KR20140136163A - Acrylic copolymer and adhesive composition - Google Patents

Abstract

The present invention relates to an acrylic copolymer and an adhesive composition and, more specifically, to an adhesive composition with improved heat resistance and permeability by including acrylic based copolymers copolymerized by using polyhedral oligomeric silsesquioxanes as a polymerizable monomer, or polyhedral oligomeric silsesquioxane as an additive of the adhesive composition.

Description

ACRYLIC COPOLYMER AND ADHESIVE COMPOSITION [0001]

The present invention relates to a pressure-sensitive adhesive composition excellent in heat resistance and transmittance.

2. Description of the Related Art In recent years, with advances in the field of electronics, the size and thickness of electrical appliances have been reduced, and various properties have been required for various types of pressure-sensitive adhesives that can be used in such electrical appliances. In particular, there is a growing demand for heat resistance. This is due to the fact that the miniaturization and ultra-thinness of the electrical device leads to a significant amount of heat buildup. Various studies for releasing generated heat have also been studied, but improvement of heat resistance to various kinds of pressure-sensitive adhesives is further demanded.

The silicone pressure-sensitive adhesive is excellent in heat resistance, but is extremely expensive and not suitable for general-purpose fields, and thus a method for improving the heat resistance of a relatively inexpensive acrylic pressure-sensitive adhesive has been studied.

Specifically, a technique of introducing an alicyclic acrylic monomer has been proposed (JP-A-2008-133408). This is excellent in adhesion to a non-polar substrate such as polyolefin, but has a disadvantage that the effect of improving heat resistance is low.

Further, a technique of copolymerizing an acrylamide-based monomer or the like has been proposed (JP-A-2008-308548). This is excellent in reworkability, but it has a heat resistance temperature of up to about 120 캜, which shows a somewhat insufficient heat resistance in the field of electronics.

Further, a technique for introducing an organic-inorganic hybrid polymer has been proposed (Korean Patent Publication No. 2011-0089832, Korean Patent Publication No. 2011-0094635). Although this has an effect of improving heat resistance, it is difficult to apply to an electronic engineering field which performs a high-temperature treatment process at 250 DEG C or more and has a disadvantage in that the transmittance is remarkably lowered by inorganic particles (silica particles, CNT particles, etc.).

It is an object of the present invention to provide a pressure-sensitive adhesive composition having a heat resistance sufficient to be applied to a high-temperature treatment process of 250 ° C or more and an excellent transmittance.

In order to achieve the above object, the present invention provides an acrylic copolymer containing polyhedral oligomeric silsesquioxane.

The polyhedral oligomeric silsesquioxane may be at least one monomer selected from the group consisting of formulas (1) to (9).

(In the formula, 1 to 9, carbon atoms, R is an aliphatic hydrocarbon group of 1 to 20 with or without a hetero atom, and a carbon number of 5-20 alicyclic hydrocarbon group or aromatic hydrocarbon group having a carbon number of 6-20 and; R ₁ is An alicyclic hydrocarbon group of 5 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms, which contains or does not contain a hetero atom, R ₂ represents hydrogen, an aliphatic hydrocarbon group of 1 to 20 carbon atoms Or an aromatic hydrocarbon group having 6 to 20 carbon atoms)

The acrylic copolymer may contain a (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms and at least one polyhedral oligomeric silsesquioxane selected from the group consisting of the general formulas (1) to (9).

The polyhedral oligomeric silsesquioxane may be contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms.

Further, the present invention can provide a pressure-sensitive adhesive composition containing the acrylic copolymer.

The pressure-sensitive adhesive composition may further contain a crosslinking agent.

In addition, the present invention can provide a pressure-sensitive adhesive composition containing an acrylic copolymer and a polyhedral oligomeric silsesquioxane.

The polyhedral oligomeric silsesquioxane may be at least one selected from the group consisting of the above formulas (1) to (9).

The polyhedral oligomeric silsesquioxane may be contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the acrylic copolymer.

The pressure-sensitive adhesive composition may further contain a crosslinking agent.

The pressure-sensitive adhesive composition according to the present invention has an advantage of being excellent in heat resistance and transmittance by introducing polyhedral oligomeric silsesquioxane having a network structure of a mixture of organic-inorganic compounds.

