CN108659732B - Adhesive composition, adhesive sheet, and optical member - Google Patents
Adhesive composition, adhesive sheet, and optical member Download PDFInfo
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- CN108659732B CN108659732B CN201810259178.6A CN201810259178A CN108659732B CN 108659732 B CN108659732 B CN 108659732B CN 201810259178 A CN201810259178 A CN 201810259178A CN 108659732 B CN108659732 B CN 108659732B
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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
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2453/00—Presence of block copolymer
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- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
Abstract
The invention provides an adhesive composition, an adhesive sheet and an optical component, wherein the adhesive composition of the invention has excellent constant load peeling resistance when forming a particularly thin adhesive layer. The adhesive composition of the present invention contains a (meth) acrylic random polymer and a (meth) acrylic triblock polymer, and the weight average molecular weight (Mw) of the (meth) acrylic triblock polymer is 3,000 to 30,000 as measured by gel permeation chromatography.
Description
Technical Field
The invention relates to an adhesive composition, an adhesive sheet and an optical component.
Background
In the past, a great deal of research has been conducted to improve the performance of adhesives. For example, patent document 1 discloses a polymer modifier for adding a binder, which has excellent compatibility with various polymers, and has excellent modifying effect without causing cloudiness or segregation when added to various polymers. However, the present inventors have found that, when a particularly thin adhesive layer is formed, a conventional adhesive composition has room for improvement.
[ background Art document ]
[ patent document ]
[ patent document 1] Japanese patent No. 4442923 publication
Disclosure of Invention
[ problems to be solved by the invention ]
The purpose of the present invention is to provide an adhesive composition that exhibits excellent constant-load peel resistance (Fixed-load peel resistance) when a particularly thin adhesive layer is formed. Further, it is an object of the present invention to provide an adhesive formed from such an adhesive composition. Further, an object of the present invention is to provide an adhesive sheet and an optical member each including an adhesive layer formed from the adhesive composition.
[ means for solving problems ]
The present inventors have made diligent studies to solve the problems. As a result, the present inventors found that: by using a (meth) acrylic triblock polymer having a relatively low molecular weight, the triblock polymer is present more on the surface in the adhesive layer, thereby obtaining particularly excellent constant-load peel resistance.
Embodiments of the present invention are described below, for example.
[1] An adhesive composition contains a (meth) acrylic random polymer and a (meth) acrylic triblock polymer having a weight average molecular weight (Mw) of 3,000 to 30,000 as measured by gel permeation chromatography.
[2] The adhesive composition according to [1], wherein the amount of the (meth) acrylic triblock polymer to be blended is in the range of 1 to 49 parts by mass relative to 100 parts by mass of the (meth) acrylic random polymer.
[3] The adhesive composition according to [1] or [2], wherein the (meth) acrylic triblock polymer has a structure represented by [ A ] - [ B ] - [ A ] with a block [ A ] and a block [ B ].
[4] The adhesive composition according to any one of [1] to [3], further comprising an isocyanate-based crosslinking agent.
[5] The adhesive composition according to any one of [1] to [4], which is used for optical applications.
[6] An adhesive formed from the adhesive composition of any one of [1] to [5 ].
[7] An adhesive sheet comprising a substrate and an adhesive layer formed on at least one surface of the substrate by the adhesive composition according to any one of [1] to [5 ].
[8] The adhesive sheet according to [7], wherein the adhesive layer has a thickness of 15 μm or less.
[9] An optical member comprising an adhesive layer formed from the adhesive composition described in any one of [1] to [5 ].
[10] The optical member according to [9], wherein the thickness of the adhesive layer is 15 μm or less.
[ Effect of the invention ]
According to the present invention, an adhesive composition exhibiting excellent constant load peel resistance in the case of forming a particularly thin adhesive layer can be provided. According to the present invention, there is also provided an adhesive formed from such an adhesive composition. Further, the present invention can provide an adhesive sheet and an optical member each having an adhesive layer formed from the adhesive composition.
Drawings
Is free of
Detailed Description
The adhesive composition, adhesive sheet, and optical member according to one embodiment of the present invention will be described below.
In the present specification, the term "polymer" includes a homopolymer (homopolymer) and a copolymer (copolymer), and the term "polymerization" includes homopolymerization and copolymerization. The compound represented by the formula (i) (i is a formula number) is also simply referred to as "compound (i)". In the present specification, the term (meth) acrylic acid means acrylic acid or methacrylic acid, the term (meth) acrylate means acrylate or methacrylate, and the term (meth) acryloyl means acryloyl or methacryloyl.
[ adhesive composition ]
The adhesive composition according to one embodiment of the present invention contains a (meth) acrylic random polymer and a (meth) acrylic triblock polymer. The (meth) acrylic triblock polymer has a weight average molecular weight (Mw) of 3,000 to 30,000 as measured by Gel Permeation Chromatography (GPC).
