KR20150035177A - Acrylic adhesive composition and silane compounds - Google Patents

Acrylic adhesive composition and silane compounds Download PDF

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Publication number
KR20150035177A
KR20150035177A KR20130115429A KR20130115429A KR20150035177A KR 20150035177 A KR20150035177 A KR 20150035177A KR 20130115429 A KR20130115429 A KR 20130115429A KR 20130115429 A KR20130115429 A KR 20130115429A KR 20150035177 A KR20150035177 A KR 20150035177A
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South Korea
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group
sensitive adhesive
alkyl group
adhesive composition
silane
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KR20130115429A
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Korean (ko)
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최한영
권혜림
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동우 화인켐 주식회사
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Publication of KR20150035177A publication Critical patent/KR20150035177A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to an acrylic pressure-sensitive adhesive composition and a silane-based compound, and more particularly, to a pressure-sensitive adhesive composition containing a silane-based compound represented by the following formula (1) The present invention relates to an acrylic pressure-sensitive adhesive composition which is excellent in adhesion durability under the conditions (high temperature or high temperature and high humidity) and does not excessively increase the pressure-sensitive adhesive even under high temperature or high temperature and humidity,
[Chemical Formula 1]

Figure pat00047

(Wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 is a C 1 -C 6 alkyl group , R 3 is a C 1 -C 8 aliphatic hydrocarbon group or a C 1 -C 8 aliphatic hydrocarbon group containing a heteroatom, R 4 , R 5 and R 6 are each independently hydrogen, C 1 -C 6 An aliphatic hydrocarbon group, a halogen group, a sulfonyl group, a hydroxy group, an amino group, a carbonyl group or a C 1 -C 6 carboxyester group).

Description

The acrylic pressure-sensitive adhesive composition and the silane-based compound (ACRYLIC ADHESIVE COMPOSITION AND SILANE COMPOUNDS)

The present invention relates to an acrylic pressure-sensitive adhesive composition and a novel silane-based compound excellent in adhesion durability and reworkability.

In general, a liquid crystal display device (LCD) includes a liquid crystal cell including a liquid crystal and a polarizing plate. In order to improve the display quality of the liquid crystal display device, various optical films (retardation plate, A brightness enhancement film or the like) is used.

The polarizing plate and the optical film are bonded to the liquid crystal cell using a pressure-sensitive adhesive. As the pressure sensitive adhesive, an acrylic pressure sensitive adhesive based on an acrylic polymer having excellent adhesiveness and transparency is often used. The crosslinking of the acrylic pressure-sensitive adhesive utilizes the bonding of the crosslinking agent and the functional monomer of the acrylic polymer.

As a pressure-sensitive adhesive, a pressure-sensitive adhesive composition containing a silane-based compound having an epoxy group (JP-A-4-223403) is known. However, the pressure-sensitive adhesive can not maintain a proper adhesive force to the extent required in an actual use environment, and the adhesive force excessively increases under high temperature and high humidity conditions, and the pressure-sensitive adhesive remains on the substrate upon re-

Further, there is proposed a pressure-sensitive adhesive composition containing a silane-based compound having cyanoacetyl group (Korean Patent No. 840114) and a pressure-sensitive adhesive composition containing a silane-based compound having an acetoacetyl group (Korean Patent No. 671400). Since the pressure-sensitive adhesive does not excessively increase the adhesive strength under high temperature or high temperature and high humidity, the pressure-sensitive adhesive does not remain on the substrate upon re-peeling, which is advantageous in terms of reworkability. However, there is a disadvantage in that the initial adhesion is relatively low and the durability to adhesion in a severe condition (high temperature or high temperature and high humidity) is lowered.

An object of the present invention is to provide an acrylic pressure-sensitive adhesive composition which is excellent in adhesion durability under severe conditions (high temperature or high temperature and high humidity), and at the same time does not excessively increase the adhesive force under the severe condition,

In order to achieve the above object, the present invention provides an acrylic pressure sensitive adhesive composition containing a silane compound represented by the following general formula (1).

Figure pat00001

(Wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 is a C 1 -C 6 alkyl group , R 3 is a C 1 -C 8 aliphatic hydrocarbon group or a C 1 -C 8 aliphatic hydrocarbon group containing a heteroatom, R 4 , R 5 and R 6 are each independently hydrogen, C 1 -C 6 An aliphatic hydrocarbon group, a halogen group, a sulfonyl group, a hydroxy group, an amino group, a carbonyl group or a C 1 -C 6 carboxyester group).