The present invention relates to a pressure-sensitive adhesive composition excellent in heat resistance and transmittance.

Hereinafter, the present invention will be described in detail.

The present invention relates to a pressure-sensitive adhesive composition containing polyhedral oligomeric silsesquioxane (hereinafter referred to as POSS), wherein the POSS is used as a polymerizable monomer in the preparation of an acrylic copolymer or as an additive contained in a pressure- Can be used.

The POSS is a network structure of a mixture of organic and inorganic materials and has a cage structure. The inside of the POSS structure is composed of a siloxane bond frame network and the outside is composed of reactive or non-reactive organic compounds. The part composed of the non-reactive organic compounds acts like a very small silica particle do.

In addition, the chemical composition of the silica (SiO ₂₎ and silicone (R ₂ SiO) a hybrid-type intermediate element (RSiO _{1 .5),} the intermediate represented by the properties of the polymer material and the ceramic by copolymerization or blending process modifications of existing processes of It is possible to improve the intended physical properties (thermal and physical properties, etc.) by mixing with a polymer material.

POSS is generally used in the art and is not particularly limited, but specifically, at least one selected from the group consisting of the following formulas (1) to (9) can be used. In the formula (2) or (6), a (meth) acrylate group is contained as a functional group and can participate in a radical reaction, so that it is more preferable from the viewpoint of enhancing cohesion and heat resistance of the pressure-sensitive adhesive.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

(In the formula, 1 to 9, carbon atoms, R is an aliphatic hydrocarbon group of 1 to 20 with or without a hetero atom, and a carbon number of 5-20 alicyclic hydrocarbon group or aromatic hydrocarbon group having a carbon number of 6-20 and; R ₁ is An alicyclic hydrocarbon group of 5 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms, which contains or does not contain a hetero atom, R ₂ represents hydrogen, an aliphatic hydrocarbon group of 1 to 20 carbon atoms Or an aromatic hydrocarbon group having 6 to 20 carbon atoms)

The present invention is characterized by copolymerized acrylic copolymer containing POSS as a polymerizable monomer.

The acrylic copolymer of the present invention preferably contains a (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms and at least one POSS selected from the group consisting of the above formulas (1) to (9). In the present invention, (meth) acrylate means acrylate and methacrylate, and the content of each component is based on the 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, (Meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (Meth) acrylate, n-butyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate and lauryl Or a mixture thereof. These may be used alone or in combination of two or more.

The at least one POSS selected from the group consisting of the above formulas (1) to (9) is preferably contained in an amount of 5 to 40 parts by weight, more preferably 10 to 40 parts by weight, per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms To 30 parts by weight. When the content is less than 5 parts by weight, the effect of improving the heat resistance may be insufficient. When the content is more than 40 parts by weight, the properties of the pressure-sensitive adhesive other than heat resistance may be deteriorated.

In addition to POSS, the acrylic copolymer of the present invention may further contain a polymerizable monomer having a crosslinkable functional group.

The polymerizable monomer acts to impart cohesive strength or cohesive strength by chemical bonding with the following crosslinking agent, and examples thereof include a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having an amide group, and a monomer having a tertiary amine group have. These may be used alone or in combination of two or more.

Examples of the monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Hydroxypropyleneglycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms in the alkylene group (e.g., methoxyethyl (meth) acrylate, Hydroxybutyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl (meth) acrylate, 4-hydroxybutyl vinyl ether, Vinyl ether, and 10-hydroxydecyl vinyl ether. Of these, 4-hydroxybutyl vinyl ether is preferable.

Examples of the monomer having a carboxyl group include monovalent acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; A succinic anhydride ring-opening addition adduct of 2-hydroxyalkyl (meth) acrylate in which the alkyl group has 2 to 4 carbon atoms, anhydrous succinic ring opening adduct of a hydroxyalkylene glycol (meth) acrylate having 2 to 4 carbon atoms in the alkylene group , Compounds obtained by ring-opening addition of succinic anhydride to caprolactone adducts of 2-hydroxyalkyl (meth) acrylates whose alkyl groups have 2-3 carbon atoms, and among these, (meth) acrylic acid is preferable.