[1] (meth) acrylic random polymer
The structure of the (meth) acrylic random polymer is not particularly limited. The (meth) acrylic random polymer may be a (meth) acrylic random polymer synthesized by a general radical polymerization method, or may be a (meth) acrylic random polymer synthesized by a living radical polymerization method. The (meth) acrylic random polymer has a weight average molecular weight (Mw) of, for example, 100,000 to 3,000,000, preferably 150,000 to 2,000,000, more preferably 200,000 to 2,000,000 as measured by GPC. The molecular weight distribution (Mw/Mn) of the (meth) acrylic random polymer measured by GPC is, for example, 30.0 or less, preferably 25.0 or less, and more preferably 20.0 or less.
< raw Material monomer >
As a raw material monomer of the (meth) acrylic random polymer, a (meth) acrylate is mainly used, but other functional group-containing monomers and copolymerizable monomers may be further used.
(meth) acrylic acid esters
Examples of the (meth) acrylate include alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, alkoxypolyalkylene glycol mono (meth) acrylates, and (meth) acrylates containing an alicyclic group or an aromatic ring. In the above method, a functional group-containing (meth) acrylate such as a hydroxyl group-containing (meth) acrylate, a carboxyl group-containing (meth) acrylate, or an amino group-containing (meth) acrylate is removed from the (meth) acrylate.
The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 to 20. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (iso-stearyl (meth) acrylate, didecyl (meth) acrylate.
Examples of the alkoxyalkyl (meth) acrylate include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
Examples of the alkoxy polyalkylene glycol mono (meth) acrylate include methoxy diethylene glycol mono (meth) acrylate, methoxy dipropylene glycol mono (meth) acrylate, ethoxy triethylene glycol mono (meth) acrylate, ethoxy diethylene glycol mono (meth) acrylate, methoxy triethylene glycol mono (meth) acrylate, and methoxy triethylene glycol mono (meth) acrylate.
Examples of the (meth) acrylate containing an alicyclic group or an aromatic ring include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.
The total amount of the (meth) acrylic acid ester used is, for example, 70 to 99.9 mass%, preferably 80 to 99.5 mass%, and more preferably 89.95 to 98.95 mass% based on the total mass of all the raw material monomers.
The (meth) acrylic acid ester may be used singly or in combination of two or more.
Monomers containing functional groups
Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, an acid group-containing monomer, an amino group-containing monomer, an amide group-containing monomer, a nitrogen-containing heterocyclic monomer, and a cyano group-containing monomer. Examples of the acid group include a carboxyl group, an acid anhydride group, a phosphoric acid group, and a sulfuric acid group.
Examples of the hydroxyl group-containing monomer include hydroxyl group-containing (meth) acrylates, and specifically, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate. The number of carbon atoms of the alkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
Examples of the carboxyl group-containing monomer include β -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloxyethyl succinate, ω -carboxypolycaprolactone mono (meth) acrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid. Examples of the acid anhydride group-containing monomer include maleic anhydride. Examples of the phosphoric acid group-containing monomer include (meth) acrylic monomers having a phosphoric acid group in a side chain, and examples of the sulfuric acid group-containing monomer include (meth) acrylic monomers having a sulfuric acid group in a side chain.
Examples of the amino group-containing monomer include amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
Examples of the amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-hexyl (meth) acrylamide. Examples of the nitrogen-containing heterocyclic monomer include vinylpyrrolidone, acryloylmorpholine, and vinylcaprolactam. Examples of the cyano group-containing monomer include cyano (meth) acrylate and (meth) acrylonitrile.
The total amount of the functional group-containing monomers to be used is preferably 0 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of all the raw material monomers.
The functional group-containing monomer may be used singly or in combination of two or more.
(copolymerizable monomer)
Examples of the copolymerizable monomer include styrene monomers such as alkylstyrene, e.g., styrene, methylstyrene, dimethylstyrene, trimethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene, styrene monomers such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodinated styrene, nitrostyrene, acetylstyrene, and methoxystyrene, and vinyl acetate.
The copolymerizable monomer may be used singly or in combination of two or more.
[2] (meth) acrylic triblock polymer
The (meth) acrylic triblock polymer used in the present invention has a weight average molecular weight (Mw) of 3,000 to 30,000 as measured by GPC. The weight average molecular weight (Mw) is preferably 3,000 to 20,000, more preferably 3,000 to 10,000. The molecular weight distribution (Mw/Mn) of the (meth) acrylic random polymer measured by GPC is, for example, 1.5 or less, preferably 1.4 or less, and more preferably 1.3 or less.
As described above, the present inventors found that: by using a (meth) acrylic triblock polymer having a relatively low molecular weight, the triblock polymer is present more on the surface in the adhesive layer, and thus particularly excellent constant-load peel resistance can be obtained. If the weight average molecular weight is too large, the triblock polymer in the adhesive layer does not exist significantly more on the surface, and thus it is difficult to achieve excellent constant-load peel resistance. On the other hand, if the weight average molecular weight is too small, the adhesive composition has insufficient cohesive force, and it is difficult to achieve excellent constant-load peel resistance.
