KR20140141814A - Adhesive composition for polarizing plate and polarizing plate using the same - Google Patents

Adhesive composition for polarizing plate and polarizing plate using the same Download PDF

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KR20140141814A
KR20140141814A KR1020130062361A KR20130062361A KR20140141814A KR 20140141814 A KR20140141814 A KR 20140141814A KR 1020130062361 A KR1020130062361 A KR 1020130062361A KR 20130062361 A KR20130062361 A KR 20130062361A KR 20140141814 A KR20140141814 A KR 20140141814A
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group
polarizing plate
compound
adhesive composition
epoxy
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KR1020130062361A
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Korean (ko)
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조천희
권혜림
최한영
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동우 화인켐 주식회사
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    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention relates to an adhesive composition for a polarizing plate and a polarizing plate using the same and, more specifically, to an adhesive composition for a polarizing plate having excellent adhesion and water resistance by containing a compound including an epoxy group and an acryl group, and to a polarizing plate using the same. The present invention has a purpose of providing an adhesive composition for a polarizing plate, which has water resistance of not being peeled off under a humidifying and heating condition and has excellent adhesion even in a case of the polarities of the polarizing plate and a protective film being different.

Description

[0001] The present invention relates to an adhesive composition for a polarizing plate and a polarizing plate using the adhesive composition.

The present invention relates to an adhesive composition for a polarizing plate having excellent adhesive strength and water resistance, and a polarizing plate using the same.

In a liquid crystal display device, a polarizing plate is disposed on both sides of a glass substrate that forms the liquid crystal panel surface in terms of the image forming method. Generally, the polarizing plate comprises a polarizer and a protective film adhered to at least one surface of the polarizer.

The polarizer is generally obtained by dying with a dichromatic material such as a polyvinyl alcohol-based film and iodine, then crosslinking using a crosslinking agent, and stretching. Since the polarizer is produced by stretching, it is likely to shrink. Further, since the polyvinyl alcohol film uses a hydrophilic polymer, it is very easy to be deformed under humidified heat conditions. Further, there is a problem that the mechanical strength of the film itself is weak.

Therefore, a polarizing plate in which a transparent protective film is adhered to both sides or one side of the polarizer to supplement the strength is used. Such a polarizing plate is manufactured by adhering a polarizer and a transparent protective film with an adhesive.

2. Description of the Related Art [0002] Recent liquid crystal display devices have widened in their use, and have been widely extended from portable terminals to large-sized household televisions. The enlargement of the use of such a liquid crystal display device further demands improvement of durability capable of operating even in harsh environments.

The polarizer is used as a polarizing plate by reinforcing the strength by a protective film. As the adhesive for the polarizing plate used for bonding the polarizer and the protective film, an aqueous adhesive is preferable. For example, a polyvinyl alcohol adhesive in which a crosslinking agent is mixed in an aqueous solution of polyvinyl alcohol is used. However, in the case of the polyvinyl alcohol-based adhesive, peeling may occur at the interface between the polarizer and the transparent protective film under the humidified heat condition. This is presumably because the polyvinyl alcohol-based resin as the main component of the adhesive is a water-soluble polymer, and therefore it is possible that dissolution of the adhesive occurs under the condition of condensation. In order to solve such a problem, Japanese Unexamined Patent Publication (Kokai) No. 7-198945 proposes an adhesive for a polarizing plate containing an acetoacetyl group-modified polyvinyl alcohol resin and a crosslinking agent.

However, a solution that satisfies both adhesion and water resistance is not yet known. Therefore, it is required to develop an adhesive composition for a polarizing plate exhibiting high adhesiveness and water resistance.

Japanese Patent Application Laid-Open No. 7-198945

An object of the present invention is to provide an adhesive composition for a polarizing plate which has water resistance that is not peeled off even under the humidifying heat condition and is excellent in adhesion even when the polarizer and the protective film have different polarities.

It is another object of the present invention to provide a polarizing plate produced using the above adhesive composition.

1. An adhesive composition for a polarizing plate comprising a compound containing an epoxy group and an acrylic group.

2. The adhesive composition for a polarizing plate according to 1 above, wherein the compound containing an epoxy group and an acrylic group is a partial epoxy (meth) acrylate

3. The adhesive composition for a polarizing plate according to 2 above, wherein the partial (meth) acrylate comprises an arylene diether group having 6 to 12 carbon atoms.

