CN101258214A - Acrylic pressure-sensitive adhesive composition for polarizing film - Google Patents
Acrylic pressure-sensitive adhesive composition for polarizing film Download PDFInfo
- Publication number
- CN101258214A CN101258214A CNA2006800325026A CN200680032502A CN101258214A CN 101258214 A CN101258214 A CN 101258214A CN A2006800325026 A CNA2006800325026 A CN A2006800325026A CN 200680032502 A CN200680032502 A CN 200680032502A CN 101258214 A CN101258214 A CN 101258214A
- Authority
- CN
- China
- Prior art keywords
- methyl
- sensitive adhesive
- acrylic
- adhesive composition
- polarizing film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Adhesive Tapes (AREA)
Abstract
The present invention relates to an acrylic pressure sensitive adhesive composition comprising (meth)acrylic copolymers including alkyl(meth)acrylic acid ester monomer having 1-12 carbon atoms of alkyl group, characterized in that the gel content is 10-55%, the swelling ratio is 30-110, the weight average molecular weight of sol eluted from the adhesive by ethyl acetate is at least 800,000, the molecular weight distribution is 2.0-7.0; and a polarizer and a liquid crystal display comprising the above composition show excellent durability under a high temperature and humidity condition, and can improve the light leakage phenomenon and provide excellent operability at the time of manufacturing polarizer by effectively providing high modulus and stress release property.
Description
Technical field
The present invention relates to be used for the acrylic pressure-sensitive adhesive composition of light polarizing film.Particularly, the present invention relates to have excellent durability, low light leak and under high temperature and/or humidity condition the acrylic pressure-sensitive adhesive composition of enhanced operability, and polarizer and comprise the liquid-crystal display of this polarizer.
Background technology
Usually,, need to comprise the liquid crystal cells and the light polarizing film of liquid crystal basically, and should use and be used to adhere to above both binder layer or pressure sensitive adhesive layer in order to make liquid-crystal display.In addition, can further phase retardation film, the compensate film that is used for wide visual angle, brightness enhancement film etc. be adhered to light polarizing film, to improve the performance of liquid-crystal display.
Typically, liquid-crystal display comprises evenly distributed liquid crystal layer, comprises light polarizing film, phase retardation film and the other functional film layer of binder layer or pressure sensitive adhesive layer.
Light polarizing film comprises evenly distributed iodine compound or dichroic polarisation material.In order to protect these polarization elements, be used to constitute multilayer such as the protective membrane of tri acetyl cellulose (TAC) etc.Light polarizing film may further include phase retardation film with anisotropic molecule arrangement or compensate film such as the liquid crystal film that is used for wide visual angle.
Above-mentioned film is made by the material that has different molecular structures and form, so have different physicalies.Particularly, under high temperature and/or humidity condition, not enough according to the contraction or the expansible dimensional stability of material with anisotropic molecule arrangement.Consequently, if light polarizing film fixes by pressure sensitive adhesive, then the caused shear-stress of contraction or expansion by light polarizing film under high temperature and/or humidity condition is held, and light leakage phenomena occurs in the zone of stress concentration thus.
In order to improve light leakage phenomena, need to reduce the contraction of light polarizing film under high temperature and/or humidity condition.Yet the stress that the accompanying liquid crystal board of being made up of the material with different physical characteristics of light polarizing film produces is to be difficult to remove.The other method of improving light leakage phenomena is to provide the stress relief function to pressure sensitive adhesive layer, so that polarizer is fixed on the liquid crystal board.Usually, rubber, acrylic acid series (acryls) and organosilicon usually are used as pressure sensitive adhesive.Wherein, acrylic pressure-sensitive adhesive is being favourable aspect pressure sensitive adhesive performance, optical property, weather resistance and the weathering resistance, therefore, has been widely used in and has made the contact adhesive composition that is used for polarizer.
Provide the universal design of stress relief function to be to pressure sensitive adhesive layer, the design pressure sensitive adhesive layer makes it have big creep property and dimensional instability.Its exemplary process is, mix with high-molecular weight polymer so that it can react with multi-functional linking agent by the low-molecular weight polymer that will have or not have insignificant functional group, the contact adhesive composition with weather resistance and stress relief function is provided with crosslinking functionality.
For example, Korean Patent spy opens the 1998-079266 plan by providing the stress relief function to solve light leakage phenomena to contact adhesive composition, described contact adhesive composition comprises that the weight-average molecular weight of 100 weight parts is 1,000,000 or the weight-average molecular weight of higher high-molecular-weight propylene acid based copolymer, 20-200 weight part be 30,000 or the lower low molecular weight propylene acid based copolymer and the multifunctional linking agent of 0.005-5 weight part.
The Japanese Patent spy opens 200247468 plans provides the stress relief function to the contact adhesive composition that is used for light polarizing film, described contact adhesive composition comprises that the weight-average molecular weight of 100 weight parts is 800,000～2,000, the weight-average molecular weight of 000 high-molecular-weight propylene acid based copolymer, 5～50 weight parts is 50,000 or lower low molecular weight propylene acid based copolymer (not having functional group (dispersity=1.0～2.5)), linking agent and silane compound.
In addition, the Japanese Patent spy opens the 2003-49141 plan by providing the stress relief function to solve light leakage phenomena to the contact adhesive composition that is used for light polarizing film, described contact adhesive composition comprises that weight average molecular weight range is 1,000,000～2,000,000 and have a high-molecular-weight propylene acid based copolymer of functional group, weight average molecular weight range is 30,000～300,000 and have an intermediate molecular weight acrylic copolymer that is less than two kinds of functional groups, weight average molecular weight range is 1,000～20,000 and do not have a low molecular weight propylene acid copolymer (dispersity=1.0～2.5) of functional group, and linking agent.
Above-mentioned reference utilisation technology feature is softened final pressure sensitive adhesive, to improve the stress releasing property of described pressure sensitive adhesive.Promptly, described pressure sensitive adhesive is designed to, by increase creep property and make more easy with respect to the distortion of external stress, thereby discharge the local stress that contraction or expansion caused, because the low molecular weight material that the modulus of pressure sensitive adhesive (modulus) is passed through to be added reduces by polarizer.But, preparing in the situation of remollescent pressure sensitive adhesive by adding low molecular weight material, the modulus of final pressure sensitive adhesive is reduced.So this pressure sensitive adhesive may have some problems, when polarizer stores with volume type (role type) in preparation process, its may be crushed easily (pit defect); And in the situation of cutting pressure sensitive adhesive, this pressure sensitive adhesive may be given prominence to from the cross section of polarizer, and perhaps polarizer may be contaminated by outstanding pressure sensitive adhesive.Equally, the weather resistance of pressure sensitive adhesive may reduce under high temperature and humidity condition, because the low molecular weight material that is added can easily be moved in the glass interface of liquid crystal board and TAC.
Provide the another kind of method of stress relief function to be to pressure sensitive adhesive, will keep very low by the gel content of the prepared final pressure sensitive adhesive of the macromolecular material with crosslinking functionality.This method has the modulus of pressure sensitive adhesive can significantly reduced advantage.Yet this method also has some shortcomings, is difficult to make pressure sensitive adhesive to keep uniform low-gel content; Need the long time of cost from crosslinked pressure sensitive adhesive up to cutting polarizer (digestion time), under the condition of high temperature and high humidity, significantly reduce its weather resistance.
