WO2013176436A1 - Photocurable and optically transparent adhesive bonding composition, and adhesive bonding sheet containing same - Google Patents

Abstract

The present invention relates to a photocurable and optically transparent adhesive bonding composition which contains aliphatic urethane acrylate, a polythiol-based chain transfer agent, a monofunctional ethylene-based monomer, a photopolymerization initiator, and a stabilizer. The composition according to the present invention contains the aliphatic urethane acrylate and the polythiol-based chain transfer agent so as to have excellent photocuring properties, high reliability in terms of resistance to high temperatures and humidity, ultraviolet rays, and the like, and excellent processability, whereby no stains are produced even in the case of interlayer curing, such as recoating and barrier formation, and thus is suitable for manufacturing adhesive bonding sheets for touch panels.

Description

Photocurable light transparent point, Adhesive composition and the point comprising the same, Adhesive sheet

The present invention relates to a photocurable light transparent point, an adhesive composition, and more particularly, including an aliphatic urethane acrylate and a polythiol chain transfer agent, because of excellent photocurability, optical properties, environmental resistance and processability, the touch panel It relates to a photocurable light transparent point, an adhesive composition which can be used as an interlayer point for the adhesive.

Due to the development of displays and touch panels, interlayer dots, adhesive compositions have been rapidly used to form a market, and for this purpose, dots, adhesive tapes in the form of films have been conventionally used.

However, in the case of using the adhesive tape in the form of a film, the process of peeling and attaching the adhesive tape is not only cumbersome, but there are also a lot of problems in the process automation. This results in very serious yield problems. In addition, in the case of performing the edge bonding process using the adhesive tape, an air layer having a low refractive index is formed, and light scattering is generated. As a result, visibility and contrast ratio of the flat panel display are reduced, resulting in high optical loss. In a variety of environmental resistance conditions, such as high humidity, there is a problem in that the adhesive force is reduced due to the decrease in cohesion.

In order to solve this problem, a process and a method of using a material for performing an interlayer point and adhesion in a liquid phase and then performing curing through photocuring have been proposed.

However, even when the liquid phase process is used, various problems such as staining of repainting have been exhibited. Specifically, when the liquid material is reformed on the partition form or formed material, the partition and the reformed material, and the material There is a problem that a stain occurs between the and the reformed material.

In addition, in the case of a material formed through photocuring, yellowing and haze phenomenon may occur for high temperature, high temperature and high humidity, and ultraviolet irradiation for a long time.

Therefore, in view of the permanent presence of materials in displays and touch panels, beyond the simple point and adhesive properties, high reliability for excellent optical properties and environmental resistance (UV, high temperature, high temperature, high humidity, etc.) has become an essential factor. As a variety of manufacturing processes emerge, materials having excellent processability are required in the market.

In order to solve the above problems, the present invention is excellent in the photocurability, optical properties and environmental resistance, such as high temperature, high temperature and high humidity, ultraviolet light, and excellent in the processability because no stain occurs even in repainting and interlayer curing. It is an object to provide a transparent point, an adhesive composition.

In order to achieve the above object, the present invention,

1) aliphatic urethane acrylates;

2) polythiol chain transfer agents;

3) monofunctional ethylene monomers;

4) photopolymerization initiator; And

5) stabilizer

It provides a photocurable light transparent point, the adhesive composition comprising a.

The present invention also provides a photocurable light transparent point, a point containing a cured product of the adhesive composition, an adhesive layer and a point for a touch panel including the same, an adhesive sheet.

The present invention also provides a touch panel including the dot and the adhesive sheet.

Photocurable light transparent point, the adhesive composition according to the present invention includes an aliphatic urethane acrylate and a polythiol chain transfer agent, optical properties such as photocurability, transparency of transparency, and environmental resistance such as high temperature, high temperature, high humidity, and ultraviolet light It is excellent in reliability and has excellent processability because stains do not occur even during interlayer hardening such as repainting and partition wall formation, and thus it is useful for the manufacture of dots and adhesive sheets for touch panels.

Photocurable light transparent point, the adhesive composition of the present invention is 1) aliphatic urethane acrylate; 2) polythiol chain transfer agents; 3) monofunctional ethylene monomers; 4) photopolymerization initiator; And 5) stabilizers.

Each component is demonstrated below.

