine resin, urea resin, dialdehyde, methylol polymkeric substance, '-aziridino compound, metallo-chelate, metal alkoxide and metal-salt, and preferably use polyisocyanate compounds.
About in this respect, can be given be that aromatic polyisocyanate is such as tolylene diisocyanate as polyisocyanate compounds, diphenylmethanediisocyanate and inferior two methylene vulcabond, aliphatic polymeric isocyanate is such as hexamethylene diisocyanate, alicyclic polymeric isocyanate is such as isophorone diisocyanate and hydrogenated diphenyl methane diisocyanate, titration main body (buret bodies) and its isocyanuric acid ester main body with and with the lower molecular weight active hydrogen-contg compound such as ethylene glycol, propylene glycol, neopentyl glycol, the reaction product of TriMethylolPropane(TMP) and Viscotrol C add zoarium (adduct bodies).
In the present invention, aforesaid linking agent can use separately or two or more are used in combination.Though depend on the type of linking agent, with respect to the aforesaid components of per 100 weight parts (A) AP-52, the consumption of linking agent is generally the 0.01-20 weight part, preferred 0.1-10 weight part.
If necessary, the silane coupling agent as component (D) can be joined in the pressure sensitive adhesive material of the present invention.The adding of above-mentioned silane coupling agent, when making on polaroid being applied to for example the liquid-crystalline glasses element, bonding between pressure sensitive adhesive and the glass elements obtained promotion.Above-mentioned silane coupling agent is suitably has at least one alkoxysilyl and silicoorganic compound good compatible with pressure sensitive adhesive component and that have light transmission in the molecule, for example, be the compound of substantial transparent.With respect to per 100 weight part pressure sensitive adhesive material (total amount of component (A) and component (B)), the add-on of preferred above-mentioned silane coupling agent is the 0.001-10 weight part, is preferably the 0.005-5 weight part especially.
The specific examples of aforesaid silane coupling agent comprises that the silicon compound that contains polymerizable unsaturated group is such as vinyltrimethoxy silane, vinyltriethoxysilane and 3-methacryloxypropyl trimethoxy silane), silicon compound with epoxy construction is such as 3-glycidoxypropyltrime,hoxysilane and 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane contains amino silicon compound such as the 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330 and N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane and 3-r-chloropropyl trimethoxyl silane.They can use separately or two or more are used in combination.
The pressure sensitive adhesive of the present invention that is used for polaroid is by preparing with the as above resulting above-mentioned pressure sensitive adhesive material of activation evergy beam irradiation.
Described activation evergy beam comprises, for example, and ultraviolet ray (UV ray) and electron beam.Aforesaid UV ray obtains by high voltage mercury lamp, electrodeless lamp and xenon lamp.On the other hand, described electron beam obtains by electron-beam accelerator.In above-mentioned activation evergy beam, the UV ray is suitable especially.When using electron beam, do not need to add the photopolymerization initiator and can form described pressure sensitive adhesive.
Quantity of X-rays X to the activation evergy beam of irradiation on above-mentioned pressure sensitive adhesive material is suitably selected, thereby can obtain having aforesaid storage modulus of elasticity and as mentioned above to the pressure sensitive adhesive of non-alkali glass bond strength.In the situation of using the UV ray, preferred illuminating value be the 50-1000 milliwatt/centimetre
2, and preferred light quantity (light quantity) be 50-1000 milli Jiao/centimetre
2In the situation of using electron beam, be preferably 10-1000 kilorad (krad).
In order to strengthen bonding between bonding coat and the polaroid, adhesion enhancer (adhesionimproving agent) can be joined in the pressure sensitive adhesive material of the present invention.Described adhesion enhancer comprises that aromatic polyisocyanate is such as tolylene diisocyanate, diphenylmethanediisocyanate and inferior two methylene vulcabond with such as being aromaticity polymeric polyisocyanate as mentioned above and the polyisocyanate compounds that add zoarium of lower molecular weight active hydrogen-contg compound such as the reaction product of ethylene glycol, propylene glycol, neopentyl glycol, TriMethylolPropane(TMP) and Viscotrol C.When functional group was present in the acrylic acid based polymer in the pressure sensitive adhesive material, above-mentioned polyisocyanate compounds played aforesaid linking agent.