Examples of the monomer having an amide group include (meth) acrylamide, N-isopropyl acrylamide, N-tertiary butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (Meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide and 2-hydroxyethylhexyl (meth) acrylamide. Of these, (meth) acrylamide is preferable.

Examples of the monomer having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) ) Acrylate, and the like.

The polymerizable monomer is preferably contained in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the total monomers used in the production of the acrylic copolymer. When the content is less than 0.05 part by weight, the cohesive force of the pressure-sensitive adhesive becomes small and durability may be deteriorated. When the content is more than 10 parts by weight, a high gel fraction may lower the adhesive strength and cause durability problems.

In addition, other polymerizable monomers other than the above-mentioned monomers may be further added in an amount not lowering the adhesive force, for example, 10 parts by weight or less based on 100 parts by weight of the total monomers used in the production of the acrylic copolymer.

The method for producing the copolymer is not particularly limited and can be produced by methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control and the like which are usually used in polymerization can be used.

The copolymer preferably has a weight average molecular weight (polystyrene conversion, Mw) of 50,000 to 2,000,000, preferably 400,000 to 2,000,000 as measured by gel permeation chromatography (GPC). If the weight-average molecular weight is less than 50,000, cohesion between co-polymers may be insufficient, which may cause problems in adhesion durability. If the weight average molecular weight is more than 2,000,000, a large amount of diluting solvent may be required in order to ensure fairness in coating.

Further, the present invention is further characterized in that the pressure-sensitive adhesive composition containing the acrylic copolymer in which the POSS is copolymerized.

The pressure-sensitive adhesive composition may further contain a crosslinking agent.

The crosslinking agent can improve the adhesion and durability, and can maintain the reliability at a high temperature and the shape of the pressure-sensitive adhesive.

The cross-linking agent may be an isocyanate-based, epoxy-based, melamine-based, peroxide-based, metal chelating-based, oxazoline-based, or the like. Preferred is a double isocyanate-based or epoxy-based.

Examples of the isocyanate-based isocyanate include isocyanate-based compounds such as tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, Diisocyanate compounds such as isocyanate; An adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate compound in which 3 moles of a diisocyanate compound is self-condensed, a diisocyanate obtained from 2 moles of 3 moles of a diisocyanate compound And multifunctional isocyanate compounds containing three functional groups such as burette, triphenylmethane triisocyanate and methylene bistriisocyanate in which the remaining one mole of diisocyanate is condensed in urea.

The epoxy system may be an ethylene glycol diglycidyl ether, a diethylene glycol diglycidyl ether, a polyethylene glycol diglycidyl ether, a propylene glycol diglycidyl ether, a tripropylene glycol diglycidyl ether, a polypropylene glycol di Hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol poly Glycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate N, N, N ', N'-tetraglycidyl-m-hexyldicyclohexyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, Xylylenediamine, and the like.

Examples of the melamine type include hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine.

Such a crosslinking agent may be contained in an amount of 0.1 to 15 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 part by weight, the cohesive strength may be decreased due to insufficient crosslinking, which may deteriorate the durability of the adhesive durability and the cutability. If the content is more than 15 parts by weight, the residual stress due to the excessive crosslinking reaction may be deteriorated.

The pressure-sensitive adhesive composition may further contain a bifunctional or higher polyfunctional acrylate monomer and a free radical initiator.

The bifunctional or higher polyfunctional acrylate monomer serves to control the curing rate, and it is preferable to use an appropriate amount in consideration of the object of the present invention and the curing rate within the control range.

Specific examples of the bifunctional or higher polyfunctional acrylate monomer include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Acrylate, dicyclopentanyl di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, ethylene oxide modified di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) Allylated cyclohexyl di (meth) acrylate, dimethylol dicyclopentane diacrylate, ethylene oxide modified hexahydrophthalic acid diacrylate, tricyclodecane dimethanol acrylate, neopentyl glycol modified trimethylol Bifunctional monomers such as propane diacrylate and adamantane diacrylate; (Meth) acrylate such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri Trifunctional monomers such as tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, glycerol tri ; Tetrafunctional monomers such as diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate; Pentafunctional monomers such as propionic acid-modified dipentaerythritol penta (meth) acrylate; And hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

The bifunctional or higher polyfunctional acrylate monomer is preferably contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total composition.

