WO2014193117A1 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
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- WO2014193117A1 WO2014193117A1 PCT/KR2014/004581 KR2014004581W WO2014193117A1 WO 2014193117 A1 WO2014193117 A1 WO 2014193117A1 KR 2014004581 W KR2014004581 W KR 2014004581W WO 2014193117 A1 WO2014193117 A1 WO 2014193117A1
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- group
- formula
- adhesive composition
- acrylate
- meth
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- 0 C1*C=C**1 Chemical compound C1*C=C**1 0.000 description 2
- NLWBEORDOPDUPM-UHFFFAOYSA-N O=C(C(CC1C(O2)=O)C3C1C2=O)OC3=O Chemical compound O=C(C(CC1C(O2)=O)C3C1C2=O)OC3=O NLWBEORDOPDUPM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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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
- 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
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
Definitions
- the present invention relates to a pressure-sensitive adhesive composition excellent in adhesion durability.
- a liquid crystal display device includes a liquid crystal cell and a polarizing plate containing liquid crystal, and various optical films (phase difference plate, viewing angle magnification film, Brightness enhancement film, etc.) is used.
- Liquid crystal displays are widely used as display devices for personal computers, televisions, car navigation systems, and the like. Accordingly, there is a demand for a pressure-sensitive adhesive that is excellent in durability even in use in a harsh environment such as high temperature and high humidity, that is, does not peel off or generate bubbles even in long-term use.
- an adhesive composition using an isocyanate compound as a crosslinking agent in an acrylic copolymer having a carboxyl group and a hydroxyl group is proposed (Japanese Patent Laid-Open No. 2004-224873). Moreover, it is proposed in the adhesive composition which used the polyfunctional metal chelate in the acryl-type copolymer which has a carboxyl group (Japanese Patent Laid-Open No. 2002-214439).
- an adhesive composition using heterogeneous curing agents such as a metal chelate curing agent and an isocyanate curing agent has been proposed in an acrylic copolymer having a carboxyl group (Korean Patent No. 1148141).
- the carboxyl group-containing acrylic copolymer ⁇ has a disadvantage that the carboxyl group is adjacent to the main chain of the acrylic copolymer, and the carboxyl group does not easily interact with the adherend, and it is difficult to secure sufficient durability and participate in the crosslinking reaction.
- An object of the present invention is to provide a pressure-sensitive adhesive composition that can be significantly applied to a large-scale liquid crystal display device by significantly improving adhesion durability under severe conditions (high temperature or high temperature and high humidity).
- the present invention provides an adhesive composition containing an acrylic copolymer having a hydroxy group, an acid anhydride of the formula (1), and a crosslinking agent.
- R is an aliphatic hydrocarbon group having 4 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms).
- the acid anhydride may be at least one selected from the group consisting of the following Chemical Formulas 2 to 8.
- R 1 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
- R 2 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
- the acrylic copolymer having a hydroxy group may contain an alkyl (meth) acrylate monomer having 4 to 12 carbon atoms and a monomer having a hydroxy group.
- the acrylic copolymer having a hydroxy group may further contain a polymerizable monomer having at least one crosslinkable functional group selected from the group consisting of a monomer having a carboxyl group, a monomer having an amide group, and a monomer having a tertiary amine group.
- the acid anhydride of Formula 1 may contain 10 to 50 functional groups with respect to 100 functional groups of the hydroxy group of the acrylic copolymer having a hydroxy group.
- the crosslinking agent may contain 0.1 to 3.0 parts by weight based on 100 parts by weight of the acrylic copolymer having a hydroxy group.
- the pressure-sensitive adhesive composition of the present invention has an advantage in that the specific acid anhydride acts as a crosslinking agent to improve adhesion and cohesion, and thus excellent adhesion durability in harsh conditions (high temperature or high temperature and high humidity).
- the present invention relates to a pressure-sensitive adhesive composition excellent in adhesion durability.
- the adhesive composition of this invention contains the acryl-type copolymer which has a hydroxyl group, the acid anhydride of following formula (1), and a crosslinking agent.
- R is an aliphatic hydrocarbon group having 4 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms
- the acid anhydride of Formula 1 performs a crosslinking reaction with the hydroxyl group of the acrylic copolymer, thereby increasing the cohesion of the composition to improve durability. That is, in the present invention, since the crosslinking agent and the acid anhydride of Formula 1, which acts as a crosslinking agent, perform the reaction together, the effect of improving cohesion is increased compared to the conventional art.
- the acid anhydride of Formula 1 reacts with the hydroxyl group of the acrylic copolymer to generate carboxylic acid functional groups as a product, thereby improving adhesion to the adherend.
- the resulting carboxylic acid functional groups are expected to contribute sufficiently to the improvement of durability since they take a three-dimensional position far enough from the main chain of the acrylic copolymer and easily interact with the adherend.
- the acryl-type copolymer of this invention contains the C4-C12 alkyl (meth) acrylate monomer and the monomer which has a hydroxyl group.
- (meth) acrylate means acrylate and methacrylate, and the content of each component is based on solid content.
- Examples of the (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth).
- Monomers having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6 Hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, and hydroxyalkylene glycol having 2 to 4 carbon atoms of an alkylene group (meth ) Acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl vinyl Ether, 10-hydroxydecylvinylether, 2-hydroxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and Etc. can be mentioned.
- the monomer which has such a hydroxyl group is contained in 0.5-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C4-C12 alkyl group, More preferably, it is 1-5 weight part. If the content is less than 0.5 parts by weight it is difficult to react with the acid anhydride may be insufficient to improve the cohesion and adhesion strength, if it exceeds 10 parts by weight crosslinking is excessively progressed, the adhesive force is reduced due to excessive improvement of the cohesion may be deteriorated durability.
- the acrylic copolymer of the present invention may further contain a polymerizable monomer having a crosslinkable functional group.
- the polymerizable monomer having a crosslinkable functional group serves to reinforce the cohesive force or the adhesive strength of the pressure-sensitive adhesive composition by chemical bonding to impart durability and cutability.