In the time of 23 ℃, and the storage modulus of elasticity of pressure sensitive adhesive of the present invention (G ') be 0.3 MPa or higher.If the storage modulus of elasticity (G ') be 0.3 MPa or higher, so just can obtain satisfied leakproof optical property.In the time of 23 ℃, the upper limit of storage modulus of elasticity (G ') is not clearly limited, but have better bonding persistent pressure sensitive adhesive in order to obtain, be preferably 50 MPas or lower, more preferably 15 MPas or lower.Based on aforesaid viewpoint, during particularly preferably in 23 ℃, described storage modulus of elasticity (G ') be the 0.35-12 MPa, most preferably be the 0.5-5 MPa.Usually, preferably in the time of 80 ℃, described storage modulus of elasticity (G ') is 0.3 MPa or higher, 0.3-10 MPa more preferably, and be preferably the 0.3-3 MPa especially.
Aforesaid storage modulus of elasticity (G ') be the value of measuring by the following method.
The measuring method of＜storage modulus of elasticity (G ') 〉
To thickness is that 30 microns pressure sensitive adhesive carries out lamination, thereby prepares the cylindrical test piece of 8 millimeters Φ * 3 millimeter thickness, by the torsional shear method it is stored modulus of elasticity (G ') under the following conditions and measures.
Surveying instrument: the dynamic viscoelastic surveying instrument " DYNAMICANALYZER RDAII " that Rheometric Corporation makes
Frequency: 1 hertz
Temperature: 23 ℃ and 80 ℃
Be used for the pressure sensitive adhesive of the present invention of polaroid, preferably its bond strength to non-alkali glass is 0.2-20 ox/25 millimeter.If bond strength is 0.2 N/25 millimeters or higher, polaroid can for example be applied on the liquid-crystalline glasses element with gratifying bond strength so.On the other hand, if above-mentioned bond strength is 20 Ns/25 millimeters or lower, so just can liquid crystal cell not produced removing of infringement.In this case, described bond strength is 24 hours bond strengths afterwards of application, and hereinafter, is expressed as initial value with using 24 hours bond strengths afterwards.Aforesaid bond strength is the value of measuring by the following method.
＜to the bond strength of non-alkali glass 〉
With width is that 25 millimeters and length are that 100 millimeters sample excises from the polaroid with pressure sensitive adhesive, thereby peel off releasing sheet (thickness of bonding coat: 25 microns) thus, and polaroid is applied to non-alkali glass (" 1737 " that Corning Incorporated makes), under 0.5 MPa and 50 ℃ of conditions, in the autoclave that Kurihara Manufactory Inc. makes, it was carried out pressure treatment 20 minutes then.After this, being 23 ℃ in envrionment temperature is 50% time with relative humidity, it was placed 24 hours, then in above-mentioned environment, at detachment rate is that 300 mm/min and peel angle are under 180 °, (Orientech Co., the Tensilon that Ltd. makes) measures its bond strength by tensile testing machine.
In addition, being used for the pressure sensitive adhesive of the present invention of polaroid, after using 168 hours, is 20% or lower to the bond strength of non-alkali glass with respect to initial value rising percentage ratio.If rising percentage ratio is 20% or lower, so just can obtain satisfied removable property.
Be used for the pressure sensitive adhesive of the present invention of polaroid, with polaroid with 100 millimeters
2The application area of (10 millimeters * 10 millimeters) is applied on the non-alkali glass and is when measuring shear-loaded under 0.1 mm/min in shearing rate, is 4000% or when lower, the maximum shear load is preferably 70 Ns or lower in torsion resistance.If the maximum shear load is 70 Ns or lower, can obtain gratifying removable property so.More preferably the maximum shear load is the 10-50 ox.
Aforesaid maximum shear load is the value of measuring by the following method.