The free radical photoinitiator has a function of sufficiently promoting the interior and surface hardening of the pressure-sensitive adhesive, and the type thereof is not particularly limited as long as it is known in the art.

Specific examples of the free radical photoinitiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, hydroxydimethylacetophenone, Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 4-chromenone 2-methyl-1-phenylpropan-1-one, 4-hydroxycyclophenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzo Anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-aminobenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, - Butylanthra 2-amino thioxanthone, 2-amino thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyldimethyl Ketene, diphenyl ketone benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, fluorene, triphenylamine, have. Further, commercially available products such as Darocur 1173, Igacure 184 and Igacure 907 (manufactured by Ciba) can also be used. These may be used alone or in combination of two or more.

The free radical photoinitiator may be used in an appropriate range in consideration of the radiation property, intensity, content of each component, etc. of the light source, and is preferably contained in an amount of 0.1 to 5% by weight based on the total content (100% by weight) of the pressure-sensitive adhesive composition.

The present invention is further characterized by the acrylic copolymer and the pressure-sensitive adhesive composition containing the POSS.

The acrylic copolymer preferably contains a (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms, and may further contain a polymerizable monomer having a crosslinkable functional group.

The polymerizable monomer includes a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having an amide group, and a monomer having a tertiary amine group.

The specific kind of the polymerizable monomer, the production method of the acrylic copolymer, the physical properties, the kind of POSS, and the like are the same as those described above.

POSS is preferably contained in an amount of 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, per 100 parts by weight of the acrylic copolymer. When the content is less than 5 parts by weight, the effect of improving the heat resistance may be insufficient. When the content is more than 40 parts by weight, the properties of the pressure-sensitive adhesive other than heat resistance may be deteriorated.

The pressure-sensitive adhesive composition may further contain at least one selected from the group consisting of a crosslinking agent, a polyfunctional acrylate-based monomer, and a free radical initiator. Their roles, kinds, contents and the like are the same as those described above.

The pressure-sensitive adhesive composition of the present invention can be cured to form a pressure-sensitive adhesive. Further, a transparent base film; The pressure-sensitive adhesive may include the pressure-sensitive adhesive formed on one side of the transparent substrate film.

The pressure-sensitive adhesive may have a thickness of 5 to 1000 mu m.

The transparent base film is not particularly limited as it is excellent in transparency, mechanical strength, thermal stability, moisture barrier property and the like.

The curing is not particularly limited as it is used in the art, but is generally photocuring using ultraviolet rays.

The light source in the polymerization using ultraviolet rays has a light emission distribution of 400 nm or less, preferably 150 to 400 nm, and more preferably 200 to 380 nm. The light source may be a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, , A black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

The intensity of the light irradiation can be appropriately adjusted according to the physical properties of the desired pressure-sensitive adhesive, and the amount of accumulated light useful for the activity of the free radical photoinitiator is preferably 10 to 5000 mJ / cm 2, more preferably 200 to 2000 mJ / cm 2. It is preferable to have an appropriate curing reaction time within the above range and to prevent the heat radiated from the lamp and the cohesive force of the cured product produced by heat generation during the polymerization reaction from deteriorating and deterioration of the yellowing or the support.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Manufacturing example  : Acrylic copolymer preparation

Manufacturing example  One

85 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate (hereinafter referred to as " And 3 parts by weight of acrylic acid, and then 100 parts by weight of ethyl acetate (EAc) was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 62 ° C. After the mixture was homogeneously mixed, 0.07 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 8 hours to prepare an acrylic copolymer (weight average molecular weight: about 1,000,000).

Manufacturing example  2

(R은 에틸기) 5중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체(중량평균분자량 약 97만)를 제조하였다.
Except that 80 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts by weight of acrylic acid,

(R is an ethyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 970,000).

Manufacturing example  3

(R은 에틸기) 10중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체(중량평균분자량 약 103만)를 제조하였다.
Except that 75 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts by weight of acrylic acid,

(R is an ethyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 1.03 million).

Manufacturing example  4

(R은 에틸기) 20중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체(중량평균분자량 약 94만)를 제조하였다.
Except that 65 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts by weight of acrylic acid,

(R is an ethyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 940,000).