4. The partial epoxide (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms as described in 3 above is obtained by reacting a compound of formula (1) or (2) with (meth) A composition for a polarizing plate which is a mixture:

[Chemical Formula 1]

Figure pat00001

(2)

Figure pat00002

(Wherein R 1 is a hydrogen atom, a methyl group or a methoxy group)

5. The adhesive composition for polarizing plate according to item 4, wherein the mixture of the reaction products obtained by reacting the compound of formula (1) with (meth) acrylic acid is a mixture of compounds represented by the following formulas (1), (3)

[Chemical Formula 1]

Figure pat00003

(3)

Figure pat00004

[Chemical Formula 4]

Figure pat00005

(Wherein R 1 is a hydrogen atom, a methyl group or a methoxy group, and R 2 is a hydrogen atom or a methyl group)

6. The adhesive composition for polarizing plate according to item 4, wherein the mixture of the reaction products obtained by reacting the compound of formula 2 with (meth) acrylic acid is a mixture of compounds represented by the following formulas (2), (5)

(2)

Figure pat00006

[Chemical Formula 5]

Figure pat00007

[Chemical Formula 6]

Figure pat00008

(Wherein R 2 is a hydrogen atom or a methyl group)

7. The adhesive composition for a polarizing plate according to item 3 above, wherein the partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms has a viscosity of 500 to 200,000 cps.

8. The adhesive composition for polarizing plate according to 1 above, further comprising a diluting monomer comprising an epoxy compound or an oxetane compound, a cationic photoinitiator and a radical photoinitiator.

9. The composition of claim 8, which comprises 5 to 35% by weight of a partial epoxy (meth) acrylate compound comprising an arylene diether group having 6 to 12 carbon atoms, 60 to 90% by weight of a diluent monomer comprising an epoxy compound or an oxetane compound, 0.1 to 5% by weight of a cationic photoinitiator and 0.1 to 5% by weight of a radical photoinitiator.

10. The adhesive composition for a polarizing plate as described in 8 above, wherein the epoxy compound of the diluting monomer comprises at least one selected from the group consisting of an aromatic epoxy compound, an alicyclic epoxy compound and an aliphatic epoxy compound.

11. The adhesive composition for a polarizing plate according to item 10, wherein the aromatic epoxy compound comprises at least one member selected from the group consisting of diglycidyl ether of bisphenol A, diclcidyl ether of bisphenol F and phenoxy glycidyl ether Composition.

12. The composition of claim 10 wherein the alicyclic epoxy compound is selected from the group consisting of dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate And a compound having an epoxidized cyclohexyl group as a bis (3,4-epoxycyclohexylmethyl) adipate.

13. The composition of claim 10, wherein the aliphatic epoxy compound is selected from the group consisting of 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl Ether and polytetramethylene glycol diglycidyl ether. ≪ RTI ID = 0.0 > 8. < / RTI >

14. The composition of claim 8 wherein the oxetane compound of the diluent monomer is selected from the group consisting of 3-ethyl-3 - [(3-ethyloxetan-3-yl) methoxymethyl] oxetane, Methoxymethyl] benzene, 1,4-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1,3-bis [ Methoxy] benzene, 4,4'-bis [(3-ethyloxetan-3-yl) methoxy] Biphenyl, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- And at least one member selected from the group consisting of phenoxymethyloxetane and 3-ethyl-3-hydroxymethyloxetane.

15. The adhesive composition for a polarizing plate as described in 8 above, wherein the cationic photoinitiator comprises at least one member selected from the group consisting of an aromatic diazonium salt photoinitiator, an aromatic halonium salt photoinitiator, and an aromatic sulfonium salt photoinitiator.

16. The adhesive composition for a polarizing plate according to the above 8, wherein the radical photoinitiator comprises at least one member selected from the group consisting of a carbonyl photoinitiator, a benzoin ether photoinitiator and an acetophenone photoinitiator.

17. A polarizing plate on which a protective film is bonded to at least one surface of a polarizer with an adhesive composition for a polarizing plate of any one of 1 to 16 above.

18. The polarizing plate according to 17 above, wherein the protective film is at least one selected from the group consisting of a cellulose-based resin film, a cycloolefin-based resin film, an acrylic resin film and a polyester-based resin film.

The adhesive composition for a polarizing plate according to the present invention contains a compound containing an epoxy group and an acrylic group, and thus exhibits excellent adhesion even when the polarizer and the protective film have different polarities.

The adhesive composition for a polarizing plate of the present invention contains a partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms, so that the viscosity is low and the coating property is excellent.

The adhesive composition for a polarizing plate of the present invention can be used in combination with a cationic photoinitiator and a radical photoinitiator, which is more economical.

When the polarizer and the protective film are adhered to each other with the adhesive composition for a polarizing plate of the present invention, they have excellent water resistance, which is not peeled off even under humid heat conditions.

1 is a diagram schematically showing an evaluation test method for water resistance.

The present invention relates to an adhesive composition for a polarizing plate, which contains a compound containing an epoxy group and an acrylic group and thus has excellent adhesion and water resistance.

Hereinafter, the present invention will be described in detail.

The compound containing an epoxy group and an acrylic group contained in the adhesive composition for a polarizing plate of the present invention is a component that imparts the binder function of the adhesive composition through a curing reaction.

The epoxy group and the acrylic group-containing compound according to the present invention simultaneously contain both a hydrophilic epoxy group and a hydrophobic acrylic group in one molecule, so that they have excellent adhesion even when the polarizers and the protective film have different polarities. In addition, since a radical photoinitiator used for polymerizing a cationic photoinitiator and an acrylate group used in polymerizing a compound having an epoxy group can be used in combination, a relatively inexpensive cationic photoinitiator can be used, so that the composition can be more economically polymerized do.