The measuring method of＜maximum shear load 〉
With width is that 10 millimeters and length are that 100 millimeters sample excises from the polaroid with pressure sensitive adhesive, thereby peel off releasing sheet (thickness of bonding coat: 25 microns) thus, and polaroid is applied to non-alkali glass (" 1737 " that Corning Incorporated makes), thereby make that using area is 10 millimeters * 10 millimeters, under 0.5 MPa and 50 ℃ of conditions, in the autoclave that Kurihara Manufactory Inc. makes, it was carried out pressure treatment 20 minutes then.After this, be under 50% the environment it to be placed 24 hours 23 ℃ and relative humidity, then in above-mentioned environment, with in the non-alkali glass not in the terminal portions of a side of application of samples and the sample terminal portions of non-application side be fixed on the tensile testing machine (making) by Instron Corporation, and under the shearing rate of 0.1 mm/min, it is drawn to shear direction, thereby measure its load.Described measurement is carried out (deflection on shear direction: 1000 microns) under up to 4000% twist angle, and distortion is reached 4000% o'clock overall loading is set at the maximum shear load.Torsion resistance is represented by the ratio of deflection on the shear direction and bondline thickness.
The gel ratio of preferred pressure sensitive adhesive of the present invention is 85% or higher.In other words, when being hanged down by the degree of the lower-molecular-weight component of organic solvent extraction, in heating or high temperature and high humidity environment, mention, peel off and all smaller from adherend painted (stain) of adherend, and the gel ratio be 85% or higher pressure sensitive adhesive have long-term persistence and high stability.More preferably the gel ratio is 90-99.9%.
If necessary, can with the multiple additive that is generally used for the acrylic pressure sensitive adhesive for example tackifier, antioxidant, UV absorption agent, photostabilizer, tenderizer and filler or the like join in the pressure sensitive adhesive of the present invention, as long as purpose of the present invention is without prejudice.
The pressure sensitive adhesive of the present invention that is used for polaroid can be applied to include only the polaroid of light polarizing film, and above-mentioned polaroid can be used for above-mentioned polaroid is applied to for example liquid-crystalline glasses element.Particularly, pressure sensitive adhesive applications to light polarizing film wherein is combined with on the polaroid of visual angle film spreading, and preferably above-mentioned polaroid can be used for above-mentioned polaroid is applied to, for example, on the liquid-crystalline glasses element.
Wherein the light polarizing film above-mentioned polaroid that is combined with the visual angle film spreading comprises, for example, polaroid that forms comprising the visual angle the planning function layer of plate-like (discotic) liquid crystal surface by the coating light polarizing film and the polaroid that wherein is pasted with the visual angle film spreading on surface of above-mentioned polaroid with tackiness agent, wherein said polarizing coating is by preparing on two surfaces that triacetyl cellulose (TAC) film sticked on PVA-based polarizer (polarizer) respectively.In this case, pressure sensitive adhesive is provided at visual angle the planning function layer one side or aforesaid visual angle film spreading one side.
Equally, when having retardation film between polaroid and liquid-crystalline glasses element, as shown in Figure 2, the pressure sensitive adhesive of the present invention that is used for polaroid can use suitably.That is, the polaroid that includes only light polarizing film is applied on the retardation film with pressure sensitive adhesive of the present invention, thereby forms optical thin film and the retardation film of above-mentioned optical thin film is applied on the liquid-crystalline glasses element with pressure sensitive adhesive.Just in this respect, retardation film is applied to the not special restriction of pressure sensitive adhesive on the liquid-crystalline glasses element, can uses to be generally used for polaroid is applied to pressure sensitive adhesive on the liquid-crystalline glasses element being used for.Particularly, described pressure sensitive adhesive comprises the contact adhesive composition that contains acrylic acid based polymer, linking agent and be disclosed in the silane compound in the Japanese Patent Application Publication 131033/1999.Pressure sensitive adhesive of the present invention also can be used for polaroid is applied to the liquid-crystalline glasses element.
The pressure sensitive adhesive of the present invention that is used for polaroid by use is applied to polaroid the liquid-crystal display for preparing on liquid-crystalline glasses element or the retarder film according to mode as mentioned above, even in high temperature and high humidity environment, all be difficult for producing light leak, and in addition, itself and polaroid and liquid-crystalline glasses element have good bonding persistence.
In addition, the invention provides and on polaroid, have the aforesaid polaroid that is used for the pressure sensitive adhesive of the present invention of polaroid with pressure sensitive adhesive.As mentioned above, above-mentioned polaroid can be for including only the polaroid of polarizing coating, and still in the situation of structure shown in Figure 1, preferred wherein light polarizing film is combined with the polaroid of visual angle film spreading.