The method for synthesizing the (meth) acrylic triblock polymer used in the present invention is not particularly limited. The (meth) acrylic triblock polymer may be a (meth) acrylic triblock polymer synthesized by a general radical polymerization method, or may be a (meth) acrylic triblock polymer synthesized by a living radical polymerization method.
The triblock polymer can be produced by a general living radical polymerization. Among them, the production can be suitably performed by atom transfer radical polymerization in terms of ease of control of polymerization reaction and the like. The atom transfer radical polymerization method is a polymerization method using an organic halide or sulfonyl halide compound as an initiator and a metal complex (metal complex) as a catalyst. When a triblock polymer is produced by living radical polymerization, a method of sequentially adding monomer units, a method of polymerizing the next polymer block using a polymer synthesized in advance as a high-molecular initiator, a method of bonding polymer blocks polymerized separately by reaction, and the like can be cited, and a triblock polymer is preferably produced by a method of sequentially adding monomer units.
The (meth) acrylic triblock polymer can also be synthesized, for example, by reversible addition fragmentation chain transfer (RAFT) polymerization. When RAFT polymerization is used, the molecular weight and molecular weight distribution of the (meth) acrylic triblock polymer can be controlled more precisely.
The RAFT polymerization method is a method of polymerizing a radical polymerizable compound as a raw material monomer in the presence of a RAFT agent. All of the raw material monomers may be added at once to carry out polymerization, or after a part of the raw material monomers are polymerized, the remaining monomer components may be added continuously or intermittently to carry out polymerization.
< RAFT agent >
As the RAFT agent, conventionally known compounds can be used, and there is no particular limitation. Examples of the RAFT agent include thiocarbonylthio compounds such as bis (thiocarbonyl) disulfide (bis (thiocarbonyl) disulfide), dithioester, Trithiocarbonate (Trithiocarbonate), dithiocarbamate, and xanthate.
Examples of bis (thiocarbonyl) disulfide compounds (bis (thiocarbonyl) disulfide compounds) include tetraethylthiuram disulfide, tetramethylthiuram disulfide, bis (octylmercapto) thiocarbonyl) disulfide, bis (n-dodecylmercapto-thiocarbonyl) disulfide, bis (benzylmercapto-thiocarbonyl) disulfide, bis (n-butylmercapto-thiocarbonyl) disulfide, bis (tert-butylmercapto-thiocarbonyl) disulfide, bis (n-heptylthio-thiocarbonyl) disulfide, bis (n-hexylmercapto-thiocarbonyl) disulfide, bis (n-pentylmercapto-thiocarbonyl) disulfide, bis (n-nonylmercapto-thiocarbonyl) disulfide, bis (n-decylthiol-thiocarbonyl) disulfide, bis (n-dodecylmercapto-thiocarbonyl) disulfide, and bis (n-dodecylmercapto-thiocarbonyl) disulfide, Bis (tertiary-dodecylthiol-thiocarbonyl) disulfide, bis (n-tetradecylthiol-thiocarbonyl) disulfide, bis (n-hexadecylthiol-thiocarbonyl) disulfide, bis (n-octadecyl thiol-thiocarbonyl) disulfide, etc.;
as the dithioester compounds, for example, 2-phenyl-2-propylphenyldithio (2-phenyl-2-propylphenylthionate), 4-Cyano-4- (phenylthiocarbonylthiol) valeric acid, 2-Cyano-2-propylbenzodithiol (2-cyanol-2-propylbenzodithionate) and the like can be listed;
examples of the trithiocarbonate compound include S- (2-cyano-2-propyl) -S-dodecyltrithiocarbonate, 4-cyano-4- [ (dodecylthiol-thiocarbonyl) thiol ] pentanoic acid, cyanomethyldodecyltrithiocarbonate, 2- (dodecylmercaptothiocarbonylthiol) (dodecylhalothiothiolthio) -2-methylpropanoic acid, bis [4- { ethyl-2- (hydroxyethyl) aminocarbonyl } -benzyl ] trithiocarbonate, and the like;
examples of the dithiocarbamate compound include cyanomethyl (phenyl) dithiocarbamate, cyanomethyl diphenyl dithiocarbamate, and the like;
examples of the xanthate compound include xanthates.
The amount of the RAFT agent used is usually 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the raw material monomers. If the amount of RAFT agent used is not less than the lower limit of the range, the reaction can be easily controlled, and if it is not more than the upper limit of the range, the weight average molecular weight of the obtained polymer can be easily adjusted to the range.
RAFT polymerisation is preferably carried out in the presence of a polymerisation initiator. Examples of the polymerization initiator include general organic polymerization initiators, specifically, peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as 2,2' -azobisisobutyronitrile. The polymerization initiator may be used singly or in combination of two or more.
When the polymerization initiator is used, the amount of the polymerization initiator used is usually 0.001 to 2 parts by mass, preferably 0.002 to 1 part by mass, based on 100 parts by mass of the raw material monomer. The amount of the polymerization initiator used is usually 0.1 to 3000 mol, preferably 1 to 1000 mol, based on 1 mol of the RAFT agent.