- Examples of the polymerizable monomer having a crosslinkable functional group include a monomer having an amide group, a monomer having a tertiary amine group, a monomer having a carboxyl group, and the like, and these may be used alone or in combination of two or more thereof.
- Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6 -Hydroxyhexyl (meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, 2-hydroxyethylhexyl (meth) acrylamide, etc. are mentioned, Among these, (meth) acrylamide is preferable.
- Monomers having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, and N, N- (dimethylamino) propyl ( Meth) acrylate, etc. are mentioned.
- Monovalent acids such as (meth) acrylic acid and a crotonic acid; Diacids such as maleic acid, itaconic acid and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; Succinic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate with 2-3 carbon atoms of an alkyl group, Succinic anhydride ring opening adduct of hydroxyalkylene glycol (meth) acrylate with 2-4 carbon atoms of an alkylene group And a compound obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 to 3 carbon atoms of an alkyl group, among which (meth) acrylic acid is preferred.
- a polymeric monomer is contained in 0.05-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C4-C12 alkyl group, More preferably, it is 0.1-8 weight part. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered by a high gel fraction may cause problems in durability.
- the acid anhydride of Formula 1 performs a crosslinking reaction with the hydroxyl group of the acrylic copolymer to improve the cohesion and at the same time the resulting carboxyl groups increase the adhesion to the adhesive agent to improve the durability.
- R in Formula 1 is preferably an aliphatic hydrocarbon group having 4 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably at least one selected from the group consisting of the following Formulas 2 to 8.
- R 1 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
- R 2 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
- Such acid anhydrides may be contained so as to have 10 to 50 functional groups, preferably 10 to 30 functional groups, based on 100 functional groups of the hydroxy group of the acrylic copolymer having a hydroxy group. If the number of functional groups is less than 10, the effect of improving cohesion and adhesion may be insufficient, and if the functional group exceeds 50 functional groups, the unreacted acid anhydride may bleed out and degrade durability.
- it may be in the range of 0.2 to 1.0 parts by weight based on 100 parts by weight of the acrylic copolymer having a hydroxyl group.
- a crosslinking agent is a component for strengthening the cohesion force of an adhesive by crosslinking a copolymer suitably,
- the kind is not specifically limited.
- an isocyanate type compound, an epoxy type compound, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
- isocyanate compound tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate
- Diisocyanate compounds such as naphthalene diisocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound
- polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate, in which the remaining 1
- epoxy compounds examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol.
- melamine type compound can be used individually or in mixture of 2 or more types together with an isocyanate type compound and an epoxy type compound.
- Hexamethylol melamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc. are mentioned as a melamine type compound.
- a crosslinking agent is contained in 0.1-3 weight part with respect to 100 weight part of acrylic copolymers, More preferably, it is 0.1-1 weight part. If the content is less than 0.1 part by weight, the cohesion force becomes small due to insufficient crosslinking degree, which may cause durability deterioration such as lifting and damage of cutting property.In the case of more than 3 parts by weight, the adhesive strength is deteriorated due to the excessive crosslinking reaction. As a result, problems with releasing residual stresses may occur.
- the acid anhydride serves as a crosslinking agent
- a small amount of the crosslinking agent may be used as compared with the conventional art.
- the pressure-sensitive adhesive composition is a silane coupling agent, tackifying resin, antioxidant, leveling agent, surface lubricant, dye, in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, etc.
- Additives, such as a pigment, an antifoamer, a filler, and a light stabilizer, can be further contained.
- the double silane coupling agent plays a role of improving the adhesion between the pressure-sensitive adhesive and the substrate, it is preferable to contain it.
- the silane coupling agent may be included in an amount of 0 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer based on the solid content, preferably 0.005 to 5 parts by weight. If the content is more than 10 parts by weight, durability may be reduced.
- the pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive for polarizing plates and a surface protective film for bonding to liquid crystal cells.
- it can be used as a general commercial adhesive sheet product as well as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an adhesive for electronic parts, and the like.
- n-butyl acrylate BA
- methacrylate MA
- 2-hydroxyethyl acrylate 2 90 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methacrylate (MA), 2-hydroxyethyl acrylate 2 in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to reflux and for easy temperature control.
- a monomer mixture consisting of parts by weight and 1 part by weight of dimethylaminoethyl acrylate
- 100 parts by weight of ethyl acetate was added as a solvent.
- purging nitrogen gas for 1 hour to remove oxygen it was maintained at 62 °C.
- 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to prepare an acrylic copolymer having a weight average molecular weight of 1 million.
- AIBN azobisisobutyronitrile
- An acrylic copolymer was prepared in the same manner as in Preparation Example 1, using hydroxyethylacrylamide instead of 2-hydroxyethyl acrylate.
- the acrylic copolymer, the acid anhydride, the crosslinking agent, and the silane coupling agent of Preparation Example 1 were mixed in the composition shown in Table 2, and then diluted to a concentration of 28% by weight in consideration of coating properties to prepare an adhesive composition.
- the pressure-sensitive adhesive composition prepared in 1) was applied on a release film coated with a silicone release agent to have a thickness of 25 ⁇ m, and dried at 100 ° C. for 1 minute, 5 minutes, and 10 minutes, respectively, to form an adhesive layer.
- a polarizing plate having a triacetyl cellulose protective film bonded to both surfaces of the polarizer was laminated to prepare a polarizing plate with an adhesive.
- the protective film surface and the adhesive layer was laminated so as to contact.
- the prepared polarizing plate was stored under curing conditions at 23 ° C. and 60% RH.
- the prepared pressure-sensitive adhesive polarizing plate was cut to a size of 90 mm x 170 mm, the release film was peeled off, and the specimens were prepared by attaching the optical absorption axis perpendicular to both surfaces of the glass substrate (110 mm x 190 mm x 0.7 mm).
- the applied pressure was 5kg / cm2 and the clean room work so as not to generate bubbles or foreign matter.