The thickness that comprises the above-mentioned layer of the pressure sensitive adhesive that is used for polaroid is generally the 5-100 micron, is preferably the 10-50 micron, and 10-30 micron more preferably.
Prepare above-mentioned method and can be any method, be provided on the polaroid, this is had no particular limits as long as comprise the layer of pressure sensitive adhesive of the present invention with polaroid of pressure sensitive adhesive.According to the inventive method as follows, can effectively make required polaroid with pressure sensitive adhesive.
In the methods of the invention, polaroid is applied on the pressure sensitive adhesive material layer that is arranged on the releasing sheet release layer, use the side of the above-mentioned releasing sheet of activation evergy beam irradiation then, thereby make the pressure sensitive adhesive material layer change into to have the layer that forms by pressure sensitive adhesive structure of the present invention of specified characteristic as mentioned above, can obtain the polaroid that the present invention has pressure sensitive adhesive thus.
Aforesaid releasing sheet comprises by releasing agent is coated in the sheet material for preparing on the polyolefin film of plastics film such as the polyester film of polyethylene terephthalate, polybutylene terephthalate or poly-naphthoic acid second diester or the like and polypropylene or polyethylene or the like such as silicone resin, thereby release layer is provided.Thickness to above-mentioned release layer does not clearly limit, and is generally the 20-150 micron.
The radiation parameter of pressure sensitive adhesive material and activation evergy beam is illustrated at the aforesaid pressure sensitive adhesive of the present invention that is used for polaroid.
Can be used for the method that the pressure sensitive adhesive material layer is provided on the demoulding synusia be, for example following method wherein is coated with method (knife coating method), print roll coating method (roll coating method), spread coating (blade coating method), die coating method (diecoating method) and intaglio plate coating method (gravure coating method) by bar coating process (bar coating method), scraper pressure sensitive adhesive material is applied to form coated membrane and the gained coated membrane is carried out the exsiccant method.Drying conditions is not clearly limited, normally following dry 10 seconds to 10 minutes at 50-150 ℃.
In the situation of structure shown in Figure 1, polaroid includes only polarizing coating in many cases, and comprises that the layer of pressure-sensitive adhesive for polarizing plates has and identical as mentioned above thickness.The method that structure shown in the shop print 1 has the polaroid of pressure sensitive adhesive can be any method, as long as can obtain the polaroid that it is provided with the layer that comprises pressure sensitive adhesive of the present invention, and it is not clearly limited.Can effectively prepare polaroid by aforesaid preparation method of the present invention.
In addition, in the situation of constructing shown in Fig. 2, be provided with the pressure-sensitive adhesive sheets of pressure-sensitive adhesive for polarizing plates as mentioned above in advance in the middle of the preparation, make it contact, and above-mentioned pressure-sensitive adhesive sheets can be used for polaroid is applied in retarder film with the release layer side of two releasing sheets.In this case, when aforesaid component (B) is used as pressure sensitive adhesive, after getting involved pressure sensitive adhesive between two releasing sheets, can carry out activation evergy beam irradiation, perhaps pressure sensitive adhesive is provided on the releasing sheet, with with the activation evergy beam it is carried out irradiation, then it is got involved another releasing sheet.Radiation parameter to the activation evergy beam is selected, thereby obtains to have the layer that is formed by pressure sensitive adhesive structure of the present invention of specified characteristic as mentioned above.
When above-mentioned pressure-sensitive adhesive sheets is used for production optical thin film of the present invention, by ordinary method the releasing sheet of pressure-sensitive adhesive sheets is peeled off, and pressure-sensitive adhesive sheets is applied on the polaroid.
Embodiment
Next, the present invention more at large illustrates below with reference to embodiment, still, should not limit the invention to these embodiment.
The pressure sensitive adhesive that obtains in embodiment 1-7 and Comparative Examples 1 and 2 is measured by method as follows with the performance with polaroid of pressure sensitive adhesive.
(1) the storage modulus of elasticity of pressure sensitive adhesive
Under 23 ℃ and 80 ℃, the described method of specification sheets is measured the storage modulus of elasticity according to the present invention.
(2) bond strength (to the bond strength of non-alkali glass)
The described method of specification sheets is measured the bonding of non-alkali glass tackiness agent according to the present invention.