< raw Material monomer >
As the raw material monomer constituting each block of the (meth) acrylic triblock polymer, a (meth) acrylate is mainly used, but other functional group-containing monomers and copolymerizable monomers may be further used. Examples of the (meth) acrylic acid ester, the functional group-containing monomer, and the copolymerizable monomer include the same raw material monomers as those described above for the raw material monomers of the (meth) acrylic random polymer.
< Block formation >
The (meth) acrylic triblock polymer used in the present invention preferably has a structure represented by [ A ] - [ B ] - [ A ] using the block [ A ] and the block [ B ]. If such a constitution is adopted, structural cohesion is easily exhibited, that is, high cohesion can be obtained even with a relatively low molecular weight, and therefore, particularly excellent constant load peeling resistance can be obtained.
The weight of the block [ A ] is, for example, 10 to 90 mass%, preferably 20 to 80 mass%, more preferably 30 to 70 mass% of the total (meth) acrylic triblock polymer. The weight of the block [ B ] is, for example, 10 to 90 mass%, preferably 20 to 80 mass%, more preferably 30 to 70 mass% of the total (meth) acrylic triblock polymer.
The block [ A ]]Preferably containing a compound represented by the formula CH2＝CY1-COOY2(Y1Is a hydrogen atom or a methyl group, Y2Alkyl group having 1 to 20 carbon atoms) is used. Furthermore, the block [ B ]]Preferably containing a compound represented by the formula CH2＝CY3-COOY4(Y3Is a hydrogen atom or a methyl group, Y4Alkyl group having 1 to 20 carbon atoms) is used. In this case, it is more preferable that Y is2Has a carbon number greater than Y4The carbon number of (c). If this is adoptedWith such a structure, the triblock polymer is more likely to be present on the surface of the adhesive layer, and particularly excellent constant-load peel resistance can be obtained.
As Y satisfying the condition2And Y4Examples of the combinations of (b) include combinations shown in table 1 below. The description of the table is merely exemplary, and combinations other than these are not excluded.
[ Table 1]
| Y2 | Y4 |
| Ethyl radical | Methyl radical |
| N-propyl radical | Methyl radical |
| Isopropyl group | Methyl radical |
| N-butyl | Methyl radical |
| Isobutyl radical | Methyl radical |
| Tertiary butyl radical | Methyl radical |
| N-propyl radical | Ethyl radical |
| Isopropyl group | Ethyl radical |
| N-butyl | N-propyl radical |
| Isobutyl radical | N-propyl radical |
| Tertiary butyl radical | N-propyl radical |
| N-butyl | Isopropyl group |
| Isobutyl radical | Isopropyl group |
| Tertiary butyl radical | Isopropyl group |
The amount of the (meth) acrylic triblock polymer having a weight average molecular weight (Mw) of 3,000 to 30,000 as measured by GPC is, for example, 1 to 49 parts by mass, preferably 1 to 39 parts by mass, based on 100 parts by mass of the (meth) acrylic random polymer. When the amount of the (meth) acrylic triblock polymer is adjusted to such a range, more excellent constant-load peel resistance can be obtained.
The adhesive composition of the present invention may further contain a triblock polymer outside the above molecular weight range, or may further contain a block polymer other than a triblock polymer.
[3] Other ingredients
The adhesive composition may further contain, as other components, a crosslinking agent, a silane coupling agent, an antistatic agent, an organic solvent, an antioxidant, a light stabilizer, a metal corrosion inhibitor, an adhesion-imparting agent, a plasticizer, a crosslinking accelerator, nanoparticles, and the like.
< crosslinking agent >
The crosslinking agent includes an isocyanate compound, an epoxy compound, a metal chelate compound, and the like, and is preferably used in order that the adhesive layer can exhibit good physical properties without preventing the triblock polymer from being present on the surface of the adhesive layer in a larger amount.
As the isocyanate compound, an isocyanate compound having an isocyanate group of 2 or more in 1 molecule is generally used. Examples of the isocyanate compound include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Examples of the aliphatic diisocyanate include aliphatic diisocyanates having 4 to 30 carbon atoms such as Ethylene diisocyanate (Ethylene diisocyanate), tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate and the like. Examples of the alicyclic diisocyanate include alicyclic diisocyanates having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Examples of the aromatic diisocyanate include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
Examples of the isocyanate compound having 3 or more isocyanate groups in 1 molecule include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specific examples thereof include toluene 2,4, 6-triisocyanate, 1,3, 5-benzene triisocyanate and 4,4' -triphenylmethane triisocyanate. Further, examples of the isocyanate compound include a trimer of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, a biuret or isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate, a reaction product of trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate (for example, a three-molecule adduct of tolylene diisocyanate or xylylene diisocyanate), a reaction product of trimethylolpropane and hexamethylene diisocyanate (for example, a three-molecule adduct of hexamethylene diisocyanate), polyether polyisocyanate, and polyester polyisocyanate.