1) Aliphatic Urethane Acrylate

In the present invention, an aliphatic urethane acrylate is used in order to have reliability and excellent points and adhesive properties for the environmental resistance of the composition.

Aliphatic urethane acrylate usable in the present invention may be a compound having a bifunctional or less than acrylate functionality, preferably a compound having a structure such as the formula (1):

[Formula 1]

Where

L ₁ is each independently alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkenyl having 3 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, and having 2 to 20 carbon atoms. Acyl, alkoxy having 1 to 20 carbon atoms, hydroxy, hydroxyalkyl having 1 to 20 carbon atoms, halo, haloalkyl having 1 to 20 carbon atoms, amino, silicon, aryl having 6 to 30 carbon atoms, arylalkyl having 6 to 30 carbon atoms Alkylene having 2 to 50 carbon atoms, unsubstituted or substituted with arylene or diisocyanate having 6 to 50 carbon atoms, preferably diisocyanate;

L ₂ is alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, alkenyl having 2 to 20 carbon atoms, cycloalkenyl having 3 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, acyl having 1 to 20 carbon atoms, Substituted by alkoxy, hydroxy having 1 to 20 carbon atoms, hydroxyalkyl having 1 to 20 carbon atoms, halo, haloalkyl having 1 to 20 carbon atoms, amino, silicon, aryl having 6 to 30 carbon atoms, arylalkyl having 6 to 30 carbon atoms, etc. Or unsubstituted C2-C50 alkylene, C2-C50 acylalkylene, C2-C50 oxyalkylene, C6-C50 arylene, C6-C50 acyl arylene or C6-C50 50 oxyarylene, preferably alkylene having 2 to 50 carbon atoms;

Each R ₁ is independently hydrogen or alkyl having 1 to 20 carbon atoms;

Each A is independently C ₁ to C ₄ alkyl;

Each X is independently an integer of 0 to 20;

Y is an integer from 0 to 40;

n is an integer of 0-80.

The diisocyanate usable in the present invention is isophorone diisocyanate, 2,4-toluene diisocyanate, hexamethylene diisocyanate, 2,2-bis-4'-propane diisocyanate, 6-isopropyl-1,3-phenyl Diisocyanate, 1,6-hexanediisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethylphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, p -Phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4- xylene diisocyanate, 1,3,-xylene diisocyanate, 4,4'- dihexyl methane diisocyanate, 1,4 -Tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4-methoxy-1,3-phenylenedi isocyanate, 4-chloro-1,3-phenylenedi isocyanate, 2 , 4-dimethyl-1,3-phenylenedi It may be selected from the group consisting of soocyanate, 4,4-diisocyanate diphenyl ether, 4,4, -diisocyanate dibenzyl and mixtures thereof.

The aliphatic urethane acrylate is preferably used in an amount of 30 to 90% by weight, preferably 40 to 80% by weight based on the total weight of the composition.

When the amount of the aliphatic urethane acrylate is less than 30% by weight, there may be a problem in terms of the viscosity and adhesive properties of the composition or a process problem due to low viscosity, and when the amount is more than 90% by weight, high viscosity May cause fairness problems.

2) Polythiol Chain Transfer Agent

In the present invention, a polythiol-based chain transfer agent is used to maintain high reliability and excellent repainting resistance.

The polythiol chain transfer agent that can be used in the present invention is β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptoprop Cypionate, methoxybutyl-3-mercaptopropionate, styryl-3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), tris (3-mercaptopropionyloxyethyl ) -Isocyanorate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) (and dipentaerythritol hexakis (3-mercaptopropio) Nate).

The polythiol-based chain transfer agent is preferably used in an amount of about 0.01 to 4% by weight, preferably 0.1 to 2.5% by weight based on the total weight of the composition.

When the amount of the chain transfer agent is less than 0.01% by weight, the hardness of the material after curing is increased, and the modulus is increased, so that various stains may be generated during reliability evaluation, and the amount of the chain transfer agent is greater than 4% by weight. In this case, the haze characteristics for environmental resistance evaluation may be deteriorated.