- the heat resistance characteristics were observed whether bubbles or peeling occurred after 1000 hours at 80 °C temperature, and the heat-resistant characteristics were bubbles or peeling after 1000 hours at 60 °C temperature and 90% RH conditions Was observed. At this time, it was observed after leaving for 24 hours at room temperature immediately before evaluating the state of the specimen.
- the pressure-sensitive adhesive composition of Examples 1 to 15 containing an acrylic copolymer having a hydroxyl group, the acid anhydride of Formula 1, and a crosslinking agent according to the present invention is superior in adhesion durability compared to Comparative Examples 1 to 3. I could confirm that.
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Abstract
Description
본 발명은 점착 내구성이 우수한 점착제 조성물에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition excellent in adhesion durability.
일반적으로 액정표시장치(Liquid crystal display device, LCD)는 액정을 포함하고 있는 액정셀과 편광판이 구비되며, 상기 액정표시장치의 표시 품위를 향상시키기 위하여 여러 가지 광학필름(위상차판, 시야각 확대필름, 휘도 향상필름 등)이 사용된다. In general, a liquid crystal display device (LCD) includes a liquid crystal cell and a polarizing plate containing liquid crystal, and various optical films (phase difference plate, viewing angle magnification film, Brightness enhancement film, etc.) is used.
액정표시장치는 퍼스널 컴퓨터나 텔레비전, 카 내비게이션 등의 표시장치로서 광범위하게 사용되고 있다. 그에 따라 고온 고습과 같은 가혹한 환경하에서의 사용에 있어서도 내구성이 우수한, 즉, 장기간의 사용에 있어서도 벗겨짐이나 기포발생 등이 발생하지 않는 점착제가 요구되고 있다.Liquid crystal displays are widely used as display devices for personal computers, televisions, car navigation systems, and the like. Accordingly, there is a demand for a pressure-sensitive adhesive that is excellent in durability even in use in a harsh environment such as high temperature and high humidity, that is, does not peel off or generate bubbles even in long-term use.
이에 카르복실기와 수산기를 갖는 아크릴계 공중합체에 이소시아네이트 화합물을 가교제로 사용한 점착제 조성물이 제시되어 있다(일본특허공개 제2004-224873호). 또한, 카르복실기를 가진 아크릴계 공중합체에, 다작용성 금속 킬레이트를 사용한 점착제 조성물에 제시되어 있다(일본특허공개 2002-214439호)Thus, an adhesive composition using an isocyanate compound as a crosslinking agent in an acrylic copolymer having a carboxyl group and a hydroxyl group is proposed (Japanese Patent Laid-Open No. 2004-224873). Moreover, it is proposed in the adhesive composition which used the polyfunctional metal chelate in the acryl-type copolymer which has a carboxyl group (Japanese Patent Laid-Open No. 2002-214439).
이들은 대형 액정표시장치에 적용하는 경우 만족할 정도의 내구성을 나타내지 못하는 단점이 있다.These are disadvantages in that they do not exhibit satisfactory durability when applied to large liquid crystal display devices.
이를 개선하기 위하여 카르복실기를 가진 아크릴계 공중합체에, 금속 킬레이트계 경화제와 이소시아네이트계 경화제 등의 이종의 경화제를 사용한 점착제 조성물이 제시되었다(한국등록특허 제1148141호). 그러나 상기 카르복실기를 함유한 아크릴계 공중합체믐 카르복실기가 아크릴계 공중합체의 주쇄에 인접하여, 상기 카르복실기가 피착체와의 상호작용이 용이하지 않고 충분한 내구성 확보 및 가교반응에 참여하기가 어렵다는 단점이 있다.In order to improve this, an adhesive composition using heterogeneous curing agents such as a metal chelate curing agent and an isocyanate curing agent has been proposed in an acrylic copolymer having a carboxyl group (Korean Patent No. 1148141). However, the carboxyl group-containing acrylic copolymer 믐 has a disadvantage that the carboxyl group is adjacent to the main chain of the acrylic copolymer, and the carboxyl group does not easily interact with the adherend, and it is difficult to secure sufficient durability and participate in the crosslinking reaction.
본 발명은 가혹 조건(고온 또는 고온 다습)에서의 점착 내구성을 월등히 향상시켜, 대형 액정표시장치에 적용이 가능한 점착제 조성물을 제공하는데 그 목적이 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a pressure-sensitive adhesive composition that can be significantly applied to a large-scale liquid crystal display device by significantly improving adhesion durability under severe conditions (high temperature or high temperature and high humidity).
상기 목적을 달성하기 위하여, 본 발명은 히드록시기를 갖는 아크릴계 공중합체, 하기 화학식 1의 산무수물, 및 가교제를 함유하는 점착제 조성물을 제공한다.In order to achieve the above object, the present invention provides an adhesive composition containing an acrylic copolymer having a hydroxy group, an acid anhydride of the formula (1), and a crosslinking agent.
[화학식 1][Formula 1]
(식 중, R은 탄소수 4 내지 8의 지방족 탄화수소기, 탄소수 4 내지 8의 지환족 탄화수소기 또는 탄소수 6 내지 20의 방향족 탄화수소기임).(Wherein R is an aliphatic hydrocarbon group having 4 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms).
상기 산무수물은 하기 화학식 2 내지 8로 이루어진 군에서 선택된 1종 이상일 수 있다.The acid anhydride may be at least one selected from the group consisting of the following Chemical Formulas 2 to 8.
[화학식 2][Formula 2]
(식 중 R1은 직접결합, CH2, O, S, CO, SO, SO2, C(CH3)2, C(CF3)2, C(CH3)2 또는 Si(CH3)2임)Wherein R 1 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
[화학식 3][Formula 3]
(식 중 R2은 직접결합, CH2, O, S, CO, SO, SO2, C(CH3)2, C(CF3)2, C(CH3)2 또는 Si(CH3)2임)Wherein R 2 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
상기 히드록시기를 갖는 아크릴계 공중합체는 탄소수 4-12인 알킬 (메타)아크릴레이트 단량체 및 히드록시기를 갖는 단량체를 함유할 수 있다. The acrylic copolymer having a hydroxy group may contain an alkyl (meth) acrylate monomer having 4 to 12 carbon atoms and a monomer having a hydroxy group.