Preferably, the above formula (1) and the silane-based compounds X and Y are each independently O, S or NH, R 1 is an alkoxy group of C 1 -C 6 alkyl group or a C 1 -C 6, R 2 is an alkyl group of C 1 -C 6, R 3 is an alkyl group of C 1 -C 8 alkyl group or containing O, S or NH of C 1 -C 8, R 4, are each independently hydrogen, R 5 and R 6 Or a C 1 -C 6 alkyl group.

More preferably, the silane compound of Formula 1 may be at least one selected from the following Formulas 2 to 6.

Figure pat00002

Figure pat00003

Figure pat00004

Figure pat00005

Figure pat00006

The pressure-sensitive adhesive composition may contain an acrylic copolymer and a silane-based compound of formula (1).

The silane compound of Formula 1 may be contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer.

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

The polymerizable monomer having a crosslinkable functional group may be contained in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms.

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

The present invention also provides a silane-based compound represented by the following general formula (1).

[Chemical Formula 1]

Figure pat00007

(Wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 is a C 1 -C 6 alkyl group , R 3 is a C 1 -C 8 aliphatic hydrocarbon group or a C 1 -C 8 aliphatic hydrocarbon group containing a heteroatom, R 4 , R 5 and R 6 are each independently hydrogen, C 1 -C 6 An aliphatic hydrocarbon group, a halogen group, a sulfonyl group, a hydroxy group, an amino group, a carbonyl group or a C 1 -C 6 carboxyester group).

Preferably, the above formula (1) and the silane-based compounds X and Y are each independently O, S or NH, R 1 is an alkoxy group of C 1 -C 6 alkyl group or a C 1 -C 6, R 2 is an alkyl group of C 1 -C 6, R 3 is an alkyl group of C 1 -C 8 alkyl group or containing O, S or NH of C 1 -C 8, R 4, are each independently hydrogen, R 5 and R 6 Or a C 1 -C 6 alkyl group.

The silane-based compound of Formula 1 may be at least one selected from the following Formulas 2 to 6.

(2)

Figure pat00008

(3)

Figure pat00009

[Chemical Formula 4]

Figure pat00010

[Chemical Formula 5]

Figure pat00011

[Chemical Formula 6]

Figure pat00012

The acrylic pressure-sensitive adhesive composition of the present invention is excellent in adhesion durability under severe conditions (high temperature or high temperature and high humidity) and does not excessively increase the pressure-sensitive adhesive even under high temperature or high temperature and high humidity, .

The present invention relates to an acrylic pressure-sensitive adhesive composition and a novel silane-based compound excellent in adhesion durability and reworkability.

Hereinafter, the present invention will be described in detail.

The acrylic pressure sensitive adhesive composition of the present invention contains a silane compound represented by the following general formula (1). The silane-based compound represented by the following formula (1) is a novel compound.

[Chemical Formula 1]

Figure pat00013

(Wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 is a C 1 -C 6 alkyl group , R 3 is a C 1 -C 8 aliphatic hydrocarbon group or a C 1 -C 8 aliphatic hydrocarbon group containing a heteroatom, R 4 , R 5 and R 6 are each independently hydrogen, C 1 -C 6 An aliphatic hydrocarbon group, a halogen group, a sulfonyl group, a hydroxy group, an amino group, a carbonyl group or a C 1 -C 6 carboxyester group).

Preferably, the above formula (1) and the silane-based compounds X and Y are each independently O, S or NH, R 1 is an alkoxy group of C 1 -C 6 alkyl group or a C 1 -C 6, R 2 is an alkyl group of C 1 -C 6, R 3 is an alkyl group of C 1 -C 8 alkyl group or containing O, S or NH of C 1 -C 8, R 4, are each independently hydrogen, R 5 and R 6 Or a C 1 -C 6 alkyl group.

More preferably, the silane compound of Formula 1 may be at least one selected from the following Formulas 2 to 6.