3) Monofunctional Ethylene Monomer

Monofunctional ethylenic monomers usable in the present invention are isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, isodecyl acrylate, methyl methacrylate, alkyl acrylate, steacrylate, cyclohexyl acrylate, Isobornyl acrylate, benzyl methacrylate, benzyl acrylate, 2-hydroxy acrylate, trimethoxybutyl acrylate, ethylcarbitol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxy Polyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl acrylate and their meta Acrylates; Acrylates containing halogen compounds such as 3-fluoroethyl acrylate and 4-fluoropropyl acrylate, and methacrylates thereof; Acrylates containing siloxane groups such as triethylsiloxane ethyl acrylate and methacrylates thereof; And it may be one kind or a mixture of two or more kinds selected from the group consisting of olefins having an aromatic such as styrene, 4-methoxy styrene.

The ethylene-based monomer is preferably used in an amount of 5 to 50% by weight, preferably 15 to 40% by weight based on the total weight of the composition.

When the amount of the ethylene monomer is less than 5% by weight, the viscosity of the solution may be high, so that material fairness such as material coating and defoaming may be deteriorated. When the amount of the ethylene monomer is greater than 50% by weight, the material is applied due to the low viscosity of the solution. Sexual problems can occur.

4) Photopolymerization Initiator

As the photopolymerization initiator that can be used in the present invention, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound or a triazine compound may be used. Specifically, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4 ' -Dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- ( Acetophenone series, such as 4- (methylthio) phenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one compound; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-bis (diethyl amino) benzo Benzophenone compounds such as phenone; Thioxanthone, 2-Chrol Thioxanthone, 2-Methyl Thioxanthone, Isopropyl Thioxanthone, 2,4-Diethyl Thioxanthone, 2,4-Diisopropyl Thioxanthone, 2-Chlorothioke Thioxanthone type compounds, such as Santon; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl dimethyl ketal; And 2,4,6, -trichloro s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl 4,6 -Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-trichloro methyl (piperonyl)- It may be one or a mixture of two or more selected from the group consisting of triazine-based compounds such as 6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine.

In addition, commercially available photoinitiators may be used as the photoinitiator, and examples thereof include Irgacure 2959, 184, 500, 651, 369, 379, 907, 819 and OXE01, Darocure 1173, 1116, 1398, and 1174 from BASF. , 1020 and TPO, CGI242, Lucirin TPO and TPO-L and Lambert's Esacure one, KS300, KS200, A144, EDB, EHA, 1001M, 1064, KTO46 and 1187 can be used alone or in combination .

The photopolymerization initiator is preferably used in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight based on the total weight of the composition.

When the amount of the photopolymerization initiator is less than 0.01% by weight, the curing rate is too slow, which may cause deterioration of processability, and the curing itself may not be achieved. In addition, when the amount of use exceeds 5% by weight, it may cause a decrease in the permeability and yellow index of the material.

5) stabilizer

In the present invention, a stabilizer may also be included in order to have long-term stability and reliability of the material in various environments (high temperature, high temperature, high humidity, excessive ultraviolet light, etc.).