The Japanese Patent spy opens the method that 60-207101 discloses a kind of duplication of production pressure sensitive adhesive, and this pressure sensitive adhesive has low-gel content and comprises high molecular weight material.The patent disclosure of this publication a kind of method that is used to prepare pressure sensitive adhesive, this method is mixed by the acrylic copolymer (A) that will have crosslinkable functionality, the acrylic copolymer (B) that does not have crosslinkable functionality and multifunctional linking agent with at least two functional groups and is prepared pressure sensitive adhesive, wherein, the weight ratio of A/B is in 1/4～4/1 scope.That is, the patent disclosure of this publication following technical characterictic: by removing free crosslinkable functionality, the preservation period that can prolong described pressure sensitive adhesive; Remove the free crosslinkable functionality by the amount that during cross-linking process, the multifunctional linking agent of respective amount is increased to crosslinkable functionality.Yet this patent does not have the open wherein molecular weight parameter of employed acrylic acid polymer, does not disclose the technical characterictic of crosslinking structure yet.Particularly, this patent does not have the technical characterictic of the stress releasing property of openly relevant with light leakage phenomena pressure sensitive adhesive.
Therefore, need a kind of light polarizing film that is used for the new type bonding agent of light polarizing film and uses this tackiness agent of exploitation, minimize by the minimizing that makes final pressure sensitive adhesive modulus, and do not damage the main characteristic of light polarizing film product, for example in life-time service and weather resistance and reliability under high temperature and humidity condition, improve light leakage phenomena and prevent that the operability of polarizer from reducing.
Summary of the invention
In order to solve the aforementioned problems in the prior, an object of the present invention is to provide a kind of acrylic pressure-sensitive adhesive composition, its improvement by stress releasing property improves light leakage phenomena, and minimize the main characteristic that does not have loss light polarizing film product by the minimizing that makes the pressure sensitive adhesive modulus, for example weather resistance and the reliability under high temperature and humidity condition prevents that the operability of polarizer from reducing.
Another object of the present invention is to provide a kind of use to have the polarizer of the acrylic pressure-sensitive adhesive composition of above-mentioned characteristic.
Another object of the present invention is, a kind of liquid-crystal display is provided, and it comprises the polarizer by the acrylic pressure-sensitive adhesive composition preparation with above-mentioned characteristic.
In order to realize these purposes, the invention provides a kind of acrylic pressure-sensitive adhesive composition light polarizing film, that comprise (methyl) acrylic copolymer that is used for, described (methyl) acrylic copolymer comprises alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl, it is characterized in that the gel content of being represented by following formula (1) is 10～55%; Swelling ratio by following formula (2) expression is 30～110; Weight-average molecular weight by ethyl acetate colloidal sol of stripping from described tackiness agent is at least 800,000; And the ratio of weight-average molecular weight and number-average molecular weight is 2.0～7.0:
Gel content (%)=B/A * 100 (1)
Swelling ratio=C/B (2)
Wherein, A represents the weight of acrylic adhesive composition, B represents to immerse at ambient temperature in the ethyl acetate dry weight of the insolubles of acrylic adhesive composition after 48 hours, and C represents to immerse at ambient temperature in the ethyl acetate after 48 hours by the weight of ethyl acetate swollen insolubles (weight of the solvent of the insolubles weight+infiltration of acrylic adhesive composition).
Equally, the invention provides a kind of pressure sensitive adhesive polarizer, comprise that on the one or both sides of light polarizing film the aforesaid propylene acid as pressure sensitive adhesive layer is contact adhesive composition.
In addition, the invention provides a kind of liquid-crystal display that comprises liquid crystal board, in this liquid crystal board, Zhi Bei polarizer is adhered to the one or both sides of liquid crystal cells as mentioned above.
The invention is characterized in, improve light leakage phenomena by the stress releasing property that increases pressure sensitive adhesive; Gel content by regulating final pressure sensitive adhesive, swelling ratio, by the molecular weight and the molecular weight distribution of the colloidal sol of solvent stripping, thereby remain on the weather resistance under high temperature and the high humidity, and with the modulus of final pressure sensitive adhesive remain to aspect the operability of polarizer without any the level of problem.
Usually, have low-gel content and when solvent impregnated, can greatly be increased when final pressure sensitive adhesive is adjusted to by the content of the gel of solvent expansion (swelling ratio or swelling index).Pressure sensitive adhesive with described crosslinking structure forms very loose crosslinking structure.Therefore, this pressure sensitive adhesive has excellent stress releasing property, can improve light leakage phenomena thus, because when from extraneous stress application, it has high creep property and easy deformation.Yet under high temperature and high humidity, the weather resistance of this pressure sensitive adhesive is non-constant.
Therefore, the present inventor addresses the above problem as possible, and find: if pressure sensitive adhesive is designed to have simultaneously low gel content and low swelling ratio, then pressure sensitive adhesive has excellent stress releasing property, and can under high temperature and high humidity, keep weather resistance, thereby finish the present invention.Although there is not theoretic restriction, but the pressure sensitive adhesive that had not only had low-gel content but also had a low swelling ratio forms the crosslinking structure of relative compact, can satisfy stress releasing property and weather resistance simultaneously, because the colloidal sol of this pressure sensitive adhesive (free copolymer that does not have crosslinking structure) links mutually with above-mentioned crosslinking structure.Therefore, it is very important regulating crosslinking structure in the present invention.If the gel content of pressure sensitive adhesive is similar, but the crosslinking structure compactness, and then weather resistance can significantly reduce, because there is not the polymkeric substance of crosslinking structure to be difficult to be penetrated between the crosslinking structure.By contrast, when crosslinking structure was too loose, weather resistance also reduced, because there is not the polymkeric substance of crosslinking structure easily to be penetrated between the crosslinking structure, but when being applied to stress on the pressure sensitive adhesive, it also can easily be deviate from from crosslinking structure.
The pressure sensitive adhesive of the present invention that is used for polarizer can be applied to various tackiness agents or pressure sensitive adhesive material, for example acrylic acid series, organosilicon, rubber, urethane, polyester or epoxy compounds, though without limits, wherein acrylic pressure-sensitive adhesive is preferred.
Description of drawings
Shown in Figure 1 is according to the gel content of the acrylic pressure-sensitive adhesive composition of one embodiment of the present invention and the relation between the swelling ratio.
Embodiment
Hereinafter the present invention will be described in further detail.
The invention provides a kind of acrylic pressure-sensitive adhesive composition light polarizing film, that comprise (methyl) acrylic copolymer that is used for, described (methyl) acrylic copolymer comprises alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl, it is characterized in that the gel content of being represented by following formula (1) is 10～55%; Swelling ratio by following formula (2) expression is 30～110; Weight-average molecular weight by ethyl acetate colloidal sol of stripping from described tackiness agent is at least 800,000; The ratio of weight-average molecular weight and number-average molecular weight is 2.0～7.0:
Gel content (%)=B/A * 100 (1)
Swelling ratio=C/B (2)
Wherein, A, B and C are as defined above.
In acrylic pressure-sensitive adhesive composition of the present invention, preferred gel content is 15～45%, and preferred gel content and swelling ratio satisfy as shown in the formula (3):
-2.83x+130≤y≤-2.83x+180 (3)
Wherein, x represents gel content, and y represents swelling ratio.
The gel content of acrylic adhesive composition of the present invention is 10～55%, is preferably 15～45%, more preferably 15～35%.
If above-mentioned gel content is greater than 55%, then the stress releasing property of this pressure sensitive adhesive significantly reduces.If gel content is less than 10%, the non-constant of the weather resistance under high temperature and high humidity then.