(2)

Figure pat00014

(3)

Figure pat00015

[Chemical Formula 4]

Figure pat00016

[Chemical Formula 5]

Figure pat00017

[Chemical Formula 6]

Figure pat00018

The silane-based compound is superior in compatibility with an acrylic copolymer in comparison with acetoacetoxy, cyanoacetoxy group, or glycidoxy group-containing silane coupling agent, so that bleed-out from the pressure-sensitive adhesive is suppressed, Is expected to rise.

Further, when heated, a small amount is bleed-out on the surface, and the pressure-sensitive adhesive reacts with the glass to increase the hot adhesion. It is predicted that the reactivity between the silane coupling agent and the crosslinking agent is small and the warming adhesion slightly increases.

The compound of formula (1) can be prepared by a method commonly used in the art and is not particularly limited. For example, the compound of formula (1) can be obtained by a nucleophilic substitution reaction between an acid chloride and a silane containing a nucleophilic substituent.

The acrylic pressure sensitive adhesive composition of the present invention contains an acrylic copolymer and a silane compound of formula (1).

In the acrylic copolymer of the present invention, the acrylic copolymer preferably contains a (meth) acrylate monomer having an alkyl group having from 1 to 12 carbon atoms and a crosslinkable monomer. In the present invention, (meth) acrylate means acrylate and methacrylate, and the content is based on the solid content.

Examples of the (meth) acrylate monomer having an alkyl group of 1-12 carbon atoms include (meth) acrylates derived from an aliphatic alcohol having 1 to 12 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, n- Butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (Meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate. These may be used alone or in combination of two or more. Of these, n-butyl acrylate, 2-ethylhexyl acrylate or a mixture thereof is preferable.

The crosslinkable monomer has a function of imparting cohesive strength or cohesive strength by chemical bonding with the following crosslinking agent, and examples thereof include monomers having a hydroxyl group, monomers having a carboxyl group, monomers having an amide group, and monomers 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 crosslinkable 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 (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms. 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 crosslinking monomers other than the above-mentioned monomers may be further added in an amount not lowering the adhesive force, for example, 40 parts by weight or less based on 100 parts by weight of the total monomers used for producing 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.

It is preferable that the silane compound of Formula 1 is contained in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. When the content is less than 0.001 part by weight, the amount is too small to improve the durability. If the content is more than 5 parts by weight, the initial adhesion may be lowered and the durability may be lowered.

The pressure-sensitive adhesive composition of the present invention 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.

In addition to the above components, the pressure-sensitive adhesive composition may further contain additives such as a tackifier resin, an antioxidant, a leveling agent, a surface lubricant, a dye, a pigment, a defoaming agent, A filler, a light stabilizer, and the like.

In addition, the pressure-sensitive adhesive composition of the present invention is preferably free of the conventional coupling agents used in the art in consideration of durability and reworkability.

Such an additive can appropriately control the content within a range that does not impair the effect of the present invention.

The pressure-sensitive adhesive composition of the present invention can be used particularly as a pressure-sensitive adhesive for a polarizing plate or a pressure-sensitive adhesive for a surface protective film for bonding with a liquid crystal cell. In addition, it can be used not only 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 electronic component adhesive, but also a general commercial adhesive sheet product or a medical patch.

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  1: Production of acrylic copolymer

Manufacturing example  1-1

85 parts by weight of n-butyl acrylate (BA), 10 parts by weight of methyl acrylate (MA), 2 parts by weight of 2-hydroxyethyl acrylate 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  1-2

84 parts by weight of n-butyl acrylate (BA), 10 parts by weight of benzyl methacrylate (BzMA), 2 parts by weight of 2-hydroxyethyl acrylate 1 , And 5 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: Silane system  Compound manufacturing

Manufacturing example  2-1: B-1

Figure pat00019
(17.6 g, 0.11 mol) was added to dichloromethane (200 mL)
Figure pat00020
(17.9 g, 0.1 mol) in dichloromethane (100 mL) and triethylamine (50 mL) was added dropwise with dropping funnel for 1 hour at room temperature with stirring. After the dropwise addition, the reaction mixture was further stirred at room temperature for 1 hour, and 300 mL of distilled water was used to extract and remove unreacted compounds and salts as reaction by-products. The solvent and triethylamine were removed by distillation under reduced pressure to obtain 28.2 g of the product. Thereafter, a part of the product was dissolved in CDCl 3 to be dissolved, and the result was confirmed by NMR.