As said stabilizer, poly (dipropylene glycol) phenyl phosphite, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, distyryl pentaerythritol diphosphite, bis (2, 4- Di-tetra-butylphenyl) pentaerythritol diphosphite, dispyl thiopropionate, dilauryl thiodipropionate, ditridecylthiodipropionate, pentaerythryl tetrakis (3-lauricopro Cypionate), Tetrakis [methylene-3- (3,5-di-tetra-butyl-4-hydroxyphenyl) propionate], Isotridecyl-3- (3,5-di-tetra-butyl- 4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-tetra-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di- Tetra-butyl-4-hydroxyphenyl) propionate, 1,2-bis (3,5-di-tetra-butyl-4-hydroxyhydrocyanamo ) Hydrazine, 2,2'-ethylidenebis (4,6-di-tetra-butylphenol), hexamethylenebis [3- (3,5-di-tetra-butyl-4-hydroxyphenyl) propionate ], N, N'hexamethylenebis (3,5-di-tetra-butyl-4-hydroxyhydrocinamide), 4,4'thiobis (6-tetra-butyl-m-cresol), 4,4 '-Butylidenebis (∂-tetra-butyl-3-methylphenol), 4,6-bis (octylthiomethyl) -o-cresol, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, octadecyl-3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, triethyleneglycol-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 2,2-methylenebis (4- Methyl-6- (1-methylcyclohexyl) -phenol), tris (2,4-di-tert-butylphenyl) phosphite, bis (1,2,2,6,6, -pentamethyl-4-pi Ferridyl) Sebacate, Bis (2,2,6,6, -tet Methyl-4-piperidyl) sebacate, bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-hydroxy-2,2,6, 6-tetramethyl-1-piperidineethanol, [2,2'-thiobis (4-tetra-octylphenolato) -ene-butylaminenickel, 2-hydroxy-4-ene-octoxybenzophenone, 2- (2'-hydroxy-5'-methylphenylbenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tetra-butylphenyl) benzotriazole, 2- (2'-hydroxy Oxy-3'-tetra-butyl-5'-methylphenyl-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tetra-butylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-3 ', 5'-di-tetra-amylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2- [2-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole, bis [2-hydroxy-5-tetra-octyl -3- (benzotriazol-2-yl) phenyl] methane, 2,4-di-tetra-butylphenyl-4'-hydroxy-3 ', 5'-di-te La-butylbenzoate, hexadecyl-3,5-di-tetra-butyl-4-hydroxybenzoate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2- Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- (4,6-bis-[[2-hydroxy-4- [ 1- (6-Methyl-heptyloxycarbonyl) -ethoxy] -phenyl]]-[1,3,5] triazin-2-yl) -3-hydroxy-phenoxy] -propionic acid 6-methyl- Heptyl ester, 2- [4- (4,6-bis-biphenyl-4-yl- [1,3,5] triazin-2-yl) -3-hydroxy-phenoxy] -propionic acid 6-methyl -Heptyl ester, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dimethylphenyl) -1,3,5-triazine, etc. 1 type (s) or 2 or more types are mixed Can be used.

In addition, a commercially available material may be used as the stabilizer, and for example, Songnox 1010, 1076, 1077, 1135, 2450, 3114, 1035, 1024, 1290, 2590, 1098, 4150, which are phenolic antioxidants of the Songwon industry. , 4425, 2246, 1330, 1790, 1520 and the like; Songnox 1680, 6260, 6180, 6280, TPP, TDP, DPDP, EHDPP DHOP, etc. as phosphite antioxidants; Songnox DSTDP, DLTDP, DTDTP, 4129 etc. as thioester antioxidant; Songlite 6220, 7700, 2920, 9440, 7830, 1190, 7910 and the like as light stabilizers; Songsolve 1084, 8100, 1000, 3200, 3260, 3270, 3280, 3290, 2340, 3600, 7120, 2908, etc. as UV observers; Anox 20, 70, 330, 1315, IC-14, PP18 and the like, which are antioxidants of Chemtura, USA; Louis Knox 1790, 22M46, 44B25, AH25, CA22, CPL, GP45, HD98, TPB6, WSP, Noward 536, PS48 and the like; Alkanox 240, UltraAnox 626, 627A, Weston 618F, 619F, DPDP, DPP, PDDP, PTP, TNPP, 399, TPP, 430, 439, 600, polyguard HR etc. as phosphite type antioxidant; As thioesters, Maianto L, S, Naugard 412S and the like; As an amine, Naugard 445, Super Q, A, PS30, Genox EP, etc .; Low light 20, 20S, 22, 24, 26, 27, 28, 29, 35, 36, 55, 234, 19, 62, 77, 92, 94, Q84, etc. as UV observers; And Shiva Co., Ltd. may be used one kind or a mixture of two or more kinds of Tin You 292,123,152,400,460,405,479.

The stabilizer is used 0.001 to 5% by weight, preferably 0.01 to 2% by weight relative to the total weight of the composition.

When the stabilizer is used at less than 0.001% by weight, yellowing may occur in an environment such as high temperature, high temperature and high humidity, or it may not function properly as a stabilizer, and when the amount of use exceeds 5% by weight, the effect as a stabilizer may be ineffective. No longer improved, or physical properties such as permeability may decrease depending on the type of stabilizer used.

The photocurable light-transparent point, adhesive composition of the present invention may also further comprise a tackifying resin in view of control of adhesion or adhesion performance.

The kind of tackifying resin which can be used by this invention is not specifically limited, For example, hydrocarbon type resin or its hydrogenated substance; Rosin resins or their hydrogenated materials; Rosin ester resins or hydrogenated substances thereof; Terpene resins or hydrogenated substances thereof; Terpene phenol resins or hydrogenated substances thereof; 1 type, or 2 or more types of mixtures, such as a polymeric rosin resin or polymeric rosin ester resin, can be used.