(3) maximum shear load
Specification sheets is described according to the present invention, and the maximum shear load that reached for 4000% when distortion is measured.
(4) has the persistence of the polaroid of pressure sensitive adhesive
By cutting unit (by OGINO SEIKI CO., LTD. the Super Cutter " PN1-600 " of Zhi Zaoing), the polaroid that will have pressure sensitive adhesive is adjusted to 233 millimeters * 309 millimeters of sizes, under 0.5 MPa and 50 ℃, in the autoclave that Kurihara Manufactory Inc. makes, it was pressurizeed 20 minutes then.Then, be placed in the environment of following corresponding permanence condition, and after 200 hours, it observed, thereby estimate its persistence according to following judge index by the magnifying glass of 10 x magnifications.
Zero:, indefectible in 0.6 millimeter of four tangential terminal portions in lateral outside of distance or farther place;
△: in 0.6 millimeter of four tangential terminal portions in lateral any one lateral outside of distance or farther place, the unusual apparent state of pressure sensitive adhesive such as mention, peel off, under foaming or the striped, flaw is less than 0.1 millimeter;
*: in 0.6 millimeter of four tangential terminal portions in lateral any one lateral outside of distance or farther place, the unusual apparent state of pressure sensitive adhesive such as mention, peel off, under foaming or the striped, flaw is 0.1 millimeter or bigger
＜permanence condition 〉
60 ℃ and relative humidity are 90% environment, 80 ℃ dry environment, 90 ℃ dry environment
Thermal shock test (heat shock test) respectively carried out 30 minutes for 60 ℃ at-20 ℃ of , carried out 200 cycles
(5) light leak performance
By cutting unit (by OGINO SEIKI CO., LTD. the Super Cutter " PN1-600 " of Zhi Zaoing), the polaroid that will have pressure sensitive adhesive is adjusted to 233 millimeters * 309 millimeters of sizes, under 0.5 MPa and 50 ℃, in the autoclave that Kurihara Manufactory Inc. makes, it was pressurizeed 20 minutes then.The polaroid that will have pressure sensitive adhesive is applied to the front side and the rear side of non-alkali glass, thereby has the polaxis that passes the Nicol prism state.Under 80 ℃, be placed on this state following 200 hours.Then, be placed on 23 ℃ and relative humidity and be in 50% the environment 2 hours, thereby under above-mentioned environment, measure its light leak performance by method shown below.
By OTSUKA ELECTRONICS CO., the MCPD-2000 that LTD. makes is used to measure the light and the luminance difference Δ L of respective area shown in Fig. 3
*Determine by following equation:
ΔL
*＝[(b+c+d+e)/4]-a
(wherein a, b, c, d and e are respectively predefined test point in a-quadrant, B zone, C zone, D zone and the E zone (at's a point of regional center position separately) light separately) and its expression light leak performance.Can show Δ L in view of the above
*Be worth more for a short time, light leak is just more little, and usually, if its value less than 4.0, this polaroid can be used for liquid-crystal display so.
(6) gel ratio
With thickness be 25 microns pressure sensitive adhesive make the sample that is of a size of 80 millimeters * 80 millimeters and with its sieve with polyester manufacture (mesh size: 200) parcel, thereby by the precision balance accurate weight of weighing pressure sensitive adhesive only.Its weight is set at M1.Use the Soxhlet extractor that pressure sensitive adhesive is immersed in the ethyl acetate solvent, and this solvent is refluxed, thereby handle 16 hours.Then, above-mentioned pressure sensitive adhesive is taken out, in the environment of 23 ℃ of temperature and relative humidity 50%, in air, is dried 24 hours, and in 80 ℃ baking oven with its further dry 12 hours.By precision balance, pressure sensitive adhesive weight after the drying is weighed.Its weight is set at M2.Gel ratio (%) is represented by (M2/M1) * 100.
Embodiment 1-7 and Comparative Examples 1 and 2
Preparation is to having shown in the table 1 pressure sensitive adhesive material (a) of forming (being converted into solids content), and toluene is added wherein as solvent, thereby obtains the coating solution that solids content is adjusted to 20 weight %.By knife coater above-mentioned coating solution being coated in thickness is on 38 microns the release layer by the mold release film of polyethylene terephthalate preparation as releasing sheet, thereby make its thickness be 25 microns after drying, be dried at 90 ℃ then and handled one minute, thereby form the pressure sensitive adhesive material layer.