상기 히드록시기를 갖는 아크릴계 공중합체는 카르복시기를 갖는 단량체, 아미드기를 갖는 단량체 및 3차 아민기를 갖는 단량체로 이루어진 군에서 선택된 1종 이상의 가교 가능한 관능기를 갖는 중합성 단량체를 추가로 함유할 수 있다.The acrylic copolymer having a hydroxy group may further contain a polymerizable monomer having at least one crosslinkable functional group selected from the group consisting of a monomer having a carboxyl group, a monomer having an amide group, and a monomer having a tertiary amine group.
상기 화학식 1의 산무수물은 히드록시기를 갖는 아크릴계 공중합체의 히드록시기의 관능기수 100에 대하여 10 내지 50관능기수를 갖도록 함유할 수 있다.The acid anhydride of Formula 1 may contain 10 to 50 functional groups with respect to 100 functional groups of the hydroxy group of the acrylic copolymer having a hydroxy group.
상기 가교제는 히드록시기를 갖는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 3.0중량부 함유할 수 있다.The crosslinking agent may contain 0.1 to 3.0 parts by weight based on 100 parts by weight of the acrylic copolymer having a hydroxy group.
본 발명의 점착제 조성물은 특정의 산무수물이 가교제 역할을 하여 점착력 및 응집력을 향상시켜 가혹 조건(고온 또는 고온 다습)에서의 점착 내구성이 우수한 이점이 있다.The pressure-sensitive adhesive composition of the present invention has an advantage in that the specific acid anhydride acts as a crosslinking agent to improve adhesion and cohesion, and thus excellent adhesion durability in harsh conditions (high temperature or high temperature and high humidity).
본 발명은 점착 내구성이 우수한 점착제 조성물에 관한 것이다. The present invention relates to a pressure-sensitive adhesive composition excellent in adhesion durability.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명의 점착제 조성물은 히드록시기를 갖는 아크릴계 공중합체, 하기 화학식 1의 산무수물, 및 가교제를 함유한다.The adhesive composition of this invention contains the acryl-type copolymer which has a hydroxyl group, the acid anhydride of following formula (1), and a crosslinking agent.
[화학식 1][Formula 1]
(식 중, R은 탄소수 4 내지 8의 지방족 탄화수소기, 탄소수 4 내지 8의 지환족 탄화수소기 또는 탄소수 6 내지 20의 방향족 탄화수소기임)(Wherein R is an aliphatic hydrocarbon group having 4 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms)
본 발명은 상기 화학식 1의 산무수물은 아크릴계 공중합체의 히드록시기와 가교반응을 수행하여, 조성물의 응집력을 증가시켜 내구성을 향상시킨다. 즉, 본 발명은 가교제와, 가교제 역할을 하는 화학식 1의 산무수물이 함께 반응을 수행하므로 종래에 비해 응집력 향상 효과가 증가하게 된다.In the present invention, the acid anhydride of Formula 1 performs a crosslinking reaction with the hydroxyl group of the acrylic copolymer, thereby increasing the cohesion of the composition to improve durability. That is, in the present invention, since the crosslinking agent and the acid anhydride of Formula 1, which acts as a crosslinking agent, perform the reaction together, the effect of improving cohesion is increased compared to the conventional art.
또한 상기 화학식 1의 산무수물은 아크릴공중합체의 히드록시기와 반응하여 생성물로 카르복시산 작용기를 생성하므로, 피착제와의 밀착력을 향상시키는 역할을 한다. 상기 생성된 카르복시산 작용기는 아크릴공중합체의 주쇄로부터 충분히 멀리 떨어져 있고 피착제와의 상호작용이 용이한 입체적 위치를 취하고 있어 내구성 향상에 충분히 기여하게 되는 것으로 예측된다.In addition, the acid anhydride of Formula 1 reacts with the hydroxyl group of the acrylic copolymer to generate carboxylic acid functional groups as a product, thereby improving adhesion to the adherend. The resulting carboxylic acid functional groups are expected to contribute sufficiently to the improvement of durability since they take a three-dimensional position far enough from the main chain of the acrylic copolymer and easily interact with the adherend.
본 발명의 아크릴계 공중합체는 탄소수 4-12인 알킬 (메타)아크릴레이트 단량체 및 히드록시기를 갖는 단량체를 함유하는 것이 바람직하다.It is preferable that the acryl-type copolymer of this invention contains the C4-C12 alkyl (meth) acrylate monomer and the monomer which has a hydroxyl group.
본 발명에 있어서, (메타)아크릴레이트는 아크릴레이트 및 메타크릴레이트를 의미하고, 각 성분의 함량은 고형분을 기준으로 한 것이다.In the present invention, (meth) acrylate means acrylate and methacrylate, and the content of each component is based on solid content.
상기 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체로는 n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 에틸(메타)아크릴레이트, 메틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 펜틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등을 들 수 있으며, 이들 중에서 n-부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 이들의 혼합물이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth). ) Acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like, among which n-butyl acrylate and 2-ethylhexyl acrylate Or mixtures thereof. These can be used individually or in mixture of 2 or more types.
히드록시기를 갖는 단량체는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 2-히드록시에틸렌글리콜(메타)아크릴레이트, 2-히드록시프로필렌글리콜(메타)아크릴레이트, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트, 4-히드록시부틸비닐에테르, 5-히드록시펜틸비닐에테르, 6-히드록시헥실비닐에테르, 7-히드록시헵틸비닐에테르, 8-히드록시옥틸비닐에테르, 9-히드록시노닐비닐에테르, 10-히드록시데실비닐에테르, 2-히드록시메틸(메타)아크릴아미드, 2-히드록시에틸(메타)아크릴아미드 및
이러한 히드록시기를 갖는 단량체는 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.5 내지 10중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 1 내지 5중량부인 것이 좋다. 함량이 0.5중량부 미만이면 산무수물과 반응이 어려워 응집력과 밀착력 향상이 부족할 수 있고 10중량부를 초과하는 경우에는 가교가 지나치게 진행되어, 응집력의 지나친 향상으로 점착력이 저하되어 내구성이 악화될 수 있다.It is preferable that the monomer which has such a hydroxyl group is contained in 0.5-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C4-C12 alkyl group, More preferably, it is 1-5 weight part. If the content is less than 0.5 parts by weight it is difficult to react with the acid anhydride may be insufficient to improve the cohesion and adhesion strength, if it exceeds 10 parts by weight crosslinking is excessively progressed, the adhesive force is reduced due to excessive improvement of the cohesion may be deteriorated durability.