As the epoxy compound, for example, an epoxy compound having an epoxy group number of 2 or more in 1 molecule is generally used. Examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N' -tetraglycidylmethylenem-xylylenediamine, N, N, N ', N' -tetraglycidylaminophenylmethane, triglycidyl isocyanurate, m-N, N-diglycidylaminophenylglycidyl ether, N, N-diglycidyltoluidine and N, N-diglycidylaniline.
Examples of the metal chelate compound include compounds in which an alkoxide, acetylacetone, ethyl acetoacetate, or the like is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, or zirconium. Specific examples thereof include aluminum isopropoxide, aluminum sec-butoxide, ethyl aluminum acetoacetate diisopropyl ester, ethyl aluminum triacetylacetate, and aluminum triacetylacetonate.
The crosslinking agent is contained in an amount of 0.01 to 5 parts by mass, preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total of the (meth) acrylic random polymer and the (meth) acrylic triblock polymer. When the crosslinking agent is contained within the above range, the durability and the stress relaxation property can be balanced.
< silane coupling agent >
The silane coupling agent firmly adheres the adhesive layer to an adherend such as a glass substrate, can prevent the adhesive layer from peeling off in a high-humidity and high-heat environment, and has a large effect of improving durability if combined with the block polymer.
Examples of the silane coupling agent include: silane coupling agents containing polymerizable unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; epoxy group-containing silane coupling agents such as 3-glycidyloxytrimethoxysilane, 3-glycidyloxytriethoxysilane, 3-glycidyloxymethyldimethoxysilane, 3-glycidyloxymethyldiethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and halogen-containing silane coupling agents such as 3-chloropropyltrimethoxysilane.
Among them, an epoxy group-containing silane coupling agent is preferable in terms of stress relaxation property and the like. In the composition of the present invention, the content of the silane coupling agent is usually 1 part by mass or less, preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the total of the (meth) acrylic random polymer and the (meth) acrylic triblock polymer. When the content is in the above range, the peeling of the adhesive layer in a high-humidity environment or the bleeding of the silane coupling agent in a high-temperature environment tends to be prevented.
< antistatic agent >
Examples of the antistatic agent include surfactants, ionic compounds, and conductive polymers.
Examples of the surfactant include: quaternary ammonium salts, quaternary ammonium amide salts, phenazopyridinium salts, cationic surfactants having a cationic group such as a primary to tertiary amino group, etc.; anionic surfactants having an anionic group such as a sulfonate group, a sulfate group, and a phosphate group; amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, and amino acid sulfates, and nonionic surfactants such as glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamine, and alkyldiethanolamine.
Further, as the surfactant, a reactive emulsifier having a polymerizable group may be mentioned, and a polymer-based surfactant obtained by polymerizing a monomer component containing the surfactant or the reactive emulsifier into a high molecular weight may be used.
The ionic compound is composed of a cation portion and an anion portion, and may be solid or liquid at room temperature (23 ℃/50% RH).
The cation portion constituting the ionic compound may be either an inorganic cation or an organic cation, or may be two. As the inorganic cation, alkali metal ions and alkaline earth metal ions are preferable, and Li having excellent antistatic property is more preferable+、Na+And K+. Examples of the organic cation include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a pyrroline cation, a pyrrole cation, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a dialkylsulfonium cation, a tetraalkylphosphonium cation, and derivatives thereof.
The anionic portion constituting the ionic compound is not particularly limited as long as it can form an ionic compound by being ionically bonded to the cationic portion. Specifically, F is exemplified-、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-And (CF)3SO2)(CF3CO)N-。
Preferred examples of the ionic compound include lithium bis (trifluoromethanesulfonyl) imide, lithium bis (difluorosulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methane, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (difluorosulfonyl) imide, 1-ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide, (N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, ammonium bis (difluorosulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methane, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (difluorosulfonyl) imide, lithium 1-ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-, Bis (trifluoromethanesulfonyl) imide N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium, 1-Octylpyridinium fluorosulfonium imide (1-Octylpyridinium fluorosulfonium imide), 1-octyl-3-methylpyridinium, trifluorosulfonium imide.
Examples of the conductive polymer include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
In the composition of the present invention, the content of the antistatic agent is usually 3 parts by mass or less, preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, based on 100 parts by mass of the total of the (meth) acrylic random polymer and the (meth) acrylic triblock polymer.
< organic solvent >
The pressure-sensitive adhesive composition of the present invention does not necessarily contain a solvent, but may contain an organic solvent to adjust the coatability of the pressure-sensitive adhesive composition. In the adhesive composition of the present invention, the content of the organic solvent is usually 50 to 90% by mass, preferably 60 to 85% by mass. In the present specification, "solid component" refers to the whole components of the binder composition excluding the organic solvent, and "solid component concentration" refers to the ratio of the solid component to 100 mass% of the binder composition.
