CN108728023B - Pressure sensitive adhesive composition and film formed using the same - Google Patents

Pressure sensitive adhesive composition and film formed using the same Download PDF

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CN108728023B
CN108728023B CN201810328104.3A CN201810328104A CN108728023B CN 108728023 B CN108728023 B CN 108728023B CN 201810328104 A CN201810328104 A CN 201810328104A CN 108728023 B CN108728023 B CN 108728023B
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sensitive adhesive
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CN108728023A (en
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雨宫正博
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Shin Etsu Chemical Co Ltd
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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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • 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
    • C09J2483/00—Presence of polysiloxane

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Abstract

The invention provides a pressure-sensitive adhesive composition which can maintain good reusability and improve durability when used for bonding an optical functional film and a liquid crystal cell. A pressure sensitive adhesive composition comprising: a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, and a copolymer represented by the formula [1a ]]At least one of the organosiloxanes represented by (a) and hydrolysates thereof.
Figure DDA0001627197820000011
(X represents a monovalent hydrocarbon group having an acid anhydride group, Y represents a monovalent hydrocarbon group having a polyether group, Z represents a monovalent hydrocarbon group having a hydrolyzable silyl group, R1Independently of each other, represents a hydrogen atom or the like, M1Independently of one another denote a group selected from X, Y, Z and R1Wherein a, b, c and d each represent an integer of 0 to 100, and when a is 0, M is1At least 1 of (a) is X, c is an integer of 1. ltoreq. c.ltoreq.100, in the case of c being 0, M1At least 1 of which is Z, a is an integer of 1. ltoreq. a.ltoreq.100).

Description

Pressure sensitive adhesive composition and film formed using the same
Technical Field
The present invention relates to a pressure-sensitive adhesive composition and a film formed using the same, and more particularly, to a pressure-sensitive adhesive composition used for bonding an optical functional film to a liquid crystal cell and a film having a layer formed using the same.
Background
The liquid crystal display device is manufactured through the following steps: first, a liquid crystal cell is produced by sandwiching a liquid crystal composition between 2 glass substrates, and then an optical functional film such as a polarizing plate or a laminate of a polarizing plate and a retardation plate is attached to the surface of the liquid crystal cell via a pressure-sensitive adhesive layer.
The liquid crystal display device has been widely used as a display device for a vehicle, an outdoor meter, a personal computer, or the like, a display device such as a television, or the like. In addition, with the expansion of the use thereof, there are also various environments in which liquid crystal display devices are used, and therefore, the pressure-sensitive adhesive composition is sometimes used in very severe environments, and performance that can cope with severe environments is also increasingly required for the pressure-sensitive adhesive composition used in the production of liquid crystal display devices.
Specifically, the following characteristics are required: even when exposed to high temperature conditions or high temperature and high humidity conditions, the optically functional film that does not foam or adhere to the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition does not peel off from the substrate (hereinafter referred to as "durability").
On the other hand, in the manufacturing process, the optical functional film and the liquid crystal cell may need to be attached again. In this case, it is required that the optical functional film can be easily peeled off without damaging the liquid crystal cell and that no adhesive remains on the surface of the liquid crystal cell (hereinafter referred to as "reusability").
That is, the pressure-sensitive adhesive used for bonding the optical functional film and the liquid crystal cell is required to have good reusability at the time of bonding and to have high durability after bonding.
As a pressure-sensitive adhesive used in such applications, an acrylic resin is often used, and for example, patent document 1 proposes a pressure-sensitive adhesive composition in which an epoxy group-containing coupling agent is contained in an acrylic polymer.
The composition of patent document 1 exhibits high durability against acrylic polymers of the type mainly containing a carboxyl group as a reactive group (hereinafter referred to as "COOH-type acrylic polymers"). However, there is a problem that durability cannot be obtained for acrylic polymers of the type mainly containing hydroxyl groups as reactive groups (hereinafter referred to as "OH-type acrylic polymers").
Further, patent documents 2 and 3 propose pressure-sensitive adhesive compositions in which an epoxy group-containing polyether modified coupling agent is contained in an acrylic polymer. The composition has both reusability and durability for COOH type acrylic polymers. However, the OH type acrylic polymer has a problem that durability cannot be obtained.