Then, will comprise that the polaroid of the light polarizing film that is equipped with the discotic mesogenic layer is applied on the described pressure sensitive adhesive material layer, thereby make the pressure sensitive adhesive material layer touch described discotic mesogenic layer.After using 30 minutes, with the UV ray irradiation is carried out in the mould release film side under the following conditions, thereby form polaroid with pressure sensitive adhesive.The thickness of gained pressure sensitive adhesive layer is 25 microns.
＜UV radiation parameter 〉
Use the electrodeless lamp of H valve, by Fusion Co., Ltd. makes
Illuminating value: 600 milliwatts/centimetre
2, light quantity: 1 50 milli Jiao/centimetre
2
With EYEGRAPHICS Co., " UVPF-36 " that Ltd. makes is as UV illuminating value and actinometry instrument.
Pressure sensitive adhesive the results are shown in the table 2 with the performance measurement with polaroid of pressure sensitive adhesive.
Table 1
| The composition of pressure sensitive adhesive material (a) | |||||||||
| Acrylic acid based polymer (A) | Multifunctional acrylic monomer (B) | Photo-induced polymerization initiator 7)(weight part) | Polyisocyanate compounds (C) 8)(weight part) | Silane coupling agent (D) 9)(weight part) | |||||
| Kind | Weight-average molecular weight (Mw) | Molecular weight distribution (Mw/Mn) | Amount (weight part) | Kind | Amount (weight ratio) | ||||
| Embodiment 1 | BA 1) | 1800000 | 4.06 | 100 | M-315 5) | 15 | 1.5 | 4 | 0.1 |
| Embodiment 2 | BA | 1800000 | 4.06 | 100 | M-315 | 15 | 1.5 | 8 | 0.1 |
| Embodiment 3 | BA | 1800000 | 4.06 | 100 | M-315 | 20 | 1.5 | 4 | 0.1 |
| Embodiment 4 | BA | 1800000 | 4.06 | 100 | R-684 6) | 24 | 1.5 | 4 | 0.1 |
| Embodiment 5 | BA | 1800000 | 4.06 | 100 | M-315 | 15 | 1.5 | 0 | 0.1 |
| Embodiment 6 | BA/AA 2)(99.8/0.2) | 1800000 | 4.22 | 100 | M-315 | 15 | 1.5 | 4 | 0.1 |
| Embodiment 7 | BA/AA 3)(99.5/0.5) | 1800000 | 4.44 | 100 | M-315 | 15 | 1.5 | 4 | 0.1 |
| Comparative Examples 1 | BA | 1800000 | 4.06 | 100 | - | 0 | - | 0 | 0.1 |
| Comparative Examples 2 | BA/A 4)(99/1) | 1800000 | 4.50 | 100 | M-315 | 15 | 1.5 | 4 | 0.1 |
Remarks:
1) BA: butyl acrylate polymkeric substance
2) BA/AA: butyl acrylate and acrylic copolymer (weight ratio 99.8/0.2)
3) BA/AA: butyl acrylate and acrylic copolymer (weight ratio 99.5/0.5)
4) BA/AA: butyl acrylate and acrylic copolymer (weight ratio 99/1)
5) M-315: three (acrylyl oxy-ethyl) isocyanuric acid ester, molecular weight=423, the trifunctional type (trade(brand)name: Aronix M-315, by Toagosei Co., Ltd. makes)
6) R-684: tristane dihydroxymethyl acrylate (by Nippon Kayaku Co., Ltd. makes for " KAYARAD R-684 ", molecular weight=336)
7) photopolymerization initiator: benzophenone and 1-hydroxy-cyclohexyl benzophenone weight ratio are 1: 1 mixture, " Irgacure 500 ", and by Ciba Specialty Chemicals Co., Ltd. makes
8) polyisocyanate compounds (linking agent, adhesion enhancer): the tolylene diisocyanate of trishydroxymethyl modification (" Coronate " L, by NIPPON POLYURETHANE INDUSTRY CO., LTD. makes)
9) silane coupling agent: 3-glycidoxy-propyltrimethoxy silane (" KBM-403 ", by Shin-EtsuChemical Co., Ltd. makes)
Table 2
| The performance of pressure sensitive adhesive | Performance with polaroid of pressure sensitive adhesive | |||||||||||