The adhesive composition of the present invention can be used without limitation. However, the present inventors have found that the adhesive composition of the present invention exerts excellent performance when forming a particularly thin adhesive layer. Thus, the adhesive composition of the present invention is particularly useful in optical applications. Examples of optical applications include various display devices (e.g., liquid crystal display devices, organic EL display devices, and electronic paper display devices), touch panels, cameras, and microscopes.
[ Binders ]
The adhesive of the present invention is formed from the adhesive composition. The gel fraction of the binder is not particularly limited, and is usually 80 mass% or less. The gel fraction is a value measured under the conditions described in examples, for example.
[ adhesive sheet ]
The adhesive sheet of the present invention comprises: a double-sided adhesive sheet having only an adhesive layer formed on a release-treated cover film (hereinafter also referred to as a separator); a double-sided adhesive sheet having a substrate and the adhesive layer formed on both sides of the substrate (in this case, the substrate is also referred to as a core material); a single-sided adhesive sheet having a substrate and the adhesive layer formed on one side of the substrate; and adhesive sheets in which a cover film subjected to a peeling treatment is attached to the surface of the adhesive layer not in contact with the substrate.
Examples of the substrate and the cover film include: polyester films such as polyethylene terephthalate (PET); polyolefin films such as polycarbonate, polyethylene, polypropylene, and ethylene-vinyl acetate copolymer, plastic films such as polarizing plates, retardation films, light diffusion films, and brightness enhancement films, and glass. In addition, various additives or a plurality of laminated layers of the plastic film and the glass may be used for the plastic film and the glass. In the present specification, the term "polarizing plate" is used to include a "polarizing film".
In particular, when the substrate is used for optical applications, for example, an optically transparent plastic film as described above is suitably used, and in particular, when transparency or the like is not required, woven fabric, nonwoven fabric, metal vapor-deposited sheet, metal mesh, or any other substrate can be used.
As a coating method of the adhesive composition, the following methods can be used: the coating is performed to a specific thickness by a known method such as spin coating, knife coating, roll coating, bar coating, knife coating, die coating, and gravure coating, and dried.
The thickness of the adhesive layer is not particularly limited, but is, for example, 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, and particularly preferably 12 μm or less. As described above, the adhesive composition of the present invention exhibits particularly excellent performance when forming a thin adhesive layer. Therefore, when the adhesive layer is a thin layer, the difference in performance is more remarkable than that in the case of using a conventional composition.
[ optical component ]
The optical member of the present invention contains an adhesive layer formed from the adhesive composition. The formation method or thickness of the adhesive layer is the same as described above.
Examples of the optical member include a polarizing plate, a liquid crystal device, a camera, and a microscope. For example, a polarizing plate includes a polarizing plate main body and an adhesive layer laminated on at least one surface of the polarizing plate main body.
[ examples ]
The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following description of examples and the like, "part" means "part by mass" unless otherwise specified.
[Mw、Mn]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined for the (meth) acrylic random polymer and the (meth) acrylic triblock polymer by Gel Permeation Chromatography (GPC) under the following conditions.
The measurement device: HLC-8320GPC (manufactured by Tosoh)
GPC column composition: the following four-post connection (all made by Tosoh)
(1) TSKgel HxL-H (protective pipe column)
(2)TSKgel GMHxL
(3)TSKgel GMHxL
(4)TSKgel G2500HxL
Flow rate: 1.0mL/min
Column temperature: 40 deg.C
Sample concentration: 1.5% (w/v) (dilution with tetrahydrofuran)
Mobile phase solvent: tetrahydrofuran (THF)
Conversion to Standard polystyrene
[ (Synthesis of a (meth) acrylic random Polymer ]
[ Synthesis examples 1 to 3]
In a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube, n-Butyl Acrylate (BA), Acrylic Acid (AA), 2-hydroxyethyl acrylate (2HEA), and methacrylic acid ester (MA) were added at the ratios shown in table 2, and 100 parts of ethyl acetate was added, and the temperature was raised to 80 ℃ while introducing nitrogen gas. Then, 0.1 part of t-butylperoxypivalate was added to conduct polymerization at 80 ℃ for 6 hours under a nitrogen atmosphere. After the reaction, the reaction mixture was diluted with ethyl acetate to prepare a polymer solution having a solid content of 30% by mass. The properties of the obtained (meth) acrylic copolymer are also shown in table 2.
[ Table 2]
[ (Synthesis of meth) acrylic Block Polymer ]
[ Synthesis example 4]
Into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 50 parts by weight of methacrylate and 10 parts by weight of bis [4- { ethyl-2- (hydroxyethyl) aminocarbonyl } -benzyl ] trithiocarbonate were charged, and the contents of the flask were heated to 80 ℃ while introducing nitrogen gas into the flask. Next, 0.03 part by weight of AIBN sufficiently substituted with nitrogen was added to the flask while stirring, and heating and cooling were performed for 2 hours so that the temperature of the contents in the flask could be maintained at 80 ℃. The acrylic polymer obtained in this way had a nonvolatile fraction at 105 ℃ of 99.5%. Then, after the temperature of the content in the flask was raised to 90 ℃, 50 parts by weight of butyl acrylate was added dropwise over 1 hour. Thereafter, the flask was heated and cooled for 3 hours so that the temperature of the contents in the flask could be maintained at 90 ℃, and finally 25 parts by weight of ethyl acetate was added.