Manufacturing example  5

(R은 에틸기) 30중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체(중량평균분자량 약 99만)를 제조하였다.
Except that 55 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts by weight of acrylic acid,

(R is an ethyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 990,000).

Manufacturing example  6

(R은 에틸기) 40중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체(중량평균분자량 약 101만)를 제조하였다.
Except that 45 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts by weight of acrylic acid,

(R is an ethyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 1.01 million).

Manufacturing example  7

(R은 에틸기) 50중량부로 이루어진 단량체를 사용하여 아크릴계 공중합체(중량평균분자량 약 100만)를 제조하였다.
Except that 35 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts by weight of acrylic acid,

(R is an ethyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 1,000,000).

Manufacturing example  8

(R은 에틸기) 대신에

(R은 이소부틸기)을 사용하여 아크릴계 공중합체(중량평균분자량 약 97만)를 제조하였다.
The procedure of Preparation Example 2 was repeated,

(R is an ethyl group) instead of

(R is isobutyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 970,000).

Manufacturing example  9

(R은 에틸기) 대신에

(R은 이소-옥틸기)을 사용하여 아크릴계 공중합체(중량평균분자량 약 92만)를 제조하였다.
The procedure of Preparation Example 2 was repeated,

(R is an ethyl group) instead of

(R is iso-octyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 920,000).

Manufacturing example  10

(R은 에틸기)

(R은 페닐기)을 사용하여 아크릴계 공중합체(중량평균분자량 약 103만)를 제조하였다.
The procedure of Preparation Example 2 was repeated,

(R is an ethyl group)

(R is a phenyl group) was used to prepare an acrylic copolymer (weight average molecular weight: about 1.03 million).

Example : Pressure-sensitive adhesive composition

Example  One

The acrylic copolymers, polyfunctional acrylate monomers, crosslinking agent and free radical initiator of Production Examples 2 to 9 were mixed in the composition shown in Table 1 and diluted with a glass solvent to prepare a pressure-sensitive adhesive composition.

division
(Parts by weight) Acrylic copolymer
(100 parts by weight) Multifunctional
Acrylate Cross-linking agent freedom
Radical
Initiator A-1 A-2 A-3 B-1 B-2 B-3 B-4 Example 1-1 Production Example 2 - - - 0.5 - - - - Examples 1-2 Production Example 2 10 - - 0.5 - - - One Example 1-3 Production Example 3 10 - - 0.5 - - - One Examples 1-4 Production Example 4 10 - - 0.5 - - - One Examples 1-5 Production Example 5 10 - - 0.5 - - - One Examples 1-6 Production Example 6 10 - - 0.5 - - - One Examples 1-7 Production Example 7 10 - - 0.5 - - - One Examples 1-8 Production Example 8 10 - - 0.5 - - - One Examples 1-9 Production Example 9 10 - - 0.5 - - - One Example 1-10 Production Example 10 10 - - 0.5 - - - One Example 1-11 Production Example 2 - 10 - 0.5 - - - One Examples 1-12 Production Example 2 - - 10 0.5 - - - One Examples 1-13 Production Example 2 10 - - - 0.5 - - One Examples 1-14 Production Example 2 10 - - - - 0.5 - One Examples 1-15 Production Example 2 10 - - - - - 0.5 One Comparative Example 1-1 Production Example 1 10 - - 0.5 - - - One A-1: Trimethylolpropane triacrylate
A-2: Tris (2-hydroxyethyl) isocyanurate triacrylate
A-3: Dipentaerythritol hexaacrylate
B-1: Coronate-L (TMP adduct of TDI, Urethane Japan)
B-2: Coronate-HXR (isocyanurate of HDI, Urethane Company of Japan)
B-3: D110N (HDI-TMP adduct, Mitsui Chemicals)
B-4: D140N (IPDI-TMP adduct, Mitsui Chemicals)
Free radical photoinitiator: Ciba, Darocur-1173

Example  2

The acrylic copolymer, the polyfunctional acrylate monomer, the crosslinking agent, the free radical initiator, and the polyhedral oligomeric silsesquioxane of Preparation Example 1 were mixed in the composition shown in Table 2 below and diluted with a glass solvent to prepare a pressure-sensitive adhesive composition .