Figure pat00021

NMR (300 MHz) CDCl 3 : 7.0-6.9 (3H), 5.9 (1H), 3.76 (2H)

Manufacturing example  2-2: B-2

The procedure of Preparation Example 2-1 was repeated,

Figure pat00022
(19.6 g, 0.1 mol).

Figure pat00023

NMR (300 MHz) CDCl 3 : 7.0-6.9 (3H), 3.5 (9H), 3.2 (2H)

Manufacturing example  2-3: B-3

Figure pat00024
0.1 mol (14.2 g) was dissolved in 200 mL of 1,4-dioxane as a solvent, and 0.15 mol of allyl chloride and 0.001 mol of tetrabutylammonium bromide were added as a catalyst, followed by reaction at 50 DEG C for 12 hours. After completion of the reaction, the reaction mixture was poured into 1 L of distilled water and extracted with toluene to obtain an allyl derivative. The obtained allyl derivative was reacted with 0.1 mol of trimethoxysilane in the presence of 0.001 mol of a ruthenium trichloride catalyst without further purification at 50 ° C for 12 hours to obtain the following structural formula (4) (30.1 g).

Figure pat00025

NMR 300MHz CDCl 3: 7.0-6.9 (3H ), 4.55 (2H), 3.76 (2H), 3.57 (9H) 1.72 (2H), 0.75 (2H)

Manufacturing example  2-4: B-4

The procedure of Preparation Example 2-2 was repeated,

Figure pat00026
16.0 g, 0.11 mol).

Figure pat00027

NMR (300 MHz) CDCl 3 : 8.1 (1H), 7.2 (1H), 6.2 (1H), 5.9 (1H)

Manufacturing example  2-5: B-5

The procedure of Preparation Example 2-2 was repeated,

Figure pat00028
(15.8 g, 0.11 mol).

Figure pat00029

NMR 300MHz CDCl 3: 8.0 (1H ), 5.9 (1H), 5.7 (1H), 5.0 (1H), 3.6 (9H), 3.5 (2H), 3.2 (2H), 1.55 (2H), 0.58 (2H)

Example  1 to 15 and Comparative Example  1 to 3

The acrylic copolymer, silane compound and crosslinking agent of Preparation Example 1 were mixed in the composition shown in Table 1 and diluted to a concentration of 14% by weight to prepare a pressure-sensitive adhesive composition.

division
(Parts by weight) Acrylic copolymer
(Production Example 1) Cross-linking agent Silane compound 1-1 1-2 A-1 A-2 A-3 A-4 B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 Example 1 100 - One - - - 0.01 - - - - - - - Example 2 100 - One - - - 0.4 - - - - - - - Example 3 100 - One - - - 0.7 - - - - - - - Example 4 100 - One - - - One - - - - - - - Example 5 100 - One - - - 2 - - - - - - - Example 6 100 - One - - - 5 - - - - - - - Example 7 100 - One - - - 7 - - - - - - - Example 8 100 - One - - - - 0.4 - - - - - - Example 9 100 - One - - - - - 0.4 - - - - - Example 10 100 - One - - - - - - 0.4 - - - - Example 11 100 - One - - - - - - - 0.4 - - - Example 12 100 - - One - - 0.4 - - - - - - - Example 13 100 - - - One - 0.4 - - - - - - - Example 14 100 - - - - One 0.4 - - - - - - - Example 15 - 100 One - - - 0.4 - - - - - - - Comparative Example 1 100 - One - - - - - - - - One - - Comparative Example 2 100 - One - - - - - - - - - One - Comparative Example 3 100 - One - - - - - - - - - - One A-1; Coronate-L (TDI TMP Adduct, Japan Urethane Co., Ltd.)
A-2; Coronate-HXR (isocyanurate of HDI, Urethane Company of Japan)
A-3: D110N (HDI-TMP adduct, Mitsui Chemicals)
A-4: D140N (IPDI-TMP adduct, Mitsui Chemicals)
B-1:

Figure pat00030

B-2:
Figure pat00031

B-3:
Figure pat00032

B-4:
Figure pat00033

B-5:
Figure pat00034

B-6; Glycidoxypropyltrimethoxysilane (Shin-Etsu, KBM403)
B-7; Acetoacetoxypropyltrimethoxysilane (Soken)
B-8; Chloropropyltrimethoxysilane (Gelest, SIC2410)

The pressure-sensitive adhesive composition prepared above was applied on a release film coated with silicone release agent to a thickness of 25 탆 and dried at 100 캜 for 1 minute to form an adhesive layer.