In this way a (meth) acrylic triblock polymer MBM1 was obtained. The properties of the triblock polymer MBM1 are shown in table 3 below.
[ Table 3]
| For short | Composition of | Mw | Mw/Mn | |
| Synthesis example 4 | MBM1 | MA-BA-MA＝25-50-25 | 9,700 | 1.3 |
| Synthesis example 5 | MBM2 | MA-BA-MA＝25-50-25 | 3,500 | 1.3 |
| Synthesis example 6 | MBM3 | MA-BA-MA＝25-50-25 | 24,800 | 1.3 |
| Synthesis example 7 | MBM4 | MA-BA-MA＝25-50-25 | 2,500 | 1.3 |
| Synthesis example 8 | MBM5 | MA-BA-MA＝25-50-25 | 84,200 | 1.3 |
| Synthesis example 9 | BMB1 | BA-MA-BA＝25-50-25 | 8,400 | 1.3 |
| Synthesis example 10 | M-B | MA-BA＝50-50 | 10,700 | 1.2 |
[ Synthesis examples 5 to 8]
(meth) acrylic triblock polymers MBM 2-5 were synthesized in the same manner as in Synthesis example 4, except that the weight average molecular weight of the polymer finally obtained was as shown in Table 3.
[ Synthesis example 9]
A (meth) acrylic triblock polymer BMB1 was synthesized in the same manner as in synthesis example 4, except that the order of charging the monomers was changed and the weight average molecular weight of the polymer finally obtained was changed as described in table 3.
[ Synthesis example 10]
(meth) acrylic diblock polymer M-B was synthesized in the same manner as in Synthesis example 4, except that bis [4- { ethyl-2- (hydroxyethyl) aminocarbonyl } -benzyl ] trithiocarbonate was changed to cyanomethyl N-methyl-N-phenyldithiocarbamate. The characteristics of the diblock polymer M-B are shown in Table 3.
Examples 1 to 10 and comparative examples 1 to 6
The (meth) acrylic polymer obtained in synthesis examples 1 to 10 and Coronate L (manufactured by Tosoh corporation) as an isocyanate-based crosslinking agent were mixed in the combinations and ratios shown in tables 4 and 5 below to obtain an adhesive composition.
Each of the obtained adhesive compositions was coated on a light release film while adjusting the thickness of the dried adhesive layer as shown in tables 4 and 5, dried, and transferred to a PET film (Lumirror, manufactured by Toray) having a thickness of 25 μm. An adhesive layer was formed on a substrate in the above manner to produce an adhesive sheet. The thicknesses of the adhesive layers are also shown in tables 4 and 5.
[ gel fraction ]
After a sample bottle was filled with 0.1g of the pressure-sensitive adhesive layer obtained in example and the like, 30cc of ethyl acetate was added to permeate the pressure-sensitive adhesive layer for 24 hours, the content of the sample bottle was separated by filtration using a 200-mesh stainless steel wire mesh, and the weight of the residue after drying the wire mesh at 100 ℃ for 2 hours was defined as the dry weight. Using the obtained weight measurement values, gel fraction was calculated from the following formula. The results are shown in tables 4 and 5.
Gel fraction (%) < 100 × (dry weight/weight of adhesive layer collected)
[ adhesive force ]
Using the adhesive sheet prepared by the procedure described above, the exposed adhesive layer side was pressure-bonded (attached) to the SUS plate using a 2kg roller under a condition of 25 ℃/50% RH. After leaving to stand for 20 minutes after the attachment, the adhesive sheet was peeled from the SUS plate at a peeling speed of 300mm/min under conditions of 25 ℃/50% RH and a peeling angle of 180 DEG, and the peeling force (adhesive force) of the adhesive layer of the adhesive sheet was measured. The results are shown in tables 4 and 5.
[ holding force ]
The holding force was measured according to JIS Z1541, the pressure-sensitive adhesive sheet was cut to a width of 20mm, attached to a stainless steel plate so as to be in contact with an area of 20X 20mm, and subjected to a load of 1Kg at a temperature of 80 ℃ to observe the presence or absence of dropping after being left for 1 hour. The results are shown in tables 4 and 5.
[ constant load peeling resistance ]
The exposed adhesive layer surface was bonded to the lower surface side of a stainless substrate disposed so that the front and back surfaces were parallel to the horizontal direction. Next, the test piece adhered to the stainless substrate was left to stand for 60 minutes with a load applied to the lower side in the vertical direction at the end portion on one end side in the longitudinal direction, and the peeling distance (mm) in the longitudinal direction of the test piece or the time (min) until the test piece was dropped at this time was measured. The load was 200g at a measurement temperature of 40 ℃ and 100g at 80 ℃. The results are shown in tables 4 and 5.