Simultaneously, if the swelling ratio by gel determination less than 30, then the stress releasing property of pressure sensitive adhesive is bad, because crosslinking structure is too compact.And, if swelling ratio greater than 110, then weather resistance reduces, because crosslinking structure is too loose.
Equally, if the molecular weight of the colloidal sol by the solvent stripping is less than 800,000, then each crosslinking structure is not fully linked by sol-fraction, thereby has reduced weather resistance.
On the other hand, if the molecular weight distribution of colloidal sol is less than 2, then stress releasing property is insufficient.And if it is greater than 7, then weather resistance is bad.Therefore, preferably the molecular weight distribution with colloidal sol is adjusted to 2.0～7.0, and more preferably 3～5.5.
Preferably, (methyl) of the present invention acrylic copolymer comprises the vinyl and/or the acrylic acid series crosslinkable monomers of (methyl) acrylate monomer with 2-14 carbon atom alkyl and 0.01～5 weight part of 80～99.8 weight parts, and described crosslinkable monomers has and crosslinkable carboxyl of multifunctional linking agent or hydroxyl.
(methyl) acrylate monomer of the above-mentioned 2-14 of a having carbon atom alkyl can be (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) dodecylacrylate and (methyl) vinylformic acid tetradecyl ester.If the carbonatoms of alkyl is in above-mentioned scope, the second-order transition temperature (T of pressure sensitive adhesive then
g) may increase, perhaps may be difficult to regulate the performance of tackiness agent, therefore, above-mentioned carbonatoms is limited in the scope of 2-14.Above-mentioned (methyl) acrylate monomer can use separately or use with form of mixtures.In order to regulate bond strength and cohesive strength, preferably use (methyl) acrylate monomer of 80～99.8 weight parts with 2-14 carbon atom alkyl.
Equally, in order to regulate bond strength and cohesive strength, (methyl) acrylic copolymer of the present invention and vinyl and/or acrylic acid series cross-linking monomer carry out copolymerization, described cross-linking monomer have can with crosslinked carboxyl or the hydroxyl of multifunctional linking agent, it is to be selected from following group one or more: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, 2-hydroxyl ethylene glycol (methyl) acrylate, 2-hydroxyl propylene glycol (methyl) acrylate, vinylformic acid, methacrylic acid, acrylic acid dimer, methylene-succinic acid, toxilic acid or maleic anhydride.Preferably, the content of vinyl and/or acrylic acid series crosslinkable monomers is 0.01～5 weight part of total monomer amount, because when this content is too high, bond strength and stripping strength can reduce.
For the second-order transition temperature of regulating pressure sensitive adhesive or some functions are provided, (methyl) of the present invention acrylic copolymer randomly comprises the vinyl monomer by following chemical formula (1) expression of 0～20 weight part:
[chemical formula (1)]
Wherein, R
4The expression hydrogen or alkyl, R
3Expression cyano group replaces or unsubstituted phenyl acetoxyl group, perhaps COR with alkyl
5, R wherein
5Expression is amino or replace or unsubstituted glycidoxypropyl with alkyl.
R at above-mentioned chemical formula
3-R
5Definition in, preferred alkyl is the alkyl of 1-6 carbon atom, more preferably methyl or ethyl.
The compound of above-mentioned chemical formula can be a styrene monomer, for example vinylbenzene or alpha-methyl styrene; Vinyl esters of carboxylic acids, for example vinyl-acetic ester; The monomer that perhaps has nitrogen-atoms, for example (methyl) acrylamide or N-butoxymethyl (methyl) acrylamide.The preferred content of above-mentioned vinyl monomer is 20 weight parts of total monomer or still less, because when content is too high, flexible and stripping strength can reduce.
The acrylic pressure-sensitive adhesive composition of the present invention that comprises mentioned component can further contain linking agent.
The linking agent that is used for the cross-linked acrylic acid based copolymer has the function of the cohesive strength that increases pressure sensitive adhesive, described acrylic copolymer comprises alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl, by the carboxyl and the hydroxyl reaction of described linking agent and acrylic acid polymer, realize the increase of the cohesive strength of this pressure sensitive adhesive.Described linking agent can be selected from: isocyanic ester, epoxy compounds, aziridine and metal-chelating linking agent.
Particularly, isocyanate crosslinking can be the reactant of toluene-2,4-diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, two isocyanic acids, six methylene esters, isomery vulcabond (isoform diisocyanate), two isocyanic acid tetramethyl xylene esters, naphthalene diisocyanate or they and polyvalent alcohol such as TriMethylolPropane(TMP).Epoxy crosslinked dose can be ethylene glycol diglycidylether, triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, N, N, N ' N '-four glycidyl group quadrol or glycerol diglycidylether.Aziridine crosslinker can be N, N '-Toluene-2,4-diisocyanate, 4-two (1-aziridine carboxide), N, N '-ditan-4,4 '-two (1-aziridine carboxide), triethylene trimeric cyanamide, bisiso-prothaloyl-1-(2-methylaziridine) or three-1-aziridine phosphine oxide.The metal-chelating linking agent can be by polyvalent metal such as Al, Fe, Zn, Sn, Ti, Sb, Mg and V and Acetyl Acetone or methyl aceto acetate are carried out the prepared compound of coordination.With respect to 100 parts by weight of acrylic acid based copolymers, preferred cross-linking agents content is 0.01～10 weight part.
Equally, contact adhesive composition of the present invention can comprise silane coupling agent in addition, and it can improve heat-resisting/wet fastness by improving the stability of pressure sensitive adhesive on substrate of glass.When keeping long-time under high temperature and high humidity, silane coupling agent has the function of the stability that increases bond properties.With respect to 100 parts by weight of acrylic based copolymers, preferred silane coupled agent content is 0.005～5 weight part.Silane coupling agent can be γ-glycidyl ether propyl trimethoxy silicane, γ-glycidyl ether propyl group methyldiethoxysilane, γ-glycidyl ether propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, 3-isocyanic ester propyl-triethoxysilicane or γ-acetylacetic ester propyl trimethoxy silicane.These silane coupling agents can use separately or use with its mixture.
In addition, if desired, acrylic pressure-sensitive adhesive composition of the present invention may further include tackifier.With respect to 100 parts by weight of acrylic acid multipolymers, the preferred content of tackifier is 1～100 weight part.If the excessive use of tackifier, then the consistency of tackiness agent and cohesive force may reduce.Described tackifier can be (hydration) hydrocarbon resin, (hydration) Gum Rosin, (hydration) rosin ester resin, (hydration) terpine resin, (hydration) terpene phenol resin, polymeric Gum Rosin or polymeric rosin ester resin.These tackifier can use separately or use with its mixture.
Equally, according to purposes, acrylic pressure-sensitive adhesive composition of the present invention may further include softening agent, Resins, epoxy, stiffening agent etc.In addition, can suitably add UV stablizer, antioxidant, tinting material, toughener, filler, defoamer, tensio-active agent etc.
In addition, the present invention relates to a kind of method that is used for the acrylic pressure-sensitive adhesive composition of light polarizing film of the present invention that is used to prepare, comprise step:
Vinyl and/or acrylic acid series crosslinkable monomers and alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl are reacted, be used for the acrylic acid polymer of crosslinking structure with preparation, described crosslinkable monomers has and crosslinkable carboxyl of multifunctional linking agent or hydroxyl;
Alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl is reacted, be used for the acrylic acid polymer of non-crosslinked structure with preparation; And
The acrylic acid polymer that will be used for crosslinking structure mixes with the acrylic acid polymer that is used for the non-crosslinked structure, perhaps
The present invention relates to a kind of method that is used for the acrylic pressure-sensitive adhesive composition of light polarizing film of the present invention that is used to prepare, comprising:
First step, vinyl and/or acrylic acid series crosslinkable monomers and alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl are reacted, be used for the acrylic acid polymer of crosslinking structure with preparation, described crosslinkable monomers have can with crosslinked carboxyl or the hydroxyl of multifunctional linking agent; And
Second step, in having first step under the condition of the prepared acrylic acid polymer that is used for crosslinking structure, alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl is reacted, be used for the acrylic acid polymer of non-crosslinked structure with preparation.