Specific examples of the compound containing an epoxy group and an acrylic group include a partial epoxy (meth) acrylate compound. The partial epoxy (meth) acrylate compound is obtained by reacting an epoxy compound with (meth) acrylic acid. When the epoxy compound is reacted with (meth) acrylic acid, the epoxy group is opened by (meth) acrylic acid, Refers to a mixture of a di (meth) acrylate compound and a mono (meth) acrylate compound in which the epoxy group is partially (meth) acrylated, and an unreacted epoxy compound remains. In the present invention, (meth) acrylic means acrylic or methacrylic.

Examples of the epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol AD type epoxy compounds, novolak type epoxy compounds, naphthalene type epoxy compounds, trisphenol methane type epoxy compounds, glycidylamine type epoxy compounds and the like Available.

The partial epoxy (meth) acrylate compound can be obtained by reacting the epoxy compound with (meth) acrylic acid in an appropriate equivalent amount. The content of the reactant is not particularly limited, but, for example, 0.01 to 5 equivalents, preferably 0.5 to 1.8 equivalents.

The catalyst for the reaction of forming the partial epoxy (meth) acrylate compound is not particularly limited and may be an amine or an inorganic alkali compound. Specific examples of the amines include triethylamine, dimethylamine, trimethylamine, triethylamine, benzylmethylamine and the like. Specific examples of the inorganic alkali compound include sodium chromate and sodium hydrogen carbonate.

More specific examples of the partial epoxy (meth) acrylate compound include a partial epoxy (meth) acrylate compound containing an arylene diether group having 6 to 12 carbon atoms. In the present invention, the arylene diether group means a structure in which two ether bonds are connected to two bonds of an arylene group.

When the partial epoxy (meth) acrylate compound according to the present invention is an arylene diether group having 6 to 12 carbon atoms, it has an excellent adhesive force due to a synergistic effect of wettability with a substrate and an effect of reducing internal stress, The applicability of the adhesive composition containing the partial epoxy (meth) acrylate compound can be improved.

The partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms can be obtained by reacting an epoxy compound with (meth) acrylic acid as described above. The epoxy compound has a carbon number of 6 Is not particularly limited as long as it contains one aryl group of 1 to 12 carbon atoms, and examples thereof include benzene diol diglycidyl ether compounds and naphthalene diol diglycidyl epoxy compounds.

The partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms is not particularly limited as long as it is a mixture of reaction products of the epoxy compound and (meth) acrylic acid, Can be a mixture of reaction products obtained by reacting a compound represented by the formula (2) with (meth) acrylic acid.

[Chemical Formula 1]

Figure pat00009

(2)

Figure pat00010

(Wherein R 1 is a hydrogen atom, a methyl group or a methoxy group)

In the above formula 1, the position of the substituent bonded to the phenyl group is not particularly limited. For example, when R 1 is a hydrogen atom, it may be meta or para. When R 1 is a methyl group or a methoxy group, , ≪ / RTI > 3,5 or 1,4,5. When the position of the substituent is the same as above, the coating property in the bonding step is excellent.

In the above formula (2), the position of the substituent bonded to the naphthalene group is not particularly limited and may be, for example, 1,5, 1,6, 1,7, 2,6, or 2,7. When the position of the substituent is the same as above, the coating property in the bonding step is excellent.

The mixture of reaction products obtained by reacting the compound represented by the formula (1) with (meth) acrylic acid may include a mixture of the compounds represented by the following formulas (1), (3)

[Chemical Formula 1]

Figure pat00011

(3)

Figure pat00012

[Chemical Formula 4]

Figure pat00013

(Wherein R 1 is a hydrogen atom, a methyl group or a methoxy group, and R 2 is a hydrogen atom or a methyl group)

The mixture of reaction products obtained by reacting the compound represented by the formula (2) with (meth) acrylic acid may include a mixture of the compounds represented by the following formulas (2), (5)

(2)

Figure pat00014

[Chemical Formula 5]

Figure pat00015

[Chemical Formula 6]

Figure pat00016

(Wherein R 2 is a hydrogen atom or a methyl group)

The compounds of formulas (1) and (2) are unreacted epoxy compounds, and the compounds of formulas (3) and (5) are monoacrylates in which a part of the epoxy groups are subjected to ring- Acrylate < / RTI > In the above formula, R 1 is a hydrogen atom, a methyl group or a methoxy group, and R 2 is a hydrogen atom or a methyl group. When an adhesive composition for a polarizing plate is formed using such a compound, it has excellent adhesive properties and is excellent in curability, Tg of a cured product, and physical properties of a cured product.

The partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms is a compound obtained by mixing the compounds of the above formulas (1), (3) and (4) Is not particularly limited. The mixing ratio can be controlled by reacting the compound of formula (1) or (2) with (meth) acrylic acid in an equivalent ratio, reaction conditions, and the like. When reacting with acrylic acid, R 2 in the above formula is a hydrogen atom, and when reacting with methacrylic acid, R 2 is a methyl group.