[ analysis of results ]
In examples 1 to 10, excellent adhesive force, holding force and constant load peel resistance were achieved by using an adhesive composition containing a (meth) acrylic random polymer and a (meth) acrylic triblock polymer having a weight average molecular weight (Mw) of 3,000 to 30,000 as measured by gel permeation chromatography. On the other hand, in comparative examples 1 to 6, since the adhesive compositions containing no (meth) acrylic triblock polymer having a weight average molecular weight (Mw) of 3,000 to 30,000 were used, at least one of the adhesive force and the constant load peel resistance was not excellent. Therefore, it was found that the adhesive compositions prepared in examples 1 to 10 are superior to those prepared in comparative examples 1 to 6.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. An adhesive composition comprising a (meth) acrylic random polymer and a (meth) acrylic triblock polymer, wherein the (meth) acrylic triblock polymer has a weight average molecular weight Mw of 3,000 to 10,000 as measured by gel permeation chromatography.
2. The adhesive composition according to claim 1, wherein the amount of the (meth) acrylic triblock polymer to be blended is in the range of 1 to 49 parts by mass relative to 100 parts by mass of the (meth) acrylic random polymer.
3. The adhesive composition according to claim 1 or 2, wherein the (meth) acrylic triblock polymer has a structure represented by [ a ] - [ B ] - [ a ] using a block [ a ] and a block [ B ].
4. The adhesive composition according to claim 1 or 2, further comprising an isocyanate-based crosslinking agent.
5. Adhesive composition according to claim 1 or 2, characterized in that it is used for optical applications.
6. An adhesive, characterized by being formed from the adhesive composition of any one of claims 1 to 5.
7. An adhesive sheet, comprising:
a substrate; and
an adhesive layer formed on at least one surface of the substrate using the adhesive composition according to any one of claims 1 to 5.
8. The adhesive sheet according to claim 7, wherein the thickness of the adhesive layer is 15 μm or less.
9. An optical member comprising an adhesive layer formed from the adhesive composition according to any one of claims 1 to 5.
10. The optical member according to claim 9, wherein the thickness of the adhesive layer is 15 μm or less.
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| JP7484158B2 (en) | 2019-12-20 | 2024-05-16 | Dic株式会社 | Adhesive sheet |
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| EP1312658A2 (en) * | 2001-11-16 | 2003-05-21 | tesa AG | Oriented acrylate blockcopolymer |
| CN101113190A (en) * | 2006-07-25 | 2008-01-30 | 蒂萨股份公司 | Bimodal acrylate adhesive mass for gluing low energy and rough surfaces |
| CN102533169A (en) * | 2010-11-12 | 2012-07-04 | 琳得科株式会社 | Acrylate adhesive composition, acrylate adhesive and optical component with adhesive layer |
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| JP4442923B2 (en) | 2002-07-04 | 2010-03-31 | 日東電工株式会社 | Polymer modifier and method for producing the same |
| JP4092152B2 (en) * | 2002-07-25 | 2008-05-28 | 日東電工株式会社 | Adhesive optical film, optical film adhesive composition and image display device |
| US20060084755A1 (en) * | 2004-10-19 | 2006-04-20 | Good David J | Reactive hot melt adhesive with block acrylic copolymer |
| JP5836943B2 (en) * | 2010-06-04 | 2015-12-24 | 株式会社クラレ | Adhesive composition for optical film |
| JP2013142131A (en) * | 2012-01-11 | 2013-07-22 | Dainippon Printing Co Ltd | Pressure-sensitive adhesive composition for triacetyl cellulose, as well as laminate using the same, optical film and optical element |
| JP6056434B2 (en) * | 2012-12-07 | 2017-01-11 | 大日本印刷株式会社 | Adhesive composition and surface protective film |
| KR102646461B1 (en) * | 2015-01-27 | 2024-03-11 | 주식회사 쿠라레 | Acrylic block copolymer and pressure-sensitive adhesive composition |
| JP6412453B2 (en) * | 2015-03-26 | 2018-10-24 | 積水化学工業株式会社 | Adhesive composition and adhesive tape |
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|---|---|---|---|---|
| EP1312658A2 (en) * | 2001-11-16 | 2003-05-21 | tesa AG | Oriented acrylate blockcopolymer |
| CN101113190A (en) * | 2006-07-25 | 2008-01-30 | 蒂萨股份公司 | Bimodal acrylate adhesive mass for gluing low energy and rough surfaces |
| CN102533169A (en) * | 2010-11-12 | 2012-07-04 | 琳得科株式会社 | Acrylate adhesive composition, acrylate adhesive and optical component with adhesive layer |
Also Published As
| Publication number | Publication date |
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| CN108659732A (en) | 2018-10-16 |
| TW201840784A (en) | 2018-11-16 |
| KR20180109720A (en) | 2018-10-08 |
| JP2018165295A (en) | 2018-10-25 |
| TWI766971B (en) | 2022-06-11 |
| KR102433205B1 (en) | 2022-08-16 |
| JP6850175B2 (en) | 2021-03-31 |
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