Further, patent document 4 describes a pressure-sensitive adhesive composition containing a mercapto group-containing silane coupling agent for an acrylic polymer. This composition also has improved durability against OH type acrylic polymers, but is not at a sufficient level.
Further, patent document 5 proposes a pressure-sensitive adhesive composition in which an acrylic polymer contains a polyether-modified coupling agent containing an acid anhydride group. The composition has both reusability and durability for OH-type acrylic polymers. However, in recent years, the demand for durability of pressure-sensitive adhesives has been increasing, and further improvement in durability has been demanded.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5826179
Patent document 2: japanese patent No. 5891534
Patent document 3: japanese patent No. 3498158
Patent document 4: japanese patent No. 5544858
Patent document 5: japanese patent No. 5990847
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a pressure-sensitive adhesive composition which can improve durability while maintaining good reusability when used for bonding an optical functional film and a liquid crystal cell, and a film having a pressure-sensitive adhesive layer formed using the composition.
Means for solving the problems
The present inventors have intensively studied to solve the above problems and, as a result, have found that: the present inventors have found that when a composition comprising a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer and an organosiloxane having at least 1 hydrolyzable silyl group and at least 1 anhydride group in the molecule or an organosiloxane having at least 1 hydrolyzable silyl group, at least 1 anhydride group, and at least one polyether group in the molecule is used for bonding an optical functional film and a liquid crystal cell, the composition can maintain good reusability and can improve durability, and is suitable as a pressure-sensitive adhesive composition.
Namely, the present invention provides:
1. a pressure sensitive adhesive composition characterized by comprising: a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, and at least one of an organosiloxane and a hydrolysate thereof represented by the following formula [1a ] and having at least 1 hydrolyzable silyl group and acid anhydride group in each molecule,
[ CHEM 1]
Figure GDA0003112833360000031
(wherein X represents a monovalent hydrocarbon group having an acid anhydride group, Y represents a monovalent hydrocarbon group having a polyether group, Z represents a monovalent hydrocarbon group having a hydrolyzable silyl group, and R represents1Independently represent a hydrogen atom or a C1-20 monovalent hydrocarbon group which may be substituted with a halogen atom, M1Independently of one another represent a group selected from X, Y, Z and R1In the group (a), b, c and d each represents an integer of 0. ltoreq. a.ltoreq.100, 0. ltoreq. b.ltoreq.100, 0. ltoreq. c.ltoreq.100, 0. ltoreq. d.ltoreq.100. Wherein, when a is 0, M1At least 1 of (a) is X, c is an integer of 1. ltoreq. c.ltoreq.100, and when c is 0, M1At least 1 of the groups is Z, and a is an integer of 1-100. The arrangement of the repeating units in parentheses denoted by a, b, c and d may be random or block. )
2. A pressure sensitive adhesive composition characterized by comprising: a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, and at least one of an organosiloxane and a hydrolysate thereof represented by the following formula [1b ] having at least 1 hydrolyzable silyl group, an acid anhydride group and a polyether group in each molecule,
[ CHEM 2]
Figure GDA0003112833360000041
(wherein X represents a monovalent hydrocarbon group having an acid anhydride group, Y represents a monovalent hydrocarbon group having a polyether group, and Z represents a monovalent hydrocarbon group having a hydrolysis groupMonovalent hydrocarbon radical of a silyl group, R1Independently represent a hydrogen atom or a C1-20 monovalent hydrocarbon group which may be substituted with a halogen atom, M1Independently of one another represent a group selected from X, Y, Z and R1Wherein a, b, c and d each represent an integer of 0. ltoreq. a.ltoreq.100, 0. ltoreq. b.ltoreq.100, 0. ltoreq. c.ltoreq.100, and 0. ltoreq. d.ltoreq.100. However, when a is 0, M1At least 1 of (a) is X, b and c are each an integer of 1. ltoreq. b.ltoreq.100, 1. ltoreq. c.ltoreq.100, and when b is 0, M1At least 1 of which is Y, a and c are each an integer of 1. ltoreq. a.ltoreq.100, 1. ltoreq. c.ltoreq.100, and when c is 0, M1At least 1 of the groups is Z, and a and b are each an integer of 1. ltoreq. a.ltoreq.100 and 1. ltoreq. b.ltoreq.100. The arrangement of the repeating units in parentheses denoted by a, b, c and d may be random or block. )
3.1 or 2, wherein the X is a monovalent hydrocarbon group having an acid anhydride group represented by the following formula [2], the Y is a monovalent hydrocarbon group having a polyether group represented by the following formula [3], the Z is a monovalent hydrocarbon group having a hydrolyzable silyl group represented by the following formula [5],
[ CHEM 3]
Figure GDA0003112833360000042
(wherein A represents an alkylene group having 2 to 6 carbon atoms.)