At least one selected from the group consisting of epoxy resins, crosslinkers, ultraviolet stabilizers, antioxidants, colorants, reinforcing agents, fillers, antifoaming agents, surfactants and plasticizers, without affecting the effects of the invention. It may further include an additive.

The photocurable light transparent point and adhesive composition of the present invention as described above includes aliphatic urethane acrylate and polythiol chain transfer agent, and excellent in photocurability, optical properties and environmental resistance such as high temperature, high temperature, high humidity, and ultraviolet light. In addition, since staining does not occur even during interlayer curing such as repainting and partition wall formation, the processability is excellent.

Therefore, the present invention also provides a photocurable light transparent point, a point containing a cured product of the adhesive composition, an adhesive layer and a point for a touch panel including the same, an adhesive sheet.

In the present invention, the method of curing the dot and adhesive composition to prepare the dot and adhesive layer is not particularly limited. In the present invention, for example, the point, the adhesive layer or the coating liquid prepared using the same, can be prepared by applying a method such as a bar coater to a suitable process substrate, and curing the point, the adhesive layer.

In the present invention, the curing process is preferably performed after sufficiently removing the bubble-causing components such as volatile components or reaction residues contained in the point, the adhesive composition or the coating solution. Accordingly, the point, the crosslinking density or molecular weight of the adhesive is too low, the elastic modulus is lowered, the bubbles present in the adhesive interface in the high temperature state is increased, it is possible to prevent the problem of forming the scattering body therein.

In addition, the method of curing the point, the adhesive composition or the coating liquid is not particularly limited, and, for example, a curing process may be performed through a process of applying appropriate heat to the coating layer or aging under predetermined conditions. .

The present invention also provides a touch panel including the dot and the adhesive sheet.

For example, the touch panel may include a transparent plastic substrate; And a touch panel formed on the transparent plastic substrate and having a dot according to the present invention, a point including a cured product of the adhesive composition, and an adhesive layer, but the specific structure of the touch panel of the present invention is limited to the present invention. According to the above point, it is not particularly limited as long as it is configured using the adhesive composition.

The present invention will now be described with reference to the following examples and comparative examples. However, these examples are only for illustrating the present invention, and the present invention is not limited thereto.

As the aliphatic urethane acrylate below, the aliphatic urethane acrylate represented by the formula (1), the polythiol chain shear agent as Showa Denko's Kalenz MT PE1, the monofunctional ethylene monomer as Osaka organic chemicals IBOA, stabilizer Chem Chura's ANOX1315 was used, and the photopolymerization initiator was used by mixing BASF's Igacure 184 and Darocure TPO in a 1: 1 ratio.

Example 1

70 parts by weight of an aliphatic urethane acrylate, 1 part by weight of a polythiol chain transfer agent, 30 parts by weight of a monofunctional ethylene monomer, 1 part by weight of a photopolymerization initiator, and 0.5 part by weight of a stabilizer are uniformly mixed for at least 6 hours at room temperature. Was prepared.

Example 2

70 parts by weight of an aliphatic urethane acrylate, 3 parts by weight of a polythiol chain transfer agent, 30 parts by weight of a monofunctional ethylene monomer, 4 parts by weight of a photopolymerization initiator and 0.5 parts by weight of a stabilizer are uniformly mixed for at least 6 hours at room temperature. Was prepared.

Example 3

70 parts by weight of an aliphatic urethane acrylate, 3 parts by weight of a polythiol chain transfer agent, 30 parts by weight of a monofunctional ethylene monomer, 1 part by weight of a photopolymerization initiator and 0.5 part by weight of a stabilizer are uniformly mixed for at least 6 hours at room temperature. Was prepared.

Example 4

70 parts by weight of an aliphatic urethane acrylate, 1 part by weight of a polythiol chain transfer agent, 30 parts by weight of a monofunctional ethylene monomer, 1 part by weight of a photopolymerization initiator and 1 part by weight of a stabilizer are uniformly mixed for at least 6 hours at room temperature. Was prepared.