본 발명의 아크릴계 공중합체는 가교 가능한 관능기를 갖는 중합성 단량체를 추가로 함유할 수 있다.The acrylic copolymer of the present invention may further contain a polymerizable monomer having a crosslinkable functional group.
가교 가능한 관능기를 갖는 중합성 단량체는 화학 결합에 의해 점착제 조성물의 응집력 또는 점착 강도를 보강하여 내구성과 절단성을 부여할 수 있는 역할을 한다.The polymerizable monomer having a crosslinkable functional group serves to reinforce the cohesive force or the adhesive strength of the pressure-sensitive adhesive composition by chemical bonding to impart durability and cutability.
상기 가교 가능한 관능기를 갖는 중합성 단량체는 예컨대 아미드기를 갖는 단량체, 3차 아민기를 갖는 단량체, 카르복시기를 갖는 단량체 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the polymerizable monomer having a crosslinkable functional group include a monomer having an amide group, a monomer having a tertiary amine group, a monomer having a carboxyl group, and the like, and these may be used alone or in combination of two or more thereof.
아미드기를 갖는 단량체로는 (메타)아크릴아미드, N-이소프로필아크릴아미드, N-3차부틸아크릴아미드, 3-히드록시프로필(메타)아크릴아미드, 4-히드록시부틸(메타)아크릴아미드, 6-히드록시헥실(메타)아크릴아미드, 8-히드록시옥틸(메타)아크릴아미드, 및 2-히드록시에틸헥실(메타)아크릴아미드 등을 들 수 있으며, 이들 중에서 (메타)아크릴아미드가 바람직하다. Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6 -Hydroxyhexyl (meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, 2-hydroxyethylhexyl (meth) acrylamide, etc. are mentioned, Among these, (meth) acrylamide is preferable.
3차 아민기를 갖는 단량체로는 N,N-(디메틸아미노)에틸(메타)아크릴레이트, N,N-(디에틸아미노)에틸(메타)아크릴레이트, 및 N,N-(디메틸아미노)프로필(메타)아크릴레이트 등을 들 수 있다. Monomers having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, and N, N- (dimethylamino) propyl ( Meth) acrylate, etc. are mentioned.
카르복시기를 갖는 단량체로는 (메타)아크릴산, 크로톤산 등의 1가산; 말레인산, 이타콘산, 푸마르산 등의 2가산 및 이들의 모노알킬에스테르; 3-(메타)아크릴로일프로피온산; 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 무수호박산 개환 부가체, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트의 무수 호박산 개환 부가체, 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 카프로락톤 부가체에 무수 호박산을 개환 부가시킨 화합물 등을 들 수 있으며, 이들 중에서 (메타)아크릴산이 바람직하다. As a monomer which has a carboxy group, Monovalent acids, such as (meth) acrylic acid and a crotonic acid; Diacids such as maleic acid, itaconic acid and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; Succinic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate with 2-3 carbon atoms of an alkyl group, Succinic anhydride ring opening adduct of hydroxyalkylene glycol (meth) acrylate with 2-4 carbon atoms of an alkylene group And a compound obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 to 3 carbon atoms of an alkyl group, among which (meth) acrylic acid is preferred.
중합성 단량체는 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.05 내지 10중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.1 내지 8중량부인 것이 좋다. 함량이 0.05중량부 미만인 경우 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 10중량부 초과인 경우 높은 겔분율에 의해 점착력이 떨어지고 내구성에 문제를 야기할 수 있다. It is preferable that a polymeric monomer is contained in 0.05-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C4-C12 alkyl group, More preferably, it is 0.1-8 weight part. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered by a high gel fraction may cause problems in durability.
상기 화학식 1의 산무수물은 아크릴계 공중합체의 히드록시기와 가교반응을 수행하여, 응집력을 향상시킴과 동시에 생성되는 카르복실기가 피착제와의 밀착력을 증가시켜 내구성을 향상시키는 역할을 한다.The acid anhydride of Formula 1 performs a crosslinking reaction with the hydroxyl group of the acrylic copolymer to improve the cohesion and at the same time the resulting carboxyl groups increase the adhesion to the adhesive agent to improve the durability.
상기 산무수물은 화학식 1에서 R이 탄소수 4 내지 8의 지방족 탄화수소기 또는 탄소수 6 내지 20의 방향족 탄화수소기인 것이 바람직하고, 보다 바람직하기로는 하기 화학식 2 내지 8로 이루어진 군에서 선택된 1종 이상이 좋다.In the acid anhydride, R in Formula 1 is preferably an aliphatic hydrocarbon group having 4 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably at least one selected from the group consisting of the following Formulas 2 to 8.
[화학식 2][Formula 2]
(식 중 R1은 직접결합, CH2, O, S, CO, SO, SO2, C(CH3)2, C(CF3)2, C(CH3)2 또는 Si(CH3)2임)Wherein R 1 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
[화학식 3][Formula 3]
(식 중 R2은 직접결합, CH2, O, S, CO, SO, SO2, C(CH3)2, C(CF3)2, C(CH3)2 또는 Si(CH3)2임)Wherein R 2 is a direct bond, CH 2 , O, S, CO, SO, SO 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , C (CH 3 ) 2 or Si (CH 3 ) 2 being)
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
이러한 산무수물은 히드록시기를 갖는 아크릴계 공중합체의 히드록시기의 관능기수 100에 대하여 10 내지 50관능기수, 바람직하기로는 10 내지 30관능기수를 갖도록 함유할 수 있다. 관능기수가 10 미만이면 응집력과 밀착력의 향상 효과가 부족할 수 있고 50관능기수를 초과하는 경우에는 미반응 산무수물이 블리드 아웃(bleed-out)되어 내구성이 저하될 수 있다.Such acid anhydrides may be contained so as to have 10 to 50 functional groups, preferably 10 to 30 functional groups, based on 100 functional groups of the hydroxy group of the acrylic copolymer having a hydroxy group. If the number of functional groups is less than 10, the effect of improving cohesion and adhesion may be insufficient, and if the functional group exceeds 50 functional groups, the unreacted acid anhydride may bleed out and degrade durability.