Below the aforesaid method that is used to prepare acrylic pressure-sensitive adhesive of the present invention will be described in more detail.
Aforesaid propylene acid is that pressure sensitive adhesive can prepare in the following way, promptly by two kinds of independent acrylic acid polymer are mixed, promptly, preparation is used for the acrylic acid polymer of crosslinking structure and is used for the acrylic acid polymer of non-crosslinked structure, with specific part by weight they is mixed; Perhaps two kinds of acrylic acid polymer of preface preparation successively in reactor react they and multifunctional linking agent then.The aforesaid propylene acid based polymer that is used for crosslinking structure must comprise crosslinkable functional group.If the amount of crosslinkable functionality is excessive, then crosslinking structure is too compact, so that does not have the polymkeric substance of crosslinking structure can not be penetrated between the crosslinking structure, and therefore, weather resistance reduces significantly, can not obtain gel content of the present invention and swelling ratio.On the contrary, if the amount of crosslinkable functionality is less than certain value, then crosslinking structure is too loose, so there is not the polymkeric substance of crosslinking structure easily to be penetrated between the crosslinking structure, but when the time to the pressure sensitive adhesive stress application, it also can easily be deviate from from crosslinking structure, so weather resistance reduces.On the other hand, the acrylic acid polymer that is used for crosslinking structure preferably has similar composition with the acrylic acid polymer that is used for the non-crosslinked structure, because if they have different compositions, then is difficult to two kinds of polymkeric substance are mixed fully.Equally, in mixing these two kinds of polymkeric substance, preferred crosslinkable functionality is a hydroxyl, rather than carboxyl.The acrylic acid polymer that is used for the non-crosslinked structure does not preferably have crosslinkable functional group (hydroxyl or carboxyl), but it can have crosslinkable functional group.
Acrylic copolymer of the present invention can prepare by traditional method, for example solution polymerization, photopolymerization, mass polymerization, suspension polymerization and letex polymerization, but solution polymerization is preferred.Herein, preferably, polymerization temperature is set at 50～140 ℃, and after the monomer uniform mixing, adds initiator.
As polymerization starter, azo-group polymerization starter such as azobis isobutyronitrile and azo bis cyclohexane nitrile or superoxide such as benzoyl peroxide and acetyl peroxide can use separately or use with its mixture.
Preparation method with contact adhesive composition of the present invention of above-mentioned composition is not particularly limited.
In the mixing process that forms pressure sensitive adhesive layer, for smooth coating, the crosslinking reaction of linking agent functional group should not take place.After applying, follow dry and wearing out, form crosslinking structure, obtain to have the strong elasticity and the pressure sensitive adhesive layer of force of cohesion thus.
Equally, the invention provides a kind of polarizer, this polarizer contains the pressure sensitive adhesive layer of acrylic pressure-sensitive adhesive composition as light polarizing film.
On the one or both sides of light polarizing film, polarizer of the present invention is made up of the pressure sensitive adhesive layer that forms from above-mentioned contact adhesive composition.The light polarizing film or the polarizing appliance that form above-mentioned polarizer are not particularly limited.
For example, preferred light polarizing film can prepare in the following way, promptly by polarisation component such as iodine or dichroic dyestuff are added on the polyvinyl alcohol resin film, then stretches.Equally, aspect the thickness of light polarizing film without limits, so this film can prepare with common thickness.As polyvinyl alcohol resin, can use polyvinyl alcohol, polyvinyl formal, polyvinylacetal and ethene and saponified vinyl acetate copolymer etc.
In the both sides of light polarizing film, can form multilayer film, wherein, by will be such as the protective membrane of cellulose membrane such as tri acetyl cellulose etc.; Polyester film such as polycarbonate membrane, polyethylene terephthalate etc.; Poly (ether sulfone) film; Polyolefin film with polyethylene or polypropylene structure; And the polyolefin film lamination with cycloolefin or norbornylene structure or the rare multipolymer of ethylene propylene, prepare described multilayer film.The thickness of these protective membranes is not concrete to be limited, and can accept common thickness.
The method of formation pressure sensitive adhesive layer without limits on light polarizing film.This method can comprise step: on the surface of light polarizing film, directly apply pressure sensitive adhesive with scraping strip coating machine, and then dry.Perhaps this method can comprise step: on the surface of peelable substrate, apply pressure sensitive adhesive, and then dry, pressure sensitive adhesive layer is transferred on the surface of light polarizing film, then aging.
Polarizer of the present invention can comprise the other layer that one or more provide supplementary functions, for example protective layer, reflecting layer, antiglare film, phase retardation film, the compensate film that is used for wide visual angle and brightness enhancement film.
Use the polarizer of pressure sensitive adhesive of the present invention can be applied to normally used all liquid-crystal displays now, to not concrete qualification of kind of liquid crystal board.Preferably, the present invention can make up such LCD, and it comprises the pressure sensitive adhesive polarizer is connected to liquid crystal board on the one or both sides of liquid crystal cells.
Explain preferred implementation of the present invention by following embodiment.But, it should be understood that those skilled in the art can make amendment and improve in essence of the present invention and scope.
Embodiment
Preparation example 1: the preparation of acrylic copolymer (A-1)
As described in the table 1, the monomer mixture of the hydroxyl-metacrylate of the n-butyl acrylate (BA) of 98 weight parts and 2.0 weight parts is put into the reactor of 1L, described reactor is equipped with cooling system and the temperature control easily that nitrogen reflux uses, and the ethyl acetate (EAc) of 120 weight parts is added wherein as solvent.For from wherein removing oxygen, with nitrogen purge 1 hour, during this period, temperature remained on 60 ℃, then the two isobutyronitriles (AIBN) of the azo of 0.03 weight part is added wherein as reaction initiator.With this mixture reaction 8 hours, with ethyl acetate (EAc) dilution, obtaining acrylic copolymer (A-1), its solids, weight-average molecular weight with 15wt% be 1,600,000 and molecular weight distribution be 4.9.
Preparation example 2,3: the preparation of acrylic copolymer (A-2, A-3)
As shown in table 1, by every kind of component that part is added or part is not added acrylic copolymer (A-1) composition in the above-mentioned preparation example 1, preparation high-molecular weight acrylic copolymer (A-2, A-3).Result data is as shown in table 1.
Preparation example 4,5,6: the preparation of acrylic copolymer (B-1, B-2, B-3)
As shown in table 1, by every kind of component that acrylic copolymer (A-1) composition in the above-mentioned preparation example 1 is added or partly be not added on to part, preparation high-molecular weight acrylic copolymer (B-1, B-2, B-3).Result data is as shown in table 1.
Preparation example 7: the preparation of acrylic copolymer (L-1)
As shown in table 1, every kind of component by acrylic copolymer (A-1) composition in the above-mentioned preparation example 1 is added or partly be not added on to part prepares low-molecular-weight acrylic copolymer (L-1).Result data is as shown in table 1.