Comparative Example 1

70 parts by weight of aliphatic urethane acrylate, 30 parts by weight of monofunctional ethylene monomer and 1 part by weight of a photopolymerization initiator were uniformly mixed at room temperature for 6 hours or more to prepare a point, adhesive composition.

Comparative Example 2

An ultraviolet curable polyurethane adhesive (SVR Series, manufactured by Sony Chemical) which is commonly used for display manufacture was used.

Test Example

Physical properties of the compositions of Examples and Comparative Examples were measured according to the following methods, and the results are shown in Table 1 below.

1) Observation of interface stain after repainting

The composition was applied to a TFT-LCD substrate at a thickness of 0.5 μm and UV cured using a metal lamp (roughness 2,000 Mw), and then the composition was recoated in a crisscross direction. The repainted substrate was again UV cured using a metallamp (roughness 2,000 Mw). The interface stain of the material on the repainted portion of the substrate formed by the above method using the naked eye and the LED lamp and the like was evaluated according to the following criteria.

A: Even when the naked eye and the LED lamp are used, the repainting part is not recognized at all.

B: barely noticeable using LED lamp

C: If you are sure of using an LED lamp

D: When it is recognized with the naked eye

2) Measurement of transmittance, yellow index and haze value at high temperature and high humidity

The composition was applied to a thickness of 0.5 μm on a degreasing washed glass for LCD and UV cured using a metal lamp (roughness 2,000 Mw). The substrate formed by the above method was placed in a high temperature and high humidity chamber at a temperature of 65 ° C / humidity 90% and 85 ° C / humidity 85%, left for 500 hours, and then the permeability, yellow index, and haze of the material were measured. Evaluation was made according to the standard.

A: less than 1% change in permeability, less than 0.1 change in yellow index, and less than 0.1 change in haze

B: permeability change 1% or more but less than 3%, yellow index change less than 0.1 and haze change less than 0.1; Permeability change less than 1%, yellow index change 0.1 or more and less than 0.3 and haze change less than 0.1; Or less than 1% change in permeability, less than 0.1 change in yellow index, and 0.1 or more and less than 0.5 change in haze

C: permeability change 1% or more and less than 3%, yellow index change 0.1 or more and less than 0.3 and haze change 0.1 or more and less than 0.5

D: permeability change 3% or more, yellow index change 0.3 or more and haze change 0.5 or more (D if at least one of the three factors changes above the indicated value).

3) Measurement of transmittance, yellow index and haze value at high temperature

Except that a high temperature chamber at 80 ° C. was used, the permeability, yellow index, and haze value of the material were measured and evaluated in the same manner as in the above-described method for measuring physical properties at high temperature and high humidity.

A: less than 1% change in permeability, less than 0.1 change in yellow index, and less than 0.1 change in haze

B: permeability change of 1% or more but less than 3%, yellow index change of less than 0.1 and haze change of less than 0.1; Permeability change less than 1%, yellow index change 0.1 or more and less than 0.3 and haze change less than 0.1; Or less than 1% change in permeability, less than 0.1 change in yellow index, and 0.1 or more and less than 0.5 change in haze

C: permeability change 1% or more and less than 3%, yellow index change 0.1 or more and less than 0.3 and haze change 0.1 or more and less than 0.5

D: permeability change 3% or more, yellow index change 0.3 or more and haze change 0.5 or more (D if at least one of the three factors changes above the indicated value)

4) UV resistance measurement

The composition was applied to a thickness of 0.5 μm on a degreasing clear glass for LCD and UV cured using a metal lamp (roughness 2,000 mW). The substrate formed by the above method was repeated 10 minutes of irradiation and 10 minutes of unirradiation using a 2,000 mW lamp. For the specimen formed under the above conditions, the transmittance, yellow index, and haze value were measured and evaluated according to the following criteria.