The mixing ratio of the partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms may be determined according to the equivalent ratio or the reaction conditions as described above. For example, 15 to 35% by weight of the unreacted epoxy compound of the formulas (1) and (2), 30 to 60% by weight of the monoacrylate compound of the formulas (3) and (5) By weight of a diacrylate compound.

The viscosity of the partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms is preferably 500 to 200,000 cps, and more preferably 1,000 to 100,000 cps. When the viscosity is 500 to 200,000 cps, the applicability of the adhesive composition for a polarizing plate containing the same can be improved.

The content of the compound including an epoxy group and an acrylic group is not particularly limited and may be 5 to 35% by weight, preferably 15 to 25% by weight, based on the total weight of the composition. When the compound containing an epoxy group and an acrylic group is contained in an amount of 5 to 35% by weight, adhesion between the polarizer and the protective film can be remarkably increased if the polarity is different.

The adhesive composition for a polarizing plate of the present invention may further include a diluent monomer, a cation photoinitiator and a radical photoinitiator, which include an epoxy compound or an oxetane compound, in addition to the above-mentioned compounds containing an epoxy group and an acrylic group.

The diluted monomer is used as a viscosity modifier in the reaction and has a function of controlling the curing degree of the composition by affecting the reactivity. In particular, the oxetane compound greatly enhances the reactivity of the ring-opening reaction because of the strong basicity of oxygen on the ring of the oxetane compound.

The type of the diluting monomer containing an epoxy compound or an oxetane compound is not particularly limited as long as it is used in the art, and generally known curing compounds can be used.

The type of the epoxy compound of the diluting monomer is not particularly limited as long as it is used in the art, and may include at least one member selected from the group consisting of an aromatic epoxy compound, an alicyclic epoxy compound and an aliphatic epoxy compound.

The kind of the aromatic epoxy compound is not particularly limited and includes, for example, at least one selected from the group consisting of diglycidyl ether of bisphenol A, diclcidyl ether of bisphenol F and phenoxyglycidyl ether .

The kind of the alicyclic epoxy compound is not particularly limited, and examples thereof include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane An epoxycyclohexyl group composed of a carboxylate and a bis (3,4-epoxycyclohexylmethyl) adipate, and the like.

The kind of the aliphatic epoxy compound is not particularly limited, and examples thereof include 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetra Glycidyl ether, and polytetramethyleneglycol diglycidyl ether. The term " glycidyl ether "

The kind of the oxetane compound of the diluting monomer is not particularly limited as long as it is used in the art, and examples thereof include 3-ethyl-3 - [(3-ethyloxetan-3-yl) methoxymethyl] oxetane, , 3-ethyloxetane-3-yl) methoxy] benzene, 1,4-bis [ (3-ethyloxetan-3-yl) methoxy] benzene, 1,2-bis [ 3-yl) methoxy] biphenyl, 3-ethyl-3- (2-ethylhexyloxymethyl) Oxetane, 3-ethyl-3-phenoxymethyloxetane and 3-ethyl-3-hydroxymethyloxetane.

The content of the diluting monomer including an epoxy or oxetane compound is not particularly limited and may include 60 to 90% by weight of a diluting monomer containing an epoxy or oxetane compound based on the total weight of the adhesive composition for a polarizing plate, Preferably 70 to 80% by weight. If the amount of the diluted monomer is more than 90% by weight, the reactivity becomes excessively high to lower the adhesive strength. When the dilution monomer is less than 60% by weight, the reactivity is deteriorated.

Since the adhesive composition for a polarizing plate according to the present invention contains a compound containing both an epoxy group and an acrylic group, a cationic photoinitiator and a radical photoinitiator can be used at the time of polymerization, and it is more economical to use a comparatively inexpensive cationic photoinitiator.

 The type of the cationic photoinitiator is not particularly limited as long as it is used in the art and may include at least one member selected from the group consisting of aromatic diazonium salt photoinitiator, aromatic halonium salt photoinitiator and aromatic sulfonium salt photoinitiator. Specific examples of commercially available cationic photoinitiators include ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-170, ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-172, Photoinitiator 2074 (Rhodia), CPI-110A (San-Efrosa), CPI-100P (San-Efrosa) and CPI-101A (San-Efrosa).

The content of the cationic photoinitiator is not particularly limited and may be, for example, 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total weight of the adhesive composition for a polarizing plate. If the content of the cationic photoinitiator is less than 0.1% by weight, the adhesive composition of the present invention may not sufficiently cure. If the content of the cationic photoinitiator exceeds 5% by weight, unreacted photopolymerization initiator Yellowing may occur.

The radical photoinitiator may be at least one selected from the group consisting of a carbonyl photoinitiator, a benzoin ether photoinitiator, and an acetophenone photoinitiator, as long as it is used in the art. Specific examples of commercially available radical photoinitiators include darocur 1173, darocur BP, darocur BP, darocur MBF, irgacure 184, irgacure 500, irgacure 2959, irgacure 754, irgacure 651, irgacure 369, irgacure 907, irgacure 1300, irgacure 819, irgacure 2022, irgacure 819DW, irgacure 2100, irgacure 784, irgacure 250, and the like.