상기 산무수물의 관능기수 범위를 함량으로 환산하는 경우, 사용된 히드록시기를 갖는 아크릴계 공중합체 및 산무수물의 종류에 따라 달라지는 바, 이를 고려하여 적절히 사용하는 것이 바람직하다.When converting the functional group range of the acid anhydride into the content, it depends on the type of the acrylic copolymer and acid anhydride having the hydroxy group used, it is preferable to use in consideration of this.
바람직하기로는 히드록시기를 갖는 아크릴계 공중합체 100중량부에 대하여 0.2 내지 1.0 중량부 범위일 수 있다. Preferably it may be in the range of 0.2 to 1.0 parts by weight based on 100 parts by weight of the acrylic copolymer having a hydroxyl group.
가교제는 공중합체를 적절히 가교함으로써 점착제의 응집력을 강화하기 위한 성분으로서, 그 종류는 특별히 한정되지 않는다. 예컨대, 이소시아네이트계 화합물, 에폭시계 화합물 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.A crosslinking agent is a component for strengthening the cohesion force of an adhesive by crosslinking a copolymer suitably, The kind is not specifically limited. For example, an isocyanate type compound, an epoxy type compound, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
이소시아네이트계 화합물로는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 2,4-디페닐메탄디이소시아네트, 4,4-디페닐메탄디이소시아네트, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트 등의 디이소시아네이트 화합물; 트리메틸올프로판 등의 다가 알콜계 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트, 메틸렌비스트리이소시아네이트 등의 3개의 관능기를 함유하는 다관능 이소시아네이트 화합물 등을 들 수 있다.As the isocyanate compound, tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate Diisocyanate compounds such as naphthalene diisocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound And polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate, in which the remaining 1 mole of diisocyanate is condensed to urea.
에폭시계 화합물로는 에틸렌글리콜디글리시딜에테르, 디에틸렌글리콜디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 트리프로필렌글리콜디글리시딜에테르, 폴리프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리테트라메틸렌글리콜디글리시딜에테르, 글리세롤디글리시딜에테르, 글리세롤트리글리시딜에테르, 디글리세롤폴리글리시딜에테르, 폴리글리세롤폴리글리시딜에테르, 레졸신디글리시딜에테르, 2,2-디브로모네오펜틸글리콜디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 펜타에리트리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르, 아디핀산디글리시딜에스테르, 프탈산디글리시딜에스테르, 트리스(글리시딜)이소시아누레이트, 트리스(글리시독시에틸)이소시아누레이트, 1,3-비스(N,N-글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일릴렌디아민 등을 들 수 있다.Examples of the epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylolpropanetriglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanur Tris (glycidoxyethyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m- Xylylenediamine etc. are mentioned.
또한, 이소시아네이트계 화합물, 에폭시계 화합물과 함께 멜라민계 화합물을 단독 또는 2종 이상 혼합하여 추가로 사용할 수 있다.Moreover, melamine type compound can be used individually or in mixture of 2 or more types together with an isocyanate type compound and an epoxy type compound.
멜리민계 화합물로는 헥사메틸올멜라민, 헥사메톡시메틸멜라민, 헥사부톡시메틸멜라민 등을 들 수 있다.Hexamethylol melamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc. are mentioned as a melamine type compound.
가교제는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 3중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.1 내지 1중량부인 것이 좋다. 함량이 0.1중량부 미만인 경우 부족한 가교도로 인해 응집력이 작아지게 되어 들뜸과 같은 내구성 저하가 유발되고 절단성을 해칠 수 있으며, 3중량부 초과인 경우 과다 가교반응에 의해 점착력이 저하되어 내구성이 악화되거나, 잔류응력 완화에 문제가 발생할 수 있다.It is preferable that a crosslinking agent is contained in 0.1-3 weight part with respect to 100 weight part of acrylic copolymers, More preferably, it is 0.1-1 weight part. If the content is less than 0.1 part by weight, the cohesion force becomes small due to insufficient crosslinking degree, which may cause durability deterioration such as lifting and damage of cutting property.In the case of more than 3 parts by weight, the adhesive strength is deteriorated due to the excessive crosslinking reaction. As a result, problems with releasing residual stresses may occur.
본 발명은 상기 산무수물이 가교제의 역할을 수행하므로, 상기 가교제는 종래에 비해 소량 사용해도 무방하다.In the present invention, since the acid anhydride serves as a crosslinking agent, a small amount of the crosslinking agent may be used as compared with the conventional art.
상기와 같은 성분 이외에, 점착제 조성물은 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도 등을 조절하기 위하여, 실란커플링제, 점착성 부여 수지, 산화방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제 등의 첨가제를 더 함유할 수 있다. In addition to the above components, the pressure-sensitive adhesive composition is a silane coupling agent, tackifying resin, antioxidant, leveling agent, surface lubricant, dye, in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, etc. Additives, such as a pigment, an antifoamer, a filler, and a light stabilizer, can be further contained.