| Storage modulus of elasticity (MPa) | Bond strength (ox/25 millimeter) | Gel ratio (%) | Maximum shear load (ox) | Persistence | Light leak performance [Δ L *] | |||||||
| 23℃ | 80℃ | 24 hours (initial value) | 168 hours | Rate of rise (%) | 60℃90％RH | 80 ℃ of dryings | 90 ℃ of dryings | Thermal shocking | ||||
| Embodiment 1 | 0.94 | 0.43 | 15 | 16 | 6.7 | 96 | 23 | ○ | ○ | ○ | ○ | 0.56 |
| Embodiment 2 | 2.34 | 1.07 | 5 | 5 | 0 | 95 | 21 | ○ | ○ | ○ | ○ | 0.52 |
| Embodiment 3 | 1.41 | 0.63 | 6 | 7 | 16.7 | 94 | 30 | ○ | ○ | ○ | ○ | 0.36 |
| Embodiment 4 | 0.95 | 0.41 | 10 | 10 | 0 | 91 | 34 | ○ | ○ | ○ | ○ | 0.48 |
| Embodiment 5 | 1.2 | 0.71 | 3.5 | 4 | 14.3 | 98 | 20 | ○ | △ | ○ | △ | 1.49 |
| Embodiment 6 | 1.31 | 0.66 | 5 | 5.5 | 10.0 | 97 | 32 | ○ | ○ | ○ | △ | 0.78 |
| Embodiment 7 | 1.31 | 0.66 | 16 | 18.9 | 18.0 | 96 | 36 | △ | ○ | △ | △ | 0.78 |
| Comparative Examples 1 | 0.11 | 0.09 | 7 | 7 | 0 | 2 | 8 | × | × | × | × | 0.39 |
| Comparative Examples 2 | 0.87 | 0.73 | 21.5 | 42 | 95.3 | 96 | 58 | ○ | ○ | ○ | ○ | 0.88 |
Industrial applicibility
The contact adhesive of the present invention that is used for polarizing plate is fit to be applied to polarizing plate, particularly be combined with the polarizing plate of visual angle film spreading or comprise the polarizing plate of lamination retarder film thereon, and can be with good bonding being applied on the above-mentioned polarizing plate, contact adhesive of the present invention is characterised in that, even thus obtained LCDs in high temperature and high humidity environment, also is not easy to produce light leak. When application site departed from, even after using a period of time, described polarizing plate also can be peeled off, and expensive liquid crystal cell can be used again.
Claims (17)
1, a kind of pressure-sensitive adhesive for polarizing plates, this pressure sensitive adhesive is by containing (A) with activation evergy beam irradiation and pressure sensitive adhesive material (B) makes, described (A) accounts for monomer ratio 0.5 weight % or the lower monomeric acrylic acid based polymer with carboxyl for containing, described (B) but be active-energy beam curing compound, and the storage modulus of elasticity G ' of described pressure sensitive adhesive in the time of 23 ℃ is 0.3 MPa or higher.
2, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, the storage modulus of elasticity G ' of described pressure sensitive adhesive in the time of 23 ℃ is the 0.3-15 MPa.
3, pressure-sensitive adhesive for polarizing plates as claimed in claim 1 or 2, wherein, the storage modulus of elasticity G ' of described pressure sensitive adhesive in the time of 80 ℃ is 0.3 MPa or higher.
4, pressure-sensitive adhesive for polarizing plates as claimed in claim 3, wherein, the storage modulus of elasticity G ' of described pressure sensitive adhesive in the time of 80 ℃ is the 0.3-10 MPa.
5, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, described pressure sensitive adhesive is used for polaroid is applied to the liquid-crystalline glasses element.
6, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, described component (B) but active-energy beam curing compound be molecular weight less than multifunctional (methyl) acrylate-based monomer of 1000.
7, pressure-sensitive adhesive for polarizing plates as claimed in claim 6, wherein, described multifunctional (methyl) acrylate-based monomer has ring texture.
8, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, described component (A) is weight ratio 100: 1-100 with the content ratio of component (B): 100.
9, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, described pressure sensitive adhesive material further comprises (C) linking agent.
10, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, described pressure sensitive adhesive material further comprises (D) silane coupling agent.
11, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, described pressure sensitive adhesive is 0.2-20 ox/25 millimeter to the bond strength of non-alkali glass.
12, pressure-sensitive adhesive for polarizing plates as claimed in claim 11, wherein, based on initial value, after using 168 hours, described pressure sensitive adhesive is 20% or lower to the rising percentage ratio of the bond strength of non-alkali glass.
13, pressure-sensitive adhesive for polarizing plates as claimed in claim 1; wherein; be applied to non-alkali glass on 10 millimeters * 10 millimeters application area polaroid and be when measuring shear-loaded under 0.1 mm/min in shearing rate; in torsion resistance is 4000% or when lower, the maximum shear load is 70 Ns or lower.
14, pressure-sensitive adhesive for polarizing plates as claimed in claim 1, wherein, the gel ratio is 85% or higher.
15, a kind of polaroid with pressure sensitive adhesive is characterized in that, has the layer that comprises pressure sensitive adhesive as claimed in claim 1 on polaroid.
16, the preparation method with polaroid of pressure sensitive adhesive as claimed in claim 15, this method comprises polaroid is applied on the pressure sensitive adhesive material layer that is arranged on the releasing sheet release layer, uses activation evergy beam irradiation releasing sheet side then.
17, a kind of pressure-sensitive adhesive sheets, this sheet material be by being placed on pressure-sensitive adhesive for polarizing plates as claimed in claim 1 between two releasing sheets, thereby make pressure sensitive adhesive contact with the release layer side of releasing sheet.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005373147 | 2005-12-26 | ||
| JP2005373147 | 2005-12-26 | ||
| JP2006203582 | 2006-07-26 |
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| Publication Number | Publication Date |
|---|---|
| CN1990802A true CN1990802A (en) | 2007-07-04 |
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ID=38213348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610161799 Pending CN1990802A (en) | 2005-12-26 | 2006-12-25 | Pressure-sensitive adhesive for polarizing plates, polarizing plate with pressure-sensitive adhesive and production process for the same |
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| CN (1) | CN1990802A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423736B (en) * | 2007-11-02 | 2011-07-06 | 日东电工株式会社 | Pressure-sensitive adhesive optical film, production method thereof, and image display |
| CN102257087A (en) * | 2008-12-18 | 2011-11-23 | Lg化学株式会社 | Adhesive composition, polarizing plate and liquid crystal display device |
| CN103314065A (en) * | 2010-12-31 | 2013-09-18 | 第一毛织株式会社 | Adhesive composition for polarizer, and polarizer having same |
-
2006
- 2006-12-25 CN CN 200610161799 patent/CN1990802A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423736B (en) * | 2007-11-02 | 2011-07-06 | 日东电工株式会社 | Pressure-sensitive adhesive optical film, production method thereof, and image display |
| CN102257087A (en) * | 2008-12-18 | 2011-11-23 | Lg化学株式会社 | Adhesive composition, polarizing plate and liquid crystal display device |
| CN102257087B (en) * | 2008-12-18 | 2014-04-09 | Lg化学株式会社 | Adhesive composition, polarizing plate and liquid crystal display device |
| TWI460240B (en) * | 2008-12-18 | 2014-11-11 | Lg Chemical Ltd | Pressure-sensitive adhesive composition, polarizing plate, and liquid crystal display |
| US9816016B2 (en) | 2008-12-18 | 2017-11-14 | Lg Chem, Ltd. | Adhesive composition, polarizing plate and liquid crystal display device |
| CN103314065A (en) * | 2010-12-31 | 2013-09-18 | 第一毛织株式会社 | Adhesive composition for polarizer, and polarizer having same |
| CN103314065B (en) * | 2010-12-31 | 2015-12-16 | 第一毛织株式会社 | For binder composition and the polaroid comprising said composition of polaroid |
| US9593268B2 (en) | 2010-12-31 | 2017-03-14 | Cheil Industries, Inc. | Adhesive composition for polarizing plate and polarizing plate prepared using the same |
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