The content of the radical photoinitiator is not particularly limited and may be, for example, 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total weight of the adhesive composition for a polarizing plate. If the amount of the radical photoinitiator is less than 0.1% by weight, the adhesive composition of the present invention may not sufficiently cure. If the amount of the photoinitiator exceeds 5% by weight, unreacted photopolymerization initiator Yellowing may occur.

The present invention also relates to a polarizing plate in which a protective film is bonded to at least one surface of a polarizer with an adhesive composition for a polarizing plate of the present invention.

The polarizer may be a polyvinyl alcohol-based resin. The polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate resin include a copolymer of vinyl acetate and other monomers copolymerizable therewith, as well as polyvinyl acetate, which is a homopolymer of vinyl acetate. Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, acrylamides having an ammonium group, and the like

The kind of the protective film is not particularly limited as long as it is excellent in transparency, mechanical strength, thermal stability, moisture barrier property and isotropy, and examples thereof include cellulose resin film, cycloolefin resin film, acrylic resin film, And various transparent resin films including at least one kind selected from the group consisting of films.

When a cellulose-based resin film is used as the protective film, it is preferable that at least a part of the cellulose is acetic acid-cellulose acetate-based resin, for example, triacetylcellulose, diacetylcellulose, cellulose acetate propionate and the like.

The cycloolefin-based resin film is a thermoplastic resin film having a monomer unit of cycloolefin such as norbornene or a polycyclic norbornene monomer, and a ring-opening polymer of the cycloolefin or a ring-opening copolymer using two or more cycloolefins Or may be an addition copolymer of a cycloolefin and an aromatic compound having a chain olefin or vinyl group. In addition, a polar group may be introduced into the cycloolefin-based resin.

In addition, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, an acrylic resin such as polymethyl methacrylate, a styrene resin such as polystyrene or acrylonitrile-styrene copolymer (AS resin), a polycarbonate resin Can be used.

The method of bonding the polarizer and the protective film using the adhesive composition for a polarizing plate of the present invention is not particularly limited, and the methods used in the art can be applied without any particular limitation. After applying the adhesive composition of the present invention, the polarizer and the protective film are bonded.

Further, in order to improve the adhesiveness, the surface of the polarizer and / or the protective film may be subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet ray irradiation treatment, frame treatment and saponification treatment. As the saponification treatment, a method of immersing in an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide can be mentioned.

The thus prepared polarizing plate can be applied to all ordinary image devices.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Manufacturing example  One - Polarizer  Produce

A polyvinyl alcohol film having a thickness of 75 탆 and an average degree of polymerization of 2,400 and a saponification degree of 99.9 mol% or more was uniaxially stretched by a dry method about 5 times and immersed in water (distilled water) at 60 캜 for 1 minute while maintaining the stretched state And immersed for 60 seconds in an aqueous solution at 28 DEG C in which the weight ratio of after-iodine: potassium iodide: distilled water was 0.05: 5: 100. Thereafter, the resultant was immersed in an aqueous 72 ° C solution of potassium iodide: boric acid: distilled water at a weight ratio of 8.5: 8.5: 100 for 300 seconds, washed with distilled water at 26 ° C for 20 seconds and dried at 65 ° C, Adsorbed polarizers were prepared.

Manufacturing example  Synthesis of 2-Epoxy Compound

(1) Benzene 1,4- Diol Diglycidyl  Ether synthesis

To 100 g of hydroquinone is added 12 equivalents of epichlorohydrin and 0.1 equivalent of tetrabutylammonium bromide, and the mixture is heated to 100 DEG C with no additional solvent. After reacting at 100 ° C for 3 hours, it was confirmed by NMR analysis that all of the phenolic hydroxyl groups disappeared and cooled to room temperature.

2 equivalents of a 20% NaOH aqueous solution is added dropwise with vigorous stirring while controlling the internal temperature not to exceed 30 占 폚. After stirring for an additional 2 hours, it is confirmed by NMR analysis that all of the epoxy ring formation reaction proceeds, and then extracted with 500 mL of water and toluene (500 mL). Dehydrated with sodium sulfate, and the remaining tetrabutylammonium bromide is prepared using silica gel. And dried under reduced pressure to obtain benzene 1,4-diglycidyl ether (130 g) of the above formula (7). The obtained product was confirmed to be a product by NMR analysis without further purification.

(7)

Figure pat00017

(2) Benzene 1,3- Diol Diglycidyl  Ether synthesis

Benzene 1,3-diglycidyl ether was synthesized in the same manner as in [Formula 7] except that 100 g of resorcinol was used instead of hydroquinone as the dihydroxy compound.

[Chemical Formula 8]

Figure pat00018

(3) Naphthalene 1,6- Diol Diglycidyl  Ether synthesis

Naphthalene 1,6-diglycidyl ether was synthesized in the same manner as in [Formula 7] except that 100 g of naphthalene 1,6-dihydroxynaphthalene was used instead of hydroquinone as the dihydroxy compound.