division
(Parts by weight) Acrylic copolymer
(100 parts by weight) Multifunctional
Acrylate Cross-linking agent freedom
Radical
Initiator POSS A-1 A-2 A-3 B-1 B-2 B-3 B-4 C-1 C-2 C-3 C-4 C-5 Example 2-1 Production Example 1 - - - 0.5 - - - - 10 - - - - Example 2-2 Production Example 1 10 - - 0.5 - - - One 10 - - - - Example 2-3 Production Example 1 10 - - 0.5 - - - One - 10 - - - Examples 2-4 Production Example 1 10 - - 0.5 - - - One - - 10 - - Example 2-5 Production Example 1 10 - - 0.5 - - - One - - - 10 - Examples 2-6 Production Example 1 10 - - 0.5 - - - One 5 - - - - Examples 2-7 Production Example 1 10 - - 0.5 - - - One 20 - - - - Examples 2-8 Production Example 1 10 - - 0.5 - - - One 30 - - - - Examples 2-9 Production Example 1 10 - - 0.5 - - - One 40 - - - - Examples 2-10 Production Example 1 10 - - 0.5 - - - One 50 - - - - Examples 2-11 Production Example 1 - 10 - 0.5 - - - One 10 - - - - Examples 2-12 Production Example 1 - - 10 0.5 - - - One 10 - - - - Examples 2-13 Production Example 1 10 - - - 0.5 - - One 10 - - - - Examples 2-14 Production Example 1 10 - - - - 0.5 - One 10 - - - - Examples 2-15 Production Example 1 10 - - - - - 0.5 One 10 - - - - Comparative Example 2-1 Production Example 1 10 - - 0.5 - - - One - - - - 10

(R은 에틸기)
C-2; 상기 C-1 구조(R= 이소부틸)
C-3: 상기 C-1 구조(R= 이소옥틸)
C-4: 상기 C-1 구조(R= 페닐)
C-5: 실리카입자(풍림무약, IPA-ST )A-1: Trimethylolpropane triacrylate
A-2: Tris (2-hydroxyethyl) isocyanurate triacrylate
A-3: Dipentaerythritol hexaacrylate
B-1: Coronate-L (TMP adduct of TDI, Urethane Japan)
B-2: Coronate-HXR (isocyanurate of HDI, Urethane Company of Japan)
B-3: D110N (HDI-TMP adduct, Mitsui Chemicals)
B-4: D140N (IPDI-TMP adduct, Mitsui Chemicals)
Free radical photoinitiator: Ciba, Darocur-1173
C-1:

(R is an ethyl group)
C-2; The C-1 structure (R = isobutyl)
C-3: The above C-1 structure (R = isooctyl)
C-4: The above C-1 structure (R = phenyl)
C-5: Silica particles (spindle-free, IPA-ST)

The pressure-sensitive adhesive composition prepared above was coated on a transparent base material film coated with a silicone release agent to a thickness of 50 占 퐉, irradiated with ultraviolet rays at a rate of 4m / min (600mJ / cm2) (600 mJ / cm < 2 >) of ultraviolet light to prepare a fully cured pressure-sensitive adhesive film.

Test Example

The physical properties of the polarizer with a pressure-sensitive adhesive prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

1. Evaluation of heat resistance

1) The prepared release film of the polarizing plate with a pressure-sensitive adhesive was removed, bonded to a Corning glass, autoclaved, left at 90 캜 for 300 hours, and bubbles and peeling phenomenon were observed.

<Evaluation Criteria>

X: Bubbles were found to be more than 3, or peeling occurred more than 1 mm

?: Two or more bubbles were identified, or peeling was confirmed in the range of more than 0.2 mm and less than 1 mm

○: One bubble was confirmed or peeling of 0.2 mm or less was confirmed

◎: No bubbles or peeling are visually confirmed

2) The temperature at which the weight of the pressure-sensitive adhesive composition was reduced by 5% was measured using Q1000 equipment of TA instruments. At this time, the higher the decreasing temperature, the more stable the heat-resistant condition and the better the heat resistance. Generally, when the temperature is 360 ° C or higher, the heat resistance is considered to be excellent.