[ CHEM 4]
-CmH2m-O(C2H4O)e(C3H6O)fR2 [3]
(in the formula, R2A hydrogen atom, a C1-6 monovalent hydrocarbon group or a compound represented by the following formula [ 4]]M represents an integer of 2 or more, and e and f represent, independently of each other, an integer of 0 or more, with the proviso that at least 1 of e and f is an integer of 1 or more. )
[ CHEM 5]
Figure GDA0003112833360000051
(in the formula, R3Represents a C1-4 monovalent hydrocarbon group. )
[ CHEM 6]
Figure GDA0003112833360000052
(in the formula, R4Represents an alkyl group having 1 to 10 carbon atoms, R5Represents a monovalent hydrocarbon group or acyl group having 1 to 10 carbon atoms, n represents an integer of 2 or more, and g represents an integer of 1 to 3. )
4.1 to 3, wherein R is1At least 1 of (a) is a monovalent hydrocarbon group having a perfluoroalkyl group,
5.1 to 4, wherein the organic siloxane and the hydrolysate thereof have an acid anhydride group equivalent of 5000g/mol or less,
6.1 to 5, wherein the copolymer contains: at least one of a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer,
7.1 to 6, wherein the amount of at least one of the organosiloxane and the hydrolysate thereof is 0.001 to 5 parts by mass based on 100 parts by mass of the copolymer,
8.1 to 7, wherein the crosslinking agent is contained in an amount of 0.01 to 40 parts by mass based on 100 parts by mass of the copolymer,
9.8 of the pressure-sensitive adhesive composition, wherein, the crosslinking agent is selected from the group consisting of isocyanate crosslinking agent, epoxy crosslinking agent, metal crosslinking agent, aziridine crosslinking agent and peroxide crosslinking agent in at least 1,
10. a film with an adhesive layer, comprising: and a layer formed by using the pressure-sensitive adhesive composition of any one of 1 to 9 on at least one side of the film.
ADVANTAGEOUS EFFECTS OF INVENTION
The pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive for an optically functional film and a liquid crystal cell in the production process of a liquid crystal display device, and is capable of being peeled off at the time of bonding, but is less likely to swell or peel under high-temperature and high-humidity conditions after bonding.
The pressure-sensitive adhesive composition of the present invention having such characteristics can realize durability and reusability which have been required to be achieved at a high level in recent years, and therefore, can be suitably used as a protective film forming agent on the surface of a substrate, a surface treatment agent for fibers and powder, a pressure-sensitive adhesive or adhesive between substrates, and the like, particularly a pressure-sensitive adhesive composition used for bonding an optical functional film in the production process of a liquid crystal display device.
Detailed Description
The present invention will be specifically described below.
The present invention relates to a pressure sensitive adhesive composition comprising: a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, and at least one of an organosiloxane represented by the above formula [1a ] or [1b ] and a hydrolysate thereof (hereinafter, abbreviated as organosiloxane).
The copolymer of the polymerizable unsaturated monomer containing the (meth) acrylate monomer is a component that functions as a matrix resin in the pressure-sensitive adhesive composition, and is not particularly limited as long as it is a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer.
Specific examples of the (meth) acrylate ester monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; aryl (meth) acrylates such as phenoxyethyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; carboxyalkyl (meth) acrylates such as β -carboxyethyl acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate; caprolactone-modified (meth) acrylates; polyalkylene glycol (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, and these monomers may be used alone or in combination of 2 or more.