[Chemical Formula 9]

Figure pat00019

Example  One

< For polarizer  Preparation of adhesive composition &gt;

700 g of the epoxy compound of the formula (7), 1 g of triethylamine and 2 g of 4-methoxyphenol as a catalyst were added and the mixture was heated to 80 ° C while stirring. Thereafter, 200 g of methacrylic acid was added dropwise, followed by reflux stirring for 5 hours. Toluene and 1% oxalic acid were added to the obtained partial epoxy (meth) acrylate compound and stirred to remove ions, followed by removal of toluene and 1% oxalic acid to obtain a partial epoxy (meth) acrylate compound. As a result of measurement of the synthesized partial epoxy (meth) acrylate compound by GPC, 30 percent by weight of the diacrylate compound in which the epoxy group was completely opened by opening the epoxy group with acrylate, and the monoacrylate compound in which the epoxy group was partially acrylated was 45 weight % And an unreacted epoxy compound in an amount of 25% by weight.

To 20 parts by weight of the synthesized partial epoxy (meth) acrylate compound, 75 parts by weight of an oxetane compound (OXT-211, Donga Synthetic Co.), 3 parts by weight of a cationic photoinitiator (CPI-110A, , Ciba Corp.) were blended to obtain an adhesive composition for a polarizing plate.

<Production of polarizing plate>

 As the protective film, the following two kinds of films were used. (70 mu m), a polymethylmethacrylate film (50 mu m), and the adhesion surfaces of the two films were subjected to corona discharge treatment, and then provided for joining with the produced polarizer.

On the corona discharge treated surface of the drawn norbornene resin film, the adhesive composition prepared above was coated to a thickness of 3 탆 by a bar coater, and the polarizer produced thereon was bonded. Separately, the polymethylmethacrylate film was coated with the same adhesive with a bar coater to a thickness of 3 탆, and the norbornene resin film was bonded to the opposite side of the polarizer bonded. Thus, a polarizer having a protective film bonded on both surfaces thereof was irradiated with ultraviolet rays at an integrated light quantity of 300 mJ / cm 2 from one surface by an ultraviolet irradiation device (Fusion H valve, Fusion) equipped with a belt conveyer to produce a polarizing plate.

Example  2

A polarizing plate was prepared in the same manner as in Example 1, except that the compound of the formula (8) was used instead of the compound of the formula (7).

[Chemical Formula 8]

Figure pat00020

Example  3

A polarizing plate was prepared in the same manner as in Example 1, except that the compound of the formula (9) was used instead of the compound of the formula (7).

[Chemical Formula 9]

Figure pat00021

Example  4 to 15, Comparative Example  1 to 6

An adhesive composition and a polarizing plate were prepared in the same manner as in Example 1, except that the components and composition ratios shown in Table 1 were used.

(weight%) Partial epoxy compound Diluted monomer Acrylate
compound Epoxy
compound Cation photoinitiator Radical photoinitiator Formula 7 8 Formula 9 A B C D E F G H I J K L CPI-110A Irg 184 Example 1 20 75 3 2 Example 2 20 75 3 2 Example 3 20 75 3 2 Example 4 20 75 3 2 Example 5 20 75 3 2 Example 6 20 75 3 2 Example 7 10 85 3 2 Example 8 10 85 3 2 Example 9 30 65 3 2 Example 10 30 65 3 2 Example 11 20 75 3 2 Example 12 20 75 3 2 Example 13 20 75 3 2 Example 14 20 75 3 2 Example 15 40 55 3 2 Comparative Example 1 40 40 15 5 Comparative Example 2 40 40 17 3 Comparative Example 3 30 50 15 5 Comparative Example 4 50 30 15 5 Comparative Example 5 40 40 15 5 Comparative Example 6 50 30 15 5

A: An aromatic epoxy compound (phenoxyglycidyl ether, Aldrich)

B: an alicyclic epoxy compound (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, Daicel)

C: aliphatic epoxy compound (1,4-butanediol diglycidyl ether, Aldrich))

D: Oxetane compound (OXT-211, Donga Synthesis)

E: Oxetane compound (3-ethyl-3 - [(3-ethyloxetan-3-yl) methoxymethyl] oxetane,

F: Oxetane compound (1,2-bis [(3-ethyloxetan-3-yl) methoxy] benzene,

G: N-Hydroxyethyl acrylamide (HEAA, TCI)

H: 4-acrylonylmorpholine (ACMO, Beijing RBL Chemical Co.)

I: Dimethylaminoethyl acrylate (DMAEA, TCI)

J: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CEL2021P, Daicel)

K: 1,4-butanediol diglycidyl ether (Aldrich)

L: bisphenol A epoxy (YD-114, Kukdo Chemical)

Test Example

The following evaluation tests were performed on each of the polarizers obtained in Examples and Comparative Examples, and the results are shown in Table 2 below.