Preparation example 8,9: the preparation of acrylic copolymer (I-1, I-2)
As shown in table 2, in first reactions steps, under the condition identical, have the high-molecular-weight propylene acid based copolymer of hydroxyl with preparation of compositions with hydroxyl with preparation example 1.The second step composition shown in the table 2 is added in the polymkeric substance prepared in first reactions steps, this mixture is reacted under same reaction conditions, to prepare final high-molecular-weight propylene acid based copolymer.
Embodiment 1
[mixing process]
In the mixture of high-molecular-weight propylene acid based copolymer (B-1) solids that high-molecular-weight propylene that 20 weight parts as above prepare acid based copolymer (A-1) solids and 80 weight parts as above prepare, add the toluene-2,4-diisocyanate adducts of the TriMethylolPropane(TMP) (TDI-1) of 0.1 weight part.Suitable this mixture of dilution, uniform mixing applies on release film, and drying is 30 microns a smooth pressure sensitive adhesive layer to obtain thickness.
[lamination process of polarizer]
Apply the iodine polarizer of 185 micron thickness with the pressure sensitive adhesive layer of above-mentioned preparation.Prepared polarizer is cut into the suitable dimension that is used to test.Use above-mentioned pressure sensitive adhesive polarizer test result as the table 3a as shown in.
Embodiment 2-7
As show as shown in the 3a, by every kind of component that part is added or part is not added embodiment 1 composition, implement to mix and lamination process in the mode identical with embodiment 1.Test weather resistance and even light transmission in the mode identical with embodiment 1, test result is as shown in table 3a.
Comparative example 2-7
As show as shown in the 3b, by every kind of component that part is added or part is not added embodiment 1 composition, implement to mix and lamination process in the mode identical with embodiment 1.Test weather resistance and even light transmission in the mode identical with embodiment 1, test result is as shown in table 3b.
The test of＜polarizer performance 〉
A. weather resistance
(90mm * 170mm) adheres to substrate of glass, and (on the both sides of 110mm * 190mm * 0.7mm), on this substrate of glass, the optical absorption axle passes across the polarizer that applies with pressure sensitive adhesive prepared among the embodiment 1.In clean cell, apply about 5kg/cm herein,
2Pressure, to prevent to produce bubble and impurity.For the humidity resistance of assess sample, specimen is retained in the moist chamber of 60 ℃ and 90%RH (relative humidity) 1000 hours, to observe the formation and the alice of bubble.Equally, for the resistance toheat of assess sample, with specimen be retained in 80 ℃ following 1000 hours, to observe the formation and the alice of bubble.Before estimating, specimen is at room temperature further adapted to 24 hours.Equally, after prepared pressure sensitive adhesive polarizer adapts to 5 months or be longer, estimate reliability according to aforesaid method.Estimate reliability in the following manner:
Zero: do not observe bubble or alice;
△: observe a spot of bubble or alice;
*: observe a large amount of bubbles or alice.
B. uniform light transmission (light leak)
By in the darkroom, using prepared sample more than the back light system observation, estimate the light leak of this sample.For the homogeneity of the printing opacity of testing them, (200mm * 200mm) sticks to substrate of glass, and (on 210mm * 210mm * 0.7mm), wherein, this polarizer and this substrate of glass meet at right angles with the polarizer that applies.Estimate the homogeneity of printing opacity in such a way:
: bore hole is observed the printing opacity heterogeneity;
Zero: observe a spot of printing opacity heterogeneity;
△: observe some printing opacity heterogeneities;
*: observe a large amount of printing opacity heterogeneities.
C. pit defect (storage modulus)
When the modulus (storage modulus) of pressure sensitive adhesive increased, the pit defect of pressure sensitive adhesive reduced.The modulus of pressure sensitive adhesive is measured by using RMS-800 (Rheometrics Co.).The modulus of pressure sensitive adhesive is measured by estimating storage modulus, estimating storage modulus is by using diameter to carry out under the following conditions as the parallel plate anchor clamps (Parallel Plate Fixture) of 8mm: temperature is 30 ℃, pressure sensitive adhesive thickness is 1mm, strain rate is 10%, and frequency is 1rad/ second.Estimate the storage modulus of being tested in the following manner:
5 points: the pit defect of pressure sensitive adhesive is (storage modulus＞1.8 * 10 seldom
4Pa);
4 points: the pit defect of pressure sensitive adhesive is a minority (1.4 * 10
4Pa＜storage modulus＜1.7 * 10
4Pa;
3 points: the pit defect of pressure sensitive adhesive is (1.0 * 10
4Pa＜storage modulus＜1.3 * 10
4Pa;
2 points: the pit defect of pressure sensitive adhesive is many (0.8 * 10
4Pa＜storage modulus＜1.0 * 10
4Pa;
1 point: the pit defect of pressure sensitive adhesive is a large amount of (0.8 * 10
4Pa＜storage modulus).
D. outstanding (but cutting) of pressure sensitive adhesive
Cut the polarizer that is obtained after the above-mentioned lamination process with Thomson (Thomson) cutting knife.The cross section of the polarizer that observation is cut, estimate in such a way:
3 points: the outstanding degree of tackiness agent that is cut side is acceptable (less than 0.2mm);
2 points: the outstanding degree of tackiness agent that is cut side has a few too many (0.2～0.5mm);
1 point: the outstanding degree very serious (greater than 0.5mm) of tackiness agent that is cut side.
E. gel content
Dry pressure sensitive adhesive in above-mentioned mixing process was placed in the chamber (23 ℃ and 60%RH) of fixed temperature and humidity 10 days.The pressure sensitive adhesive of 0.3g is poured in the #200 stainless steel mesh screen, and it is dipped in the ethyl acetate of 100mL, is stored in the darkroom 2 days.After wherein isolating insolubles, in baking oven and under 70 ℃,, weigh dry 4 hours of resulting tackiness agent.
F. swelling ratio
When measuring gel content, after separating insolubles, by with insolubles with comprise the dry weight of the weight of (swelling) solvent in insolubles, thereby measure swelling ratio divided by insolubles.
Table 1: the composition of acrylic copolymer
The composition of table 2. acrylic copolymer
In above-mentioned table 1 and 2, various writing a Chinese character in simplified form is defined as:
N-BA: n-butyl acrylate; EHA: ethylhexyl acrylate; 2-HEMA:2-hydroxyethyl methacrylic ester; AIBN: azobis isobutyronitrile; EAc: ethyl acetate.
Table 3a: the composition of the performance of acrylic copolymer
The composition of the performance of table 3b. acrylic copolymer
As show as shown in the 3a, embodiments of the invention 1-7 demonstrates favorable durability and excellent light leak performance, and relevant with operability in the pressure sensitive adhesive preparation process, the low of pressure sensitive adhesive given prominence to and low pit defect.By contrast, comparative example 1 demonstrates very high swelling ratio, so weather resistance is not enough good, because the crosslinkable structure is too loose.In comparative example 2, the gel content height, swelling ratio is low, so stress releasing property is not enough well consequently can not improve the light leak performance, because crosslinking structure is too compact.In comparative example 3, because the lower molecular weight of colloidal sol causes poor durability.In comparative example 4, improve light leak by mixing low molecular weight material of the prior art, but modulus reduces significantly, thereby reduced the operability of polarizer.In comparative example 5, by as in the prior art, adding a spot of multifunctional linking agent, kept low gel content, but crosslinking structure is loose, so that has increased swelling ratio, so the non-constant of weather resistance.Equally, in comparative example 6, because its common gel content condition, so the non-constant of the stress relief of pressure sensitive adhesive.