The pressure-sensitive adhesive layer prepared above was laminated to an iodine-based polarizing plate having a thickness of 185 μm by pressure-sensitive adhesive processing to produce a polarizer with a pressure-sensitive adhesive. The prepared polarizing plate was stored for a curing period under the conditions of 23 캜 and 60% RH.

Test Example

The properties of the pressure-sensitive adhesive composition and 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 2 below.

1. Adhesive strength (N / 25 mm)

The polarizer with a pressure-sensitive adhesive was cut into a size of 25 mm x 100 mm and the release film was peeled off. The glass substrate (# 1737, Corning) was laminated at a pressure of 0.25 MPa and autoclaved to prepare a specimen.

The initial adhesive strength of the specimens after being left for 24 hours under the conditions of 23 ° C. and 50% RH and the temperature bonding strength after 48 hours at 50 ° C. and 50% RH were measured using a universal tensile tester (UTM, Instron) The peeling speed was 300 mm / min, and the peeling angle was 180 deg. At this time, measurement was carried out under conditions of 23 캜 and 50% RH.

2. Durability (heat resistance, Wet heat )

The polarizing plate with a pressure-sensitive adhesive was cut into a size of 90 mm x 170 mm and the release film was peeled off. The polarizing plate was attached to both sides of a glass substrate (110 mm x 190 mm x 0.7 mm) such that the absorption axes of the respective polarizing plates were orthogonal. At this time, the applied pressure was 5 kg / cm 2 , and a clean room operation was performed so that bubbles or foreign matter would not be generated.

The heat resistance of the specimen was maintained at a temperature of 80 ° C for 1000 hours, and then the occurrence of bubbles or peeling was observed. The specimens were allowed to stand at room temperature for 24 hours immediately before evaluating the state of the specimens. In addition, the moisture resistance of the specimen was measured for 1000 hours under the conditions of a temperature of 60 ° C and a humidity of 90% RH, and then the occurrence of bubbles or peeling was observed.

<Evaluation Criteria>

No bubble or peeling: ⓞ

Less than 5 bubbles or peeling: ○

Bubbles or exfoliation Less than 5: Less than 10

10 or more bubbles or peeling: x

3. Re-workability

The polarizing plate was cut to a size of 25 mm in width and 100 mm in length, and the release film was peeled off. The release film was then laminated on Corning's # 1737 glass at a pressure of 0.25 MPa and autoclaved for 20 minutes under conditions of 5 atm and 50 캜 Evaluation samples were prepared. After putting it in an oven at 80 ° C, which was a heat-resistant condition, it was taken out after 10 hours, left at room temperature for 120 hours, and peeled at a rate of 1.3 cm / s.

<Evaluation Criteria>

- No residue of adhesive on glass substrate and cleanly peeled off without tearing of polarizer: ○

- Adhesive is left on the panel or the polarizer is torn in the process of peeling: x

division adhesiveness durability Re-workability Early Warming Heat resistance Wet heat Example 1 5.6 8.3 ○ ○ ○ Example 2 4.6 7.5 Ⓞ Ⓞ ○ Example 3 4.4 7.2 Ⓞ Ⓞ ○ Example 4 4.0 6.8 Ⓞ Ⓞ ○ Example 5 3.6 5.9 ○ Ⓞ ○ Example 6 3.4 5.6 ○ Ⓞ ○ Example 7 3.0 5.8 ○ Ⓞ ○ Example 8 4.5 8.2 Ⓞ Ⓞ ○ Example 9 3.7 8.1 Ⓞ Ⓞ ○ Example 10 5.1 6.9 Ⓞ Ⓞ ○ Example 11 5.5 7.5 Ⓞ Ⓞ ○ Example 12 5.5 8.5 Ⓞ Ⓞ ○ Example 13 7.2 10.4 ○ Ⓞ ○ Example 14 6.6 11.3 ○ Ⓞ ○ Example 15 8.9 12.5 Ⓞ Ⓞ ○ Comparative Example 1 2.3 18.9 Ⓞ Ⓞ × Comparative Example 2 1.9 5.3 × Ⓞ ○ Comparative Example 3 2.5 4.6 × ○ ○

As shown in Table 2, the acrylic pressure-sensitive adhesive compositions of Examples 1 to 15 containing the silane-based compound of Formula 1 according to the present invention had better adhesion and adhesive durability under severe conditions (high temperature or high temperature and high humidity) , It was confirmed that the reworkability was excellent.