[1] Adhesion (Cutter) Evaluation

Each polarizing plate was allowed to stand at room temperature for 1 hour, and then a cutter blade was inserted between each polarizing plate (between the polarizer and the protective film), and the blade was pushed forward.

A: The cutter blade does not enter any film.

A: The cutter blade stops when it reaches about 2 mm between the films.

B: When pushing the blade, it stops when the blade reaches 4 to 5 mm between at least one of the films.

X: When pushing the blade, the blade is easily inserted between at least one of the films (if the blade is easily inserted between the two films, the blade does not enter the other blade, ㎜ It includes stopping when entering.)

[2] Evaluation of water resistance

Each of the polarizing plates left for 24 hours in an environment of 23 캜 and 55% relative humidity was subjected to the following water resistance test (hot water immersion test) to evaluate the water resistance. First, a polarizing plate was cut into a rectangular shape of 5 cm x 2 cm with the absorption axis (stretching direction) of the polarizing plate as a long side to prepare a sample, and the dimension in the long side direction was measured accurately. Here, the sample uniformly exhibits a unique color over the entire surface due to the iodine adsorbed on the polarizing film. Here, FIG. 1 is a diagram schematically showing an evaluation test method for water resistance. FIG. 1 (A) shows sample 1 before immersion in hot water, and FIG. 1 (B) shows sample 1 after immersion in hot water. As shown in Fig. 1 (A), one short side of the sample was held by a gripping section (5), and about 80% of the sample in the longitudinal direction was immersed in a water bath at 60 DEG C and held for 4 hours. Thereafter, the sample (1) was taken out from the water tank to wipe out the water.

By the immersion in hot water, the polarizing film 4 of the polarizing plate shrinks. The degree of shrinkage of the polarizing film 4 is set to be the distance from the end 1a of the sample 1 at the center of the short side of the sample 1 to the end of the polarizing film 4 And the shrinkage length was determined. As shown in Fig. 1 (B), the polarizing film 4 located in the center of the polarizing plate shrinks due to the immersion of hot water, so that the region 2 in which the polarizing film 4 is not present between the protective films is formed .

Further, iodine elutes from the peripheral portion of the polarizing film 4 which is in contact with the hot water due to the hot water immersion, and a portion 3 in which the color is missing in the peripheral portion of the sample 1 is generated. The degree of discoloration was evaluated by measuring the distance from the end of the shrunk polarizing film 4 at the center of the shorter side of the sample 1 to the area where the color unique to the polarizing plate remained, and the value was regarded as the iodine dropout length. The total length of the shrinkage length and the iodine dropout length was defined as the total erosion length (X). That is, the total erosion length X is the distance from the end 1a of the sample 1 (the end of the protective film) at the center of the short side of the sample 1 to the region where the color unique to the polarizer remains. It can be judged that the smaller the shrinkage length, the iodine dropout length and the total erosion length X, the higher the adhesiveness (water resistance) in the presence of water.

◎: total erosion length X less than 2 mm

○: total erosion length X is 2 mm or more to less than 3 mm

DELTA: total erosion length X is not less than 3 mm and not more than 5 mm

X: total erosion length X of not less than 5 mm

The results of the above experiment are shown in Table 2 below.

Adhesiveness Water resistance Example 1 ◎ ◎ Example 2 ◎ ◎ Example 3 ◎ ◎ Example 4 ◎ ◎ Example 5 ◎ ○ Example 6 ◎ ○ Example 7 ○ ◎ Example 8 ◎ ○ Example 9 ◎ ◎ Example 10 ◎ ◎ Example 11 ◎ ○ Example 12 ◎ ○ Example 13 ◎ ○ Example 14 ◎ ○ Example 15 ○ ○ Comparative Example 1 ○ X Comparative Example 2 ○ X Comparative Example 3 △ X Comparative Example 4 ○ X Comparative Example 5 ○ ○ Comparative Example 6 ○ ○

As shown in Table 2, it was confirmed that the adhesive composition for a polarizing plate according to the present invention had excellent adhesive water resistance.

Further, Example 15 was slightly out of the content range of the present invention, and it was confirmed that adhesiveness and water resistance were slightly lowered at the same time as in Examples 1 to 14. However, it could be confirmed that these compositions were equivalent to or higher than those of Comparative Examples 5 and 6 containing only conventional epoxy compounds.

However, it was confirmed that the adhesiveness and water resistance of Comparative Examples 1 to 4 containing only an acrylate compound other than the partial epoxy (meth) acrylate compound were lower than those of the examples.