Industrial applicability
Just as described above, the present invention is long-time by being released under high temperature, the high humidity The stress that is caused by the contraction of polarizer between the operating period, and do not damage key property such as durability, Thereby effectively be used for improving light leakage phenomena. Equally, the present invention can provide a kind of for polarizer Acrylic pressure-sensitive adhesive composition, final contact adhesive has high modulus. Cause This, the present invention can be applied to above-mentioned contact adhesive composition the polarizer of liquid crystal display, Preventing by the light leakage phenomena that concentrated stress was caused between the long-time operating period, and because High modulus can provide excellent operability.
Claims (17)
1. acrylic pressure-sensitive adhesive composition that comprises (methyl) acrylic copolymer that is used for light polarizing film, described (methyl) acrylic copolymer comprises alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl, it is characterized in that, be 10～55% by the gel content as shown in the formula (1) expression; By the swelling ratio as shown in the formula (2) expression is 30～110; Weight-average molecular weight by ethyl acetate colloidal sol of stripping from described tackiness agent is at least 800,000; And
The ratio of weight-average molecular weight and number-average molecular weight is 2.0～7.0:
Gel content (%)=B/A * 100 (1)
Swelling ratio=C/B (2)
Wherein, A represents the weight of acrylic adhesive composition, B represents to immerse at ambient temperature in the ethyl acetate dry weight of the insolubles of acrylic adhesive composition after 48 hours, and C represents to immerse at ambient temperature in the ethyl acetate after 48 hours by the weight of ethyl acetate swollen insolubles (weight of the solvent of the weight+infiltration of the insolubles of acrylic adhesive composition).
2. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 1, wherein, described gel content is 15～45%.
3. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 1, wherein, described gel content and described swelling ratio satisfy as shown in the formula (3):
-2.83x+130≤y≤-2.83x+180 (3)
Wherein, x represents gel content, and y represents swelling ratio.
4. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 1, wherein, described (methyl) acrylic copolymer comprises the vinyl and/or the acrylic acid series crosslinkable monomers of (methyl) acrylate monomer and 0.01～5 weight part of 80～99.8 weight parts, described (methyl) acrylate monomer has the alkyl of 2-14 carbon atom, and described crosslinkable monomers has and crosslinkable carboxyl of multifunctional linking agent or hydroxyl.
5. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 4, wherein, described (methyl) acrylate monomer is to be selected from following one or more: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) dodecylacrylate and (methyl) vinylformic acid tetradecyl ester.
6. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 4, wherein, described crosslinkable monomers is to be selected from following one or more: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, 2-hydroxyl ethylene glycol (methyl) acrylate, 2-hydroxyl propylene glycol (methyl) acrylate, vinylformic acid, methacrylic acid, acrylic acid dimer, methylene-succinic acid, toxilic acid and maleic anhydride.
7. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 4, wherein, but described composition further comprises 20 or the vinyl monomer of the copolymerization of weight part still less.
8. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 4, wherein, described multifunctional linking agent is to be selected from following one or more: isocyanic ester, epoxy compounds, aziridine and metal chelate compound.
9. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 1, wherein, based on 100 parts by weight of acrylic based copolymers, described composition further comprises the silane coupling agent of 0.05～5 weight part and the tackifier of 1～100 weight part.
10. the acrylic pressure-sensitive adhesive composition that is used for light polarizing film as claimed in claim 1, wherein, described composition further comprises and is selected from one or more following additives: softening agent, Resins, epoxy, solidifying agent, UV stablizer, antioxidant, tinting material, toughener, filler, defoamer and tensio-active agent.
11. be used to prepare the method that is used for the acrylic pressure-sensitive adhesive composition of light polarizing film as claimed in claim 1, comprise step:
Vinyl and/or acrylic acid series crosslinkable monomers and alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl are reacted, be used for the acrylic acid polymer of crosslinking structure with preparation, described crosslinkable monomers has and crosslinkable carboxyl of multifunctional linking agent or hydroxyl;
Alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl is reacted, be used for the acrylic acid polymer of non-crosslinked structure with preparation; And
The acrylic acid polymer that will be used for crosslinking structure mixes with the acrylic acid polymer that is used for the non-crosslinked structure.
12. be used to prepare the method that is used for the acrylic pressure-sensitive adhesive composition of light polarizing film as claimed in claim 1, comprise:
First step, vinyl and/or acrylic acid series crosslinkable monomers and alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl are reacted, be used for the acrylic acid polymer of crosslinking structure with preparation, described crosslinkable monomers has and crosslinkable carboxyl of multifunctional linking agent or hydroxyl; And
Second step, under the condition that the prepared acrylic acid polymer that is used for crosslinking structure exists in first step, alkyl (methyl) acrylate monomer with 1-12 carbon atom alkyl is further reacted, be used for the acrylic acid polymer of non-crosslinked structure with preparation.
13. as claim 11 or the 12 described preparation methods that are used for the acrylic pressure-sensitive adhesive composition of light polarizing film, wherein, described reaction is undertaken by being selected from following polymerization process: solution polymerization, photopolymerization, mass polymerization, suspension polymerization and letex polymerization.
14. as claim 11 or the 12 described preparation methods that are used for the acrylic pressure-sensitive adhesive composition of light polarizing film, wherein, described vinyl and/or acrylic acid series crosslinkable monomers comprise hydroxyl.
15. a pressure sensitive adhesive polarizer, it comprises the acrylic pressure-sensitive adhesive composition as claimed in claim 1 as pressure sensitive adhesive layer on the one or both sides of light polarizing film.
16. pressure sensitive adhesive polarizer as claimed in claim 15, wherein, described polarizer further comprises and is selected from following one layer or more: protective layer, reflecting layer, phase retardation plate, the compensate film that is used for wide visual angle and brightness enhancement film.