2. Transmittance

The transmittance at a wavelength of 500 nm was measured using a UV-3100PC instrument manufactured by Shimadzu Corporation.

division Heat resistance Transmittance 5% weight reduction temperature Example 1-1 ○ 95 365 Examples 1-2 ◎ 95 370 Example 1-3 ◎ 95 369 Examples 1-4 ◎ 95 371 Examples 1-5 ◎ 95 370 Examples 1-6 ○ 96 368 Examples 1-7 ◎ 90 379 Examples 1-8 ◎ 93 373 Examples 1-9 ◎ 93 373 Example 1-10 ◎ 91 375 Example 1-11 ◎ 95 370 Examples 1-12 ◎ 95 370 Examples 1-13 ◎ 95 368 Examples 1-14 ◎ 95 368 Examples 1-15 ◎ 95 369 Example 2-1 ○ 94 365 Example 2-2 ◎ 95 370 Example 2-3 ◎ 95 369 Examples 2-4 ◎ 95 371 Example 2-5 ◎ 95 370 Examples 2-6 ○ 96 365 Examples 2-7 ◎ 94 372 Examples 2-8 ◎ 93 373 Examples 2-9 ◎ 93 374 Examples 2-10 ◎ 90 379 Examples 2-11 ◎ 95 370 Examples 2-12 ◎ 95 370 Examples 2-13 ◎ 95 368 Examples 2-14 ◎ 94 368 Examples 2-15 ◎ 95 369 Comparative Example 1-1 × 97 355 Comparative Example 2-1 ○ 88 365

As shown in Table 2, the pressure-sensitive adhesive compositions of Examples 1 and 2, which were prepared using the acrylic copolymer containing polyhedral oligomeric silsesquioxane according to the present invention, The occurrence and exfoliation phenomenon was low and the temperature at which the weight was reduced by 5% was high, so that it was confirmed that the heat resistance was excellent and the transmittance was improved.

Claims (10)

An acrylic copolymer containing polyhedral oligomeric silsesquioxane.
The acrylic copolymer as set forth in claim 1, wherein the polyhedral oligomeric silsesquioxane is at least one selected from the group consisting of formulas (1) to (9)
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

(In the formula, 1 to 9, carbon atoms, R is an aliphatic hydrocarbon group of 1 to 20 with or without a hetero atom, and a carbon number of 5-20 alicyclic hydrocarbon group or aromatic hydrocarbon group having a carbon number of 6-20 and; R ₁ is An alicyclic hydrocarbon group of 5 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms, which contains or does not contain a hetero atom, R ₂ represents hydrogen, an aliphatic hydrocarbon group of 1 to 20 carbon atoms Or an aromatic hydrocarbon group having 6 to 20 carbon atoms)
[Claim 2] The acrylic copolymer according to claim 2, wherein the acrylic copolymer comprises a (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms and at least one polyhedral oligomeric silsesquioxane selected from the group consisting of the general formulas Acrylic copolymer.
4. The acrylic copolymer according to claim 3, wherein the polyhedral oligomeric silsesquioxane contains 5 to 40 parts by weight per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms.
A pressure-sensitive adhesive composition containing the acrylic copolymer according to any one of claims 1 to 4.
The pressure-sensitive adhesive composition according to claim 5, wherein the pressure-sensitive adhesive composition further comprises a crosslinking agent.
Acrylic copolymer and polyhedral oligomeric silsesquioxane.
The pressure-sensitive adhesive composition according to claim 7, wherein the polyhedral oligomeric silsesquioxane is at least one selected from the group consisting of the following formulas (1) to (9):
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

(In the formula, 1 to 9, carbon atoms, R is an aliphatic hydrocarbon group of 1 to 20 with or without a hetero atom, and a carbon number of 5-20 alicyclic hydrocarbon group or aromatic hydrocarbon group having a carbon number of 6-20 and; R ₁ is An alicyclic hydrocarbon group of 5 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms, which contains or does not contain a hetero atom, R ₂ represents hydrogen, an aliphatic hydrocarbon group of 1 to 20 carbon atoms Or an aromatic hydrocarbon group having 6 to 20 carbon atoms)
The pressure-sensitive adhesive composition according to claim 7, wherein the polyhedral oligomeric silsesquioxane is contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the acrylic copolymer.
The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition further comprises a crosslinking agent.