Claims (11)

An acrylic pressure-sensitive adhesive composition comprising a silane-based compound represented by the following formula (1):
[Chemical Formula 1]
Figure pat00035

(Wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 is a C 1 -C 6 alkyl group , R 3 is a C 1 -C 8 aliphatic hydrocarbon group or a C 1 -C 8 aliphatic hydrocarbon group containing a heteroatom, R 4 , R 5 and R 6 are each independently hydrogen, C 1 -C 6 An aliphatic hydrocarbon group, a halogen group, a sulfonyl group, a hydroxy group, an amino group, a carbonyl group or a C 1 -C 6 carboxyester group).
The silane compound of claim 1, wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 Is a C 1 -C 6 alkyl group, R 3 is a C 1 -C 8 alkyl group or a C 1 -C 8 alkyl group containing O, S or NH, and R 4 , R 5 and R 6 are each independently Is hydrogen or a C 1 -C 6 alkyl group.
The acrylic pressure-sensitive adhesive composition according to claim 2, wherein the silane compound of Formula 1 is at least one selected from the following Formulas 2 to 6:
(2)
Figure pat00036

(3)
Figure pat00037

[Chemical Formula 4]
Figure pat00038

[Chemical Formula 5]
Figure pat00039

[Chemical Formula 6]
Figure pat00040

 The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition comprises an acrylic copolymer and a silane-based compound.
The acrylic pressure-sensitive adhesive composition according to claim 4, wherein the silane-based compound of Formula 1 is contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer.
The acrylic pressure-sensitive adhesive composition according to claim 4, wherein the acrylic copolymer contains a (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms and a polymerizable monomer having a crosslinkable functional group.
[7] The acrylic pressure-sensitive adhesive composition according to claim 6, wherein the polymerizable monomer having a crosslinkable functional group contains 0.05 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms.
The acrylic pressure-sensitive adhesive composition according to claim 4, wherein the pressure-sensitive adhesive composition further contains a crosslinking agent.
A silane-based compound represented by the following formula (1):
[Chemical Formula 1]
Figure pat00041

(Wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 is a C 1 -C 6 alkyl group , R 3 is a C 1 -C 8 aliphatic hydrocarbon group or a C 1 -C 8 aliphatic hydrocarbon group containing a heteroatom, R 4 , R 5 and R 6 are each independently hydrogen, C 1 -C 6 An aliphatic hydrocarbon group, a halogen group, a sulfonyl group, a hydroxy group, an amino group, a carbonyl group or a C 1 -C 6 carboxyester group).
The silane compound of claim 1, wherein X and Y are each independently O, S or NH, R 1 is a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, R 2 Is a C 1 -C 6 alkyl group, R 3 is a C 1 -C 8 alkyl group or a C 1 -C 8 alkyl group containing O, S or NH, and R 4 , R 5 and R 6 are each independently a silane-based compound to the group of hydrogen or C 1 -C 6.
The silane-based compound according to claim 9, wherein the silane compound represented by Formula 1 is at least one selected from the following Formulas 2 to 6:
(2)
Figure pat00042

(3)
Figure pat00043

[Chemical Formula 4]
Figure pat00044

[Chemical Formula 5]
Figure pat00045

[Chemical Formula 6]
Figure pat00046
KR20130115429A 2013-09-27 2013-09-27 Acrylic adhesive composition and silane compounds KR20150035177A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180073377A (en) * 2016-12-22 2018-07-02 삼성에스디아이 주식회사 Compound comprising amide bonding connected with cycle and alkoxysilan group, epoxy resin composition comprising the same and apparatus prepared using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180073377A (en) * 2016-12-22 2018-07-02 삼성에스디아이 주식회사 Compound comprising amide bonding connected with cycle and alkoxysilan group, epoxy resin composition comprising the same and apparatus prepared using the same

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