이중 실란커플링제는 점착제와 기재와의 밀착력을 향상시키는 역할을하므로 이를 함유하는 것이 바람직하다. 예컨대 비닐클로로실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필디에톡시실란, 3-글리시독시프로필트리에톡시실란, p-스티릴트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-아크릴옥시프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸부틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, 3-클로로프로필트리메톡시실란, 3-머캅토프로필메틸디메톡시실란, 3-머캅토프로필트리메톡시실란, 비스(트리에톡시실릴프로필)테트라설파이드, 3-이소시아네이트프로필트리에톡시실란 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Since the double silane coupling agent plays a role of improving the adhesion between the pressure-sensitive adhesive and the substrate, it is preferable to contain it. For example, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-metha Krilloxypropyl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyla Min, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilyl Propyl) tetrasulfide, 3-isocyanate propyl triethoxysilane, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
실란커플링제는 고형분 함량을 기준으로 아크릴계 공중합체 100중량부에 대하여 0 내지 10중량부로 포함될 수 있으며, 바람직하게 0.005 내지 5중량부로 포함되는 것이 좋다. 함량이 10중량부 초과인 경우 내구성이 저하될 수 있다.The silane coupling agent may be included in an amount of 0 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer based on the solid content, preferably 0.005 to 5 parts by weight. If the content is more than 10 parts by weight, durability may be reduced.
본 발명의 점착제 조성물은 특히 액정셀과의 접합을 위한 편광판용 점착제, 표면보호필름용 점착제로 사용할 수 있다. 또한, 보호필름, 반사시트, 구조용 점착시트, 사진용 점착시트, 차선표시용 점착시트, 광학용 점착제품, 전자부품용 점착제뿐만 아니라 일반 상업용 점착시트제품으로도 사용 가능하다. In particular, the pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive for polarizing plates and a surface protective film for bonding to liquid crystal cells. In addition, it can be used as a general commercial adhesive sheet product as well as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an adhesive for electronic parts, and the like.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.
제조예: 아크릴계 공중합체Preparation Example: Acrylic Copolymer
제조예 1Preparation Example 1
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1 L의 반응기에 n-부틸아크릴레이트(BA) 90중량부, 메타크릴레이트(MA) 7중량부, 2-히드록시에틸아크릴레이트 2중량부 및 디메틸아미노에틸아크릴레이트 1중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 62℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량이 100만인 아크릴계 공중합체를 제조하였다.90 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methacrylate (MA), 2-hydroxyethyl acrylate 2 in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to reflux and for easy temperature control. After adding a monomer mixture consisting of parts by weight and 1 part by weight of dimethylaminoethyl acrylate, 100 parts by weight of ethyl acetate was added as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ℃. After the mixture was uniform, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to prepare an acrylic copolymer having a weight average molecular weight of 1 million.
제조예 2Preparation Example 2
상기 제조예 1과 동일하게 실시하되, 2-히드록시에틸아크릴레이트 대신에 4-히드록시부틸아크릴레이트를 사용하여 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1, an acrylic copolymer was prepared using 4-hydroxybutyl acrylate instead of 2-hydroxyethyl acrylate.
제조예 3Preparation Example 3
상기 제조예 1과 동일하게 실시하되, 2-히드록시에틸아크릴레이트 대신에 히드록시에틸아크릴아미드를 사용하여 아크릴계 공중합체를 제조하였다.An acrylic copolymer was prepared in the same manner as in Preparation Example 1, using hydroxyethylacrylamide instead of 2-hydroxyethyl acrylate.
제조예 4Preparation Example 4
상기 제조예 1과 동일하게 실시하되, 2-히드록시에틸아크릴레이트 대신에
제조예 5Preparation Example 5
상기 제조예 1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 87중량부, 메타크릴레이트(MA) 7중량부, 2-히드록시에틸아크릴레이트 5중량부 및 디메틸아미노에틸아크릴레이트 1중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1, 87 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methacrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate and 1 weight of dimethylaminoethyl acrylate An acrylic copolymer was prepared using the monomer consisting of parts.
제조예 6Preparation Example 6
상기 제조예 1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 82중량부, 메타크릴레이트(MA) 7중량부, 2-히드록시에틸아크릴레이트 10중량부 및 디메틸아미노에틸아크릴레이트 1중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1, 82 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methacrylate (MA), 10 parts by weight of 2-hydroxyethyl acrylate and 1 weight of dimethylaminoethyl acrylate An acrylic copolymer was prepared using the monomer consisting of parts.
제조예 7Preparation Example 7
상기 제조예 1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 90중량부, 메타크릴레이트(MA) 8중량부, 2-히드록시에틸아크릴레이트 2중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체를 제조하였다.The same procedure as in Preparation Example 1, except that 90 parts by weight of n-butyl acrylate (BA), 8 parts by weight of methacrylate (MA), and 2 parts by weight of 2-hydroxyethyl acrylate are used for the acrylic copolymer. Was prepared.
비교 제조예 1Comparative Production Example 1
상기 제조예 1과 동일하게 실시하되, 2-히드록시에틸아크릴레이트 대신에 아크릴산을 사용하여 아크릴계 공중합체를 제조하였다 In the same manner as in Preparation Example 1, an acrylic copolymer was prepared using acrylic acid instead of 2-hydroxyethyl acrylate.
실시예 1-12 및 비교예 1-3Examples 1-12 and Comparative Examples 1-3
1)점착제 조성물1) Adhesive Composition
상기 제조예 1의 아크릴계 공중합체, 산무수물, 가교제 및 실란커플링제를 하기 표 2의 조성으로 혼합한 후, 코팅성을 고려하여 28중량%의 농도로 희석하여 점착제 조성물을 제조하였다.The acrylic copolymer, the acid anhydride, the crosslinking agent, and the silane coupling agent of Preparation Example 1 were mixed in the composition shown in Table 2, and then diluted to a concentration of 28% by weight in consideration of coating properties to prepare an adhesive composition.
[표 1]TABLE 1
2)점착제 부착 편광판2) polarizer with adhesive
1)에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 경화 후 두께가 25㎛가 되도록 도포하고 100℃에서 각각 1분, 5분 및 10분 동안 건조시켜 점착층을 형성하였다. The pressure-sensitive adhesive composition prepared in 1) was applied on a release film coated with a silicone release agent to have a thickness of 25 μm, and dried at 100 ° C. for 1 minute, 5 minutes, and 10 minutes, respectively, to form an adhesive layer.