A: less than 1% change in permeability, less than 0.1 change in yellow index, and less than 0.1 change in haze

B: permeability change of 1% or more but less than 3%, yellow index change of less than 0.1 and haze change of less than 0.1; Permeability change less than 1%, yellow index change 0.1 or more and less than 0.3 and haze change less than 0.1; Or less than 1% change in permeability, less than 0.1 change in yellow index, and 0.1 or more and less than 0.5 change in haze

C: permeability change 1% or more and less than 3%, yellow index change 0.1 or more and less than 0.3 and haze change 0.1 or more and less than 0.5

D: permeability change 3% or more, yellow index change 0.3 or more and haze change 0.5 or more (D if at least one of the three factors changes above the indicated value)

Table 1

division	Repainting	High temperature and high humidity	High temperature	UV resistant
Example 1	A	A	B	A
Example 2	A	B	B	B
Example 3	A	B	B	A
Example 4	A	A	A	A
Comparative Example 1	D	B	C	B
Comparative Example 2	D	B	B	B

As shown in Table 1, the photocurable light-transparent point, the adhesive composition according to the present invention showed not only very excellent repainting properties, but also excellent results in various environmental resistance evaluation conditions.

Photocurable light transparent point, the adhesive composition according to the present invention includes an aliphatic urethane acrylate and polythiol chain transfer agent, optical properties such as photocurability, transparency of transparency, and environmental resistance such as high temperature, high temperature, high humidity, ultraviolet It is excellent in reliability and excellent in processability because stains do not occur even during interlayer curing such as repainting and partition wall formation, and thus, it is useful for the manufacture of dots and adhesive sheets for touch panels.

Claims (13)

1) aliphatic urethane acrylates;

2) polythiol chain transfer agents;

3) monofunctional ethylene monomers;

4) photopolymerization initiator; And

5) Photocurable light transparent point, adhesive composition comprising a stabilizer.

The method of claim 1,

1) 30 to 90% by weight of aliphatic urethane acrylate;

2) 0.01 to 4% by weight of a polythiol chain transfer agent;

3) 5 to 50% by weight monofunctional ethylene monomer;

4) 0.01 to 5 wt% of a photopolymerization initiator; And

5) Photocurable light transparent point, adhesive composition comprising a 0.001 to 5% by weight stabilizer.

The method of claim 1,

The aliphatic urethane acrylate is a compound having a bifunctional or less acrylate functionality, photocurable light transparent point, adhesive composition.

The method of claim 1,

Photo-curable light transparent point, the adhesive composition, characterized in that the aliphatic urethane acrylate is a compound of Formula 1 below:

[Formula 1]

Where

L ₁ is each independently alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkenyl having 3 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, and having 2 to 20 carbon atoms. Acyl, alkoxy having 1 to 20 carbon atoms, hydroxy, hydroxyalkyl having 1 to 20 carbon atoms, halo, haloalkyl having 1 to 20 carbon atoms, amino, silicon, aryl having 6 to 30 carbon atoms, arylalkyl having 6 to 30 carbon atoms Alkylene having 2 to 50 carbon atoms, arylene or diisocyanate having 6 to 50 carbon atoms, unsubstituted or the like;

L ₂ is alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, alkenyl having 2 to 20 carbon atoms, cycloalkenyl having 3 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, acyl having 1 to 20 carbon atoms, Substituted by alkoxy, hydroxy having 1 to 20 carbon atoms, hydroxyalkyl having 1 to 20 carbon atoms, halo, haloalkyl having 1 to 20 carbon atoms, amino, silicon, aryl having 6 to 30 carbon atoms, arylalkyl having 6 to 30 carbon atoms, etc. Or unsubstituted C2-C50 alkylene, C2-C50 acylalkylene, C2-C50 oxyalkylene, C6-C50 arylene, C6-C50 acyl arylene or C6-C50 50 oxyarylene;

Each R ₁ is independently hydrogen or alkyl having 1 to 20 carbon atoms;

Each A is independently C ₁ to C ₄ alkyl;

Each X is independently an integer of 0 to 20;

Y is an integer from 0 to 40;

n is an integer of 0-80.

The method of claim 4, wherein

Said L ₁ is a diisocyanate, The photocurable light-transparent point, adhesive composition characterized by the above-mentioned.

The method of claim 1,

The polythiol chain transfer agent is β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxy Butyl-3-mercaptopropionate, styryl-3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), tris (3-mercaptopropionyloxyethyl) -isocyano In the group consisting of latex, pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) Photocurable light transparent point, adhesive composition, characterized in that selected.