17. a liquid-crystal display that comprises liquid crystal board in described liquid crystal board, adheres on the one or both sides of liquid crystal cells as claim 15 or 16 described polarizers.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050082331 | 2005-09-05 | ||
| KR10-2005-0082331 | 2005-09-05 | ||
| KR20050082331 | 2005-09-05 | ||
| KR1020060066537A KR100784995B1 (en) | 2005-09-05 | 2006-07-14 | Acrylic Pressure-Sensitive Adhesive Composition for the Polarizing Film |
| KR1020060066537 | 2006-07-14 | ||
| KR10-2006-0066537 | 2006-07-14 | ||
| PCT/KR2006/003404 WO2007029936A1 (en) | 2005-09-05 | 2006-08-29 | Acrylic pressure-sensitive adhesive composition for polarizing film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101258214A true CN101258214A (en) | 2008-09-03 |
| CN101258214B CN101258214B (en) | 2010-12-15 |
Family
ID=38100125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800325026A Active CN101258214B (en) | 2005-09-05 | 2006-08-29 | Acrylic pressure-sensitive adhesive composition for polarizing film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5128478B2 (en) |
| KR (1) | KR100784995B1 (en) |
| CN (1) | CN101258214B (en) |
| TW (1) | TWI335932B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127183A (en) * | 2010-01-20 | 2011-07-20 | 3M创新有限公司 | Crosslinkable acrylate adhesive polymer composite |
| CN102212317A (en) * | 2010-04-02 | 2011-10-12 | 素塔电子科技(上海)有限公司 | Adhesive agent of polaroid and preparation method for polaroid by using adhesive agent |
| CN103146323A (en) * | 2011-03-31 | 2013-06-12 | 琳得科株式会社 | An adhesive and adhesion sheet |
| CN104053736A (en) * | 2012-01-18 | 2014-09-17 | 三菱树脂株式会社 | Transparent Double-sided Adhesive Sheet For Image Display Device And Image Display Device Using Same |
| CN104610884A (en) * | 2014-01-09 | 2015-05-13 | 苏州斯迪克新材料科技股份有限公司 | Scratch-resistant protective film for display screen |
| CN104812580A (en) * | 2012-12-27 | 2015-07-29 | 日东新兴有限公司 | Insulating paper for oil-immersed motors |
| US9441141B2 (en) | 2012-01-18 | 2016-09-13 | Mitsubishi Plastics, Inc. | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| US9574111B2 (en) | 2012-01-18 | 2017-02-21 | Mitsubishi Plastics, Inc. | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| CN107148587A (en) * | 2014-11-04 | 2017-09-08 | 综研化学株式会社 | Polarizer adhesive composition and the polarizer with adhesive phase |
| CN107674618A (en) * | 2012-05-31 | 2018-02-09 | Lg化学株式会社 | Pressure-sensitive adhesive composition |
| CN107849410A (en) * | 2015-07-10 | 2018-03-27 | 株式会社Lg化学 | Pressure-sensitive adhesion Polarizer |
| CN108130026A (en) * | 2013-11-07 | 2018-06-08 | 积水化学工业株式会社 | Adhesive tape |
| CN108368397A (en) * | 2015-12-15 | 2018-08-03 | 住友化学株式会社 | The optical film and optical laminate of subsidiary adhesive phase |
| CN109906208A (en) * | 2016-05-23 | 2019-06-18 | 康宁股份有限公司 | Glass-making processes and equipment |
| CN111148811A (en) * | 2017-12-11 | 2020-05-12 | 株式会社Lg化学 | Adhesive composition for foldable displays and foldable displays comprising the same |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100831558B1 (en) * | 2005-11-18 | 2008-05-21 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive compositions for polarizing film |
| KR100932888B1 (en) * | 2006-07-21 | 2009-12-21 | 주식회사 엘지화학 | Optically compensated acrylic pressure sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| JP5047556B2 (en) * | 2006-07-26 | 2012-10-10 | リンテック株式会社 | Adhesive for bonding optical functional film, optical functional film with adhesive, and method for producing the same |
| KR20100009472A (en) * | 2008-07-18 | 2010-01-27 | 주식회사 엘지화학 | Liquid crystal display |
| KR20100009473A (en) * | 2008-07-18 | 2010-01-27 | 주식회사 엘지화학 | Polarizer and liquid crystal display |
| JP4806730B2 (en) * | 2008-10-15 | 2011-11-02 | 三菱樹脂株式会社 | Transparent adhesive sheet and image display device |
| JP5544858B2 (en) * | 2009-12-11 | 2014-07-09 | サイデン化学株式会社 | Adhesive composition for polarizing plate |
| KR101552741B1 (en) * | 2010-04-05 | 2015-09-11 | (주)엘지하우시스 | Pressure-sensitive adhesive composition for touch panel, pressure-sensitive adhesive film and touch panel |
| KR101362879B1 (en) | 2010-12-31 | 2014-02-14 | 제일모직주식회사 | Adhesive composition for polarizing plate |
| JP6324651B2 (en) * | 2011-03-29 | 2018-05-16 | 住友化学株式会社 | Liquid crystal display |
| KR101687446B1 (en) | 2013-06-19 | 2016-12-16 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
| CN103980847B (en) * | 2014-05-21 | 2015-11-25 | 天津大学 | Self cure Polyacrylic Ester and Epoxy Resin sizing agent and Preparation method and use |
| KR102301157B1 (en) | 2014-07-18 | 2021-09-10 | 미쯔비시 케미컬 주식회사 | Adhesive composition and adhesive using same, and adhesive for polarizing plate |
| JP6472040B2 (en) * | 2014-10-28 | 2019-02-20 | フジコピアン株式会社 | Double-sided adhesive film and protective member for information display screen using the same |
| CN109844048B (en) | 2016-10-14 | 2021-10-15 | 信越化学工业株式会社 | Heat-conductive composite silicone rubber sheet and method for producing same |
| JP6691091B2 (en) * | 2017-11-30 | 2020-04-28 | 住友化学株式会社 | Liquid crystal display |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0312471A (en) * | 1989-06-10 | 1991-01-21 | Nitto Denko Corp | Pressure-adhesive layer and polarizing plate |
| JP3142865B2 (en) * | 1990-11-09 | 2001-03-07 | 旭化成工業株式会社 | Manufacturing method of strong adhesive emulsion type pressure sensitive adhesive |
| JPH09145925A (en) * | 1995-09-22 | 1997-06-06 | Sekisui Chem Co Ltd | Self-adhesive polarizing plate |
| JP4672118B2 (en) * | 2000-08-02 | 2011-04-20 | サイデン化学株式会社 | Adhesive-coated polarizing plate and pressure-sensitive adhesive composition used therefor |
| JP5230879B2 (en) * | 2000-09-29 | 2013-07-10 | 株式会社日本触媒 | Adhesive products |
| JP4822034B2 (en) * | 2001-02-19 | 2011-11-24 | 綜研化学株式会社 | Method for producing pressure-sensitive adhesive sheet for optical member |
| JP2002341141A (en) * | 2001-05-15 | 2002-11-27 | Nitto Denko Corp | Adhesion type optical film and liquid crystal display device |
| JP4803524B2 (en) * | 2001-05-15 | 2011-10-26 | 綜研化学株式会社 | Optical member pressure-sensitive adhesive and optical member provided with the pressure-sensitive adhesive |
| JP2003049143A (en) * | 2001-05-31 | 2003-02-21 | Soken Chem & Eng Co Ltd | Adhesive for optical film and optical film using the adhesive |
| JP4799778B2 (en) * | 2001-08-23 | 2011-10-26 | 日東電工株式会社 | Medical pressure-sensitive adhesive composition and pressure-sensitive adhesive tape or sheet using the composition |
| KR100446664B1 (en) * | 2002-02-20 | 2004-09-04 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive composition for the polarizing firm |
| JP2004059893A (en) * | 2002-06-04 | 2004-02-26 | Sekisui Chem Co Ltd | Acrylic adhesive composition and adhesive tape |
| JP4134350B2 (en) | 2002-08-29 | 2008-08-20 | 綜研化学株式会社 | Optical member pressure-sensitive adhesive and optical member using the pressure-sensitive adhesive |
| JP2005179467A (en) * | 2003-12-18 | 2005-07-07 | Nitto Denko Corp | Adhesive composition for optical film, adhesive layer for optical film, adherent type optical film and image display device |
| US7285313B2 (en) * | 2004-01-20 | 2007-10-23 | Lg Chem Ltd. | Acrylic pressure-sensitive adhesive composition for polarizing film |