Claims (18)

An adhesive composition for a polarizing plate, comprising a compound containing an epoxy group and an acrylic group.
The adhesive composition for a polarizing plate according to claim 1, wherein the compound containing an epoxy group and an acrylic group is a partial epoxy (meth) acrylate
The adhesive composition for a polarizing plate according to claim 2, wherein the partial (meth) acrylate comprises an arylene diether group having 6 to 12 carbon atoms.
4. The epoxy resin composition according to claim 3, wherein the partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms is a mixture of reaction products obtained by reacting a compound represented by the following formula (1) or Adhesive composition for polarizing plate:
[Chemical Formula 1]
Figure pat00022

(2)
Figure pat00023

(Wherein R 1 is a hydrogen atom, a methyl group or a methoxy group)
The adhesive composition for a polarizing plate according to claim 4, wherein the mixture of the reaction products obtained by reacting the compound of formula (1) with (meth) acrylic acid is a mixture of compounds represented by the following formulas (1), (3)
[Chemical Formula 1]
Figure pat00024

(3)
Figure pat00025

[Chemical Formula 4]
Figure pat00026

(Wherein R 1 is a hydrogen atom, a methyl group or a methoxy group, and R 2 is a hydrogen atom or a methyl group)
The adhesive composition for polarizing plate according to claim 4, wherein the mixture of reaction products obtained by reacting the compound of formula (2) with (meth) acrylic acid is a mixture of compounds represented by the following formulas (2), (5)
(2)
Figure pat00027

[Chemical Formula 5]
Figure pat00028

[Chemical Formula 6]
Figure pat00029

(Wherein R 2 is a hydrogen atom or a methyl group)
The adhesive composition for a polarizing plate according to claim 3, wherein the partial epoxy (meth) acrylate compound having an arylene diether group having 6 to 12 carbon atoms has a viscosity of 500 to 200,000 cps.
The adhesive composition for a polarizing plate according to claim 1, further comprising a diluting monomer containing an epoxy compound or an oxetane compound, a cationic photoinitiator and a radical photoinitiator.
The composition according to claim 8, which comprises 5 to 35% by weight of a compound comprising an epoxy group and an acrylate group, 60 to 90% by weight of a dilute monomer comprising an epoxy compound or an oxetane compound, 0.1 to 5% by weight of a cationic photoinitiator and 0.1 to 5% And an adhesive agent for a polarizer.
The adhesive composition for a polarizing plate according to claim 8, wherein the epoxy compound of the diluting monomer comprises at least one selected from the group consisting of an aromatic epoxy compound, an alicyclic epoxy compound and an aliphatic epoxy compound.
The adhesive composition for a polarizing plate according to claim 10, wherein the aromatic epoxy compound comprises at least one member selected from the group consisting of diglycidyl ether of bisphenol A, diclcidyl ether of bisphenol F, and phenoxyglycidyl ether.
[10] The method of claim 10, wherein the alicyclic epoxy compound is at least one selected from the group consisting of dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, (3,4-epoxycyclohexylmethyl) adipate having at least one epoxidized cyclohexyl group.
[10] The method of claim 10, wherein the aliphatic epoxy compound is selected from the group consisting of 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, And at least one member selected from the group consisting of polytetramethylene glycol diglycidyl ether.
9. The method of claim 8, wherein the oxetane compound of the diluent monomer is selected from the group consisting of 3-ethyl-3 - [(3-ethyloxetan-3- yl) methoxymethyl] oxetane, 1,4-bis [ (3-ethyloxetan-3-yl) methoxy] benzene, 1,3-bis [ (3-ethyloxetan-3-yl) methoxy] benzene, 4,4'-bis [ , 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-phenoxy Methyl oxetane, and 3-ethyl-3-hydroxymethyloxetane.
The adhesive composition for a polarizing plate according to claim 8, wherein the cationic photoinitiator comprises at least one selected from the group consisting of an aromatic diazonium salt photoinitiator, an aromatic halonium salt photoinitiator, and an aromatic sulfonium salt photoinitiator.
The adhesive composition for a polarizing plate according to claim 8, wherein the radical photoinitiator comprises at least one selected from the group consisting of a carbonyl photoinitiator, a benzoin ether photoinitiator, and an acetophenone photoinitiator.
Wherein a protective film is bonded to at least one surface of the polarizer with the adhesive composition for a polarizing plate according to any one of claims 1 to 16.
[17] The polarizing plate according to claim 17, wherein the protective film is at least one selected from the group consisting of a cellulose resin film, a cycloolefin resin film, an acrylic resin film and a polyester resin film.
KR1020130062361A 2013-05-31 2013-05-31 Adhesive composition for polarizing plate and polarizing plate using the same KR20140141814A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160001716A (en) * 2014-06-27 2016-01-06 주식회사 엘지화학 Adhesive Composition and Polarizing Plate Comprising the same
JP2016085369A (en) * 2014-10-27 2016-05-19 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． Polarizing plate and image display device including the same
KR20180035246A (en) 2016-09-07 2018-04-06 애경화학 주식회사 A novel cycloaliphatic epoxy acrylic compound having cation curing and UV curing mechanizm

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160001716A (en) * 2014-06-27 2016-01-06 주식회사 엘지화학 Adhesive Composition and Polarizing Plate Comprising the same
JP2016085369A (en) * 2014-10-27 2016-05-19 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． Polarizing plate and image display device including the same
KR20180035246A (en) 2016-09-07 2018-04-06 애경화학 주식회사 A novel cycloaliphatic epoxy acrylic compound having cation curing and UV curing mechanizm

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