The method of claim 1,

The monofunctional ethylene monomer isobutyl acrylate, tert- butyl acrylate, lauryl acrylate, isodecyl acrylate, methyl methacrylate, alkyl acrylate, steacrylate, cyclohexyl acrylate, isobornyl acrylate , Benzyl methacrylate, benzyl acrylate, 2-hydroxy acrylate, trimethoxy butyl acrylate, ethyl carbitol acrylate, phenoxy ethyl acrylate, 4-hydroxy butyl acrylate, phenoxy polyethylene glycol acrylate , 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl acrylate, and methacrylates thereof; Acrylates containing halogen compounds and methacrylates thereof; Acrylates containing siloxane groups and methacrylates thereof; And one or two or more kinds of mixtures selected from the group consisting of olefins having an aromatic composition.

The method of claim 1,

The photocuring initiator is a photocurable light transparent point, characterized in that one or two or more mixtures selected from the group consisting of acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds and triazine compounds , Adhesive composition.

The method of claim 1,

The stabilizer is poly (dipropylene glycol) phenyl phosphite, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, distyryl pentaerythritol diphosphite, bis (2,4-di -Tetra-butylphenyl) pentaerythritol diphosphite, dispylthiopropionate, dilauryl thiodipropionate, ditridecyl thiodipropionate, pentaerytrityl tetrakis (3-lauritriopio ), Tetrakis [methylene-3- (3,5-di-tetra-butyl-4-hydroxyphenyl) propionate], isotridecyl-3- (3,5-di-tetra-butyl-4 -Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-tetra-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tetra -Butyl-4-hydroxyphenyl) propionate, 1,2-bis (3,5-di-tetra-butyl-4-hydroxyhydrocyanamo ) Hydrazine, 2,2'-ethylidenebis (4,6-di-tetra-butylphenol), hexamethylenebis [3- (3,5-di-tetra-butyl-4-hydroxyphenyl) propionate ], N, N'hexamethylenebis (3,5-di-tetra-butyl-4-hydroxyhydrocinamide), 4,4'thiobis (6-tetra-butyl-m-cresol), 4,4 '-Butylidenebis (∂-tetra-butyl-3-methylphenol), 4,6-bis (octylthiomethyl) -o-cresol, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, octadecyl-3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, triethyleneglycol-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 2,2-methylenebis (4- Methyl-6- (1-methylcyclohexyl) -phenol), tris (2,4-di-tert-butylphenyl) phosphite, bis (1,2,2,6,6, -pentamethyl-4-pi Ferridyl) Sebacate, Bis (2,2,6,6, -tet Methyl-4-piperidyl) sebacate, bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-hydroxy-2,2,6, 6-tetramethyl-1-piperidineethanol, [2,2'-thiobis (4-tetra-octylphenolato) -ene-butylaminenickel, 2-hydroxy-4-ene-octoxybenzophenone, 2- (2'-hydroxy-5'-methylphenylbenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tetra-butylphenyl) benzotriazole, 2- (2'-hydroxy Oxy-3'-tetra-butyl-5'-methylphenyl-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tetra-butylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-3 ', 5'-di-tetra-amylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2- [2-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole, bis [2-hydroxy-5-tetra-octyl -3- (benzotriazol-2-yl) phenyl] methane, 2,4-di-tetra-butylphenyl-4'-hydroxy-3 ', 5'-di-tet La-butyl benzoate, hexadecyl-3,5-di-tetra-butyl-4-hydroxybenzoate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2- Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- (4,6-bis-[[2-hydroxy-4- [ 1- (6-Methyl-heptyloxycarbonyl) -ethoxy] -phenyl]]-[1,3,5] triazin-2-yl) -3-hydroxy-phenoxy] -propionic acid 6-methyl- Heptyl ester, 2- [4- (4,6-bis-biphenyl-4-yl- [1,3,5] triazin-2-yl) -3-hydroxy-phenoxy] -propionic acid 6-methyl 1 type selected from the group consisting of -heptyl ester and 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dimethylphenyl) -1,3,5-triazine or Photocurable light transparent point, adhesive composition, characterized in that the mixture of two or more kinds.

The method of claim 1,

A photocurable light transparent point and adhesive composition, further comprising a tackifying resin.

The photocurable light transparent point according to any one of claims 1 to 10, comprising a cured product of the adhesive composition, the adhesive layer.

The point according to claim 11, the point for the touch panel comprising the adhesive layer, the adhesive sheet.

The touch panel comprising a dot for a touch panel according to claim 12, an adhesive sheet.