| KR100668943B1 (en) * | 2004-04-23 | 2007-01-12 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition for polarizing plate |
| JP3916638B2 (en) * | 2004-12-02 | 2007-05-16 | 日東電工株式会社 | Adhesive optical film and image display device |
-
2006
- 2006-07-14 KR KR1020060066537A patent/KR100784995B1/en active Active
- 2006-08-29 CN CN2006800325026A patent/CN101258214B/en active Active
- 2006-08-29 JP JP2008528937A patent/JP5128478B2/en active Active
- 2006-09-01 TW TW095132311A patent/TWI335932B/en active
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127183A (en) * | 2010-01-20 | 2011-07-20 | 3M创新有限公司 | Crosslinkable acrylate adhesive polymer composite |
| CN102127183B (en) * | 2010-01-20 | 2014-08-20 | 3M创新有限公司 | Crosslinkable acrylate adhesive polymer composite |
| CN102212317A (en) * | 2010-04-02 | 2011-10-12 | 素塔电子科技(上海)有限公司 | Adhesive agent of polaroid and preparation method for polaroid by using adhesive agent |
| CN103146323A (en) * | 2011-03-31 | 2013-06-12 | 琳得科株式会社 | An adhesive and adhesion sheet |
| US9574111B2 (en) | 2012-01-18 | 2017-02-21 | Mitsubishi Plastics, Inc. | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| CN104356969B (en) * | 2012-01-18 | 2017-06-13 | 三菱树脂株式会社 | Device used for image display transparent double face bonding sheet and the image display device using the double-sided adhesive sheet |
| CN104356969A (en) * | 2012-01-18 | 2015-02-18 | 三菱树脂株式会社 | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| CN104053736A (en) * | 2012-01-18 | 2014-09-17 | 三菱树脂株式会社 | Transparent Double-sided Adhesive Sheet For Image Display Device And Image Display Device Using Same |
| TWI588030B (en) * | 2012-01-18 | 2017-06-21 | Mitsubishi Plastics Inc | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| CN104053736B (en) * | 2012-01-18 | 2016-03-23 | 三菱树脂株式会社 | Device used for image display transparent double face adhesive sheet and use the image display device of this double-sided adhesive sheet |
| US9353293B2 (en) | 2012-01-18 | 2016-05-31 | Mitsubishi Plastics, Inc. | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| US9441141B2 (en) | 2012-01-18 | 2016-09-13 | Mitsubishi Plastics, Inc. | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| CN104312470A (en) * | 2012-01-18 | 2015-01-28 | 三菱树脂株式会社 | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| CN104312470B (en) * | 2012-01-18 | 2017-04-12 | 三菱树脂株式会社 | Transparent double-sided adhesive sheet for image display device and image display device using the same |
| CN107674618B (en) * | 2012-05-31 | 2020-12-08 | Lg化学株式会社 | Pressure sensitive adhesive composition |
| CN107674618A (en) * | 2012-05-31 | 2018-02-09 | Lg化学株式会社 | Pressure-sensitive adhesive composition |
| US9931812B2 (en) | 2012-12-27 | 2018-04-03 | Nitto Shinko Corporation | Insulating paper for oil-immersed motors |
| CN104812580A (en) * | 2012-12-27 | 2015-07-29 | 日东新兴有限公司 | Insulating paper for oil-immersed motors |
| CN108130026B (en) * | 2013-11-07 | 2020-03-03 | 积水化学工业株式会社 | Adhesive tape |
| CN108130026A (en) * | 2013-11-07 | 2018-06-08 | 积水化学工业株式会社 | Adhesive tape |
| CN104610884A (en) * | 2014-01-09 | 2015-05-13 | 苏州斯迪克新材料科技股份有限公司 | Scratch-resistant protective film for display screen |
| CN107148587A (en) * | 2014-11-04 | 2017-09-08 | 综研化学株式会社 | Polarizer adhesive composition and the polarizer with adhesive phase |
| CN107148587B (en) * | 2014-11-04 | 2020-07-07 | 综研化学株式会社 | Adhesive composition for polarizing plate and polarizing plate with adhesive layer |
| US10851268B2 (en) | 2015-07-10 | 2020-12-01 | Lg Chem, Ltd. | Compound |
| CN107849410B (en) * | 2015-07-10 | 2019-11-19 | 株式会社Lg化学 | Pressure-sensitive adhesion polarizer |
| CN107849410A (en) * | 2015-07-10 | 2018-03-27 | 株式会社Lg化学 | Pressure-sensitive adhesion Polarizer |
| US10883019B2 (en) | 2015-07-10 | 2021-01-05 | Lg Chem, Ltd. | Cross-linkable composition |
| US10883020B2 (en) | 2015-07-10 | 2021-01-05 | Lg Chem, Ltd. | Pressure-sensitive adhesive polarizing plate |
| US10889735B2 (en) | 2015-07-10 | 2021-01-12 | Lg Chem, Ltd. | Cross-linkable composition |
| CN108368397A (en) * | 2015-12-15 | 2018-08-03 | 住友化学株式会社 | The optical film and optical laminate of subsidiary adhesive phase |
| CN109906208A (en) * | 2016-05-23 | 2019-06-18 | 康宁股份有限公司 | Glass-making processes and equipment |
| US11130697B2 (en) | 2016-05-23 | 2021-09-28 | Corning Incorporated | Glass manufacturing method and apparatus |
| CN109906208B (en) * | 2016-05-23 | 2022-06-10 | 康宁股份有限公司 | Glass manufacturing method and apparatus |
| CN111148811A (en) * | 2017-12-11 | 2020-05-12 | 株式会社Lg化学 | Adhesive composition for foldable displays and foldable displays comprising the same |
| CN111148811B (en) * | 2017-12-11 | 2021-12-28 | 株式会社Lg化学 | Adhesive composition for foldable display and foldable display comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI335932B (en) | 2011-01-11 |
| KR100784995B1 (en) | 2007-12-11 |
| TW200720387A (en) | 2007-06-01 |
| CN101258214B (en) | 2010-12-15 |
| JP5128478B2 (en) | 2013-01-23 |
| JP2009507255A (en) | 2009-02-19 |
| KR20070025980A (en) | 2007-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101258214B (en) | Acrylic pressure-sensitive adhesive composition for polarizing film | |
| CN101309991B (en) | Acrylic pressure-sensitive adhesive composition for polarizing film | |
| CN101331202B (en) | Acrylic pressure-sensitive adhesive compositions | |
| KR100932888B1 (en) | Optically compensated acrylic pressure sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same | |
| KR101171977B1 (en) | Acrylic pressure-sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same | |
| EP1931744B1 (en) | Acrylic pressure-sensitive adhesive composition for polarizing film | |
| CN100551985C (en) | Acrylic pressure sensitive adhesive composition for polarizing film | |
| KR101019064B1 (en) | Acrylic pressure-sensitive adhesive composition | |
| US9399695B2 (en) | Pressure-sensitive adhesive compositions, polarizers and liquid crystal displays comprising the same | |
| KR101340546B1 (en) | Binder for adhesive composition, method for preparing thereof, adhesive composition comprising the same and optical member using the same | |
| KR101023839B1 (en) | Pressure-sensitive adhesive composition, polarizing plate and liquid crystal display including the above | |
| KR101171976B1 (en) | Acrylic pressure-sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same | |
| KR100694446B1 (en) | Acrylic pressure sensitive adhesive resin composition | |
| KR101233901B1 (en) | Acrylic pressure-sensitive adhesive compositions | |
| KR101202532B1 (en) | Acrylic pressure-sensitive adhesive composition | |
| KR101584892B1 (en) | Pressure sensitive adhsive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210609 Address after: Room 1, room 2, room 3, No. 2, Tangqiao Middle Road, Tangshi street, yangshe Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee after: Shanjin Optoelectronics (Suzhou) Co.,Ltd. Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231103 Address after: 510799 No. 50, Dongxiang Road, Huangpu District, Guangzhou, Guangdong Patentee after: Shanjin photoelectric (Guangzhou) Co.,Ltd. Address before: 215699 room 1 room 2 Room 3, No.2 Tangqiao Middle Road, Tangshi street, yangshe Town, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee before: Shanjin Optoelectronics (Suzhou) Co.,Ltd. |