상기 점착층 위에, 편광자의 양면에 트리아세틸셀룰로오스 보호필름이 접합된 편광판을 라미네이션하여 점착제 부착 편광판을 제조하였다. 이때, 보호필름면과 점착층이 접촉하도록 적층하였다. 상기 제조된 편광판을 23℃, 60%RH의 조건 하에서 양생 기간 동안 보관하였다. On the adhesive layer, a polarizing plate having a triacetyl cellulose protective film bonded to both surfaces of the polarizer was laminated to prepare a polarizing plate with an adhesive. At this time, the protective film surface and the adhesive layer was laminated so as to contact. The prepared polarizing plate was stored under curing conditions at 23 ° C. and 60% RH.
시험예Test Example
상기 실시예 및 비교예에서 제조된 점착제 부착 편광판의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다.The physical properties of the pressure-sensitive adhesive polarizing plate prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
내구성(내열, 내습열)Durability (Heat Resistant, Moisture-Resistant)
제조된 점착제 부착 편광판을 90㎜×170㎜ 크기로 절단하고 이형필름을 박리한 후 유리 기판(110㎜×190㎜×0.7㎜)의 양면에 광학 흡수축이 직교하도록 부착하여 시편을 제작하였다. 이때, 가해진 압력은 5㎏/㎠이며 기포나 이물이 생기지 않도록 크린룸 작업을 하였다. 내열 특성은 80℃의 온도에서 1000시간 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하였고, 내습열 특성은 60℃의 온도 및 90%RH의 조건 하에서 1000시간 방치한 후에 기포나 박리의 발생 여부를 관찰하였다. 이때, 시편의 상태를 평가하기 직전에 상온에서 24시간 방치한 후 관찰하였다.The prepared pressure-sensitive adhesive polarizing plate was cut to a size of 90 mm x 170 mm, the release film was peeled off, and the specimens were prepared by attaching the optical absorption axis perpendicular to both surfaces of the glass substrate (110 mm x 190 mm x 0.7 mm). At this time, the applied pressure was 5kg / ㎠ and the clean room work so as not to generate bubbles or foreign matter. The heat resistance characteristics were observed whether bubbles or peeling occurred after 1000 hours at 80 ℃ temperature, and the heat-resistant characteristics were bubbles or peeling after 1000 hours at 60 ℃ temperature and 90% RH conditions Was observed. At this time, it was observed after leaving for 24 hours at room temperature immediately before evaluating the state of the specimen.
<평가 기준><Evaluation Criteria>
ⓞ: 기포나 박리 없음.Ⓞ: No bubbles or peeling.
○: 기포나 박리 < 5개○: bubble or peeling <5 pieces
△: 5개 ≤ 기포나 박리 < 10개△: 5 ≤ air bubbles or exfoliation <10
×: 10개 ≤ 기포나 박리×: 10 ≤ air bubbles or peeling
××: 전면에 기포나 박리××: air bubbles or peeling off the entire surface
[표 2]TABLE 2
상기 표 2와 같이, 본 발명에 따라 히드록시기를 갖는 아크릴계 공중합체, 상기 화학식 1의 산무수물, 및 가교제를 함유하는 실시예 1 내지 15의 점착제 조성물은 비교예 1 내지 3에 비해 점착 내구성이 우수하다는 것을 확인할 수 있었다. As shown in Table 2, the pressure-sensitive adhesive composition of Examples 1 to 15 containing an acrylic copolymer having a hydroxyl group, the acid anhydride of Formula 1, and a crosslinking agent according to the present invention is superior in adhesion durability compared to Comparative Examples 1 to 3. I could confirm that.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130060746A KR20140140225A (en) | 2013-05-29 | 2013-05-29 | Composition for adhesive |
| KR10-2013-0060746 | 2013-05-29 |
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| Publication Number | Publication Date |
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| WO2014193117A1 true WO2014193117A1 (en) | 2014-12-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/KR2014/004581 Ceased WO2014193117A1 (en) | 2013-05-29 | 2014-05-22 | Adhesive composition |
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| WO (1) | WO2014193117A1 (en) |
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| KR102198346B1 (en) * | 2014-12-29 | 2021-01-04 | 동우 화인켐 주식회사 | Adhesive composition for polarizing plate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH059452A (en) * | 1991-06-28 | 1993-01-19 | Toyo Ink Mfg Co Ltd | Curable adhesive composition and sheet or tape using the same |
| KR20060130386A (en) * | 2005-06-14 | 2006-12-19 | 엘지.필립스 엘시디 주식회사 | LCD and its manufacturing method |
| KR20090077664A (en) * | 2008-01-11 | 2009-07-15 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition, polarizing plate and liquid crystal display including the above |
| JP2011063639A (en) * | 2009-09-15 | 2011-03-31 | Soken Chem & Eng Co Ltd | Adhesive composition |
| KR20110064979A (en) * | 2009-12-09 | 2011-06-15 | 이명천 | Acrylic adhesive resin composition, photocurable re-peelable adhesive resin composition comprising the same, and adhesive tape comprising the same |
-
2013
- 2013-05-29 KR KR20130060746A patent/KR20140140225A/en not_active Withdrawn
-
2014
- 2014-05-22 WO PCT/KR2014/004581 patent/WO2014193117A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH059452A (en) * | 1991-06-28 | 1993-01-19 | Toyo Ink Mfg Co Ltd | Curable adhesive composition and sheet or tape using the same |
| KR20060130386A (en) * | 2005-06-14 | 2006-12-19 | 엘지.필립스 엘시디 주식회사 | LCD and its manufacturing method |
| KR20090077664A (en) * | 2008-01-11 | 2009-07-15 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition, polarizing plate and liquid crystal display including the above |
| JP2011063639A (en) * | 2009-09-15 | 2011-03-31 | Soken Chem & Eng Co Ltd | Adhesive composition |
| KR20110064979A (en) * | 2009-12-09 | 2011-06-15 | 이명천 | Acrylic adhesive resin composition, photocurable re-peelable adhesive resin composition comprising the same, and adhesive tape comprising the same |
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| KR20140140225A (en) | 2014-12-09 |
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