The copolymer of the present invention preferably contains 60 to 100% by mass, more preferably 80 to 100% by mass of a repeating unit derived from the (meth) acrylate monomer.
In addition, if it is considered that the resin used for bonding the optical functional film and the liquid crystal cell has pressure-sensitive adhesiveness, the copolymer of the present invention preferably contains: at least one of a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer.
Specific examples of the carboxyl group-and/or hydroxyl group-containing monomer that can be used as such a structural unit include (meth) acrylic acid, N- (2-hydroxyethyl) (meth) acrylamide and the like in addition to the above-mentioned carboxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate and polyalkylene glycol (meth) acrylate, and these monomers may be used alone or in combination of 2 or more.
In particular, the content of the repeating unit derived from the carboxyl group-and/or hydroxyl group-containing monomer in the copolymer used in the present invention is preferably 1 to 20% by mass, more preferably 2 to 10% by mass.
Further, the copolymer used in the present invention may contain a repeating unit derived from a monomer other than the above-mentioned monomers.
Specific examples of the other monomer include styrene monomers such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, nitrostyrene, acetylstyrene, and methoxystyrene; vinyl monomers such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, divinylbenzene, vinyl acetate, acrylonitrile, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, and vinylidene chloride, and these monomers may be used alone or in combination of 2 or more.
The content of the repeating unit derived from the other monomer in the copolymer used in the present invention is preferably 0 to 20% by mass, more preferably 0 to 10% by mass.
The copolymer used in the present invention is not particularly limited in the arrangement rule of the monomers, and may be a random copolymer, a block copolymer, or another copolymer.
The weight average molecular weight of the copolymer is not particularly limited, and is preferably 100000 to 2000000, more preferably 300000 to 1500000, in view of improving the cohesion of the pressure-sensitive adhesive layer, suppressing foaming and peeling of the pressure-sensitive adhesive layer, improving the durability, and maintaining the viscosity of the pressure-sensitive adhesive composition in an appropriate range to improve the workability.
The weight average molecular weight is a polystyrene equivalent value obtained by Gel Permeation Chromatography (GPC).
The copolymer used in the present invention can be produced by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and particularly preferably by solution polymerization in which the copolymer is obtained as a solution.
The solvent for the solution polymerization is an organic solvent, and specific examples thereof include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as n-propanol and isopropanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
The reaction solvent is preferably used in an amount of 50 to 300 parts by mass based on 100 parts by mass of the total amount of the monomers.
Further, as the polymerization initiator used in the polymerization, it can be suitably selected from known polymerization initiators, and specific examples thereof include peroxides such as di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, and (3,5, 5-trimethylhexanoyl) peroxide; azobis compounds such as azobisisobutyronitrile, azobisvaleronitrile, 1 ' -azobis (cyclohexane-1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl-2, 2 ' -azobis (2-methylpropionate), 2 ' -azobis (2-hydroxymethylpropionitrile), and the like, and a polymer azo polymerization initiator may be used alone or in combination of 2 or more.
The reaction initiator is usually used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the monomers.
The temperature of the polymerization reaction is usually 50 to 90 ℃, and the reaction time is usually 2 to 20 hours, preferably 4 to 12 hours.
In another aspect, the organosiloxane used in the pressure-sensitive adhesive composition of the present invention is represented by the formula [1a ] or [1b ] as described above. This organosiloxane is different from the compound described in patent document 5 (japanese patent No. 5990847) in that it has an alkoxy group, an acid anhydride group, and a polyether group in the molecule in the structure of the silicone skeleton. The silicone skeleton of the compound described in patent document 5 has a three-dimensional structure, whereas the silicone skeleton of the organosiloxane used in the present invention has a linear structure. In this case, when the acrylic resin is used in addition, the migration property to the resin surface is improved, and therefore, the functionality of the resin surface can be further improved. In addition, the reactivity of the alkoxy group with respect to an inorganic substrate such as glass is improved due to the structure of the compound. Therefore, the durability can be further improved in the bonding of the optical functional film and the liquid crystal cell.
[ CHEM 7]
Figure GDA0003112833360000091
In each of the above formulae, X represents a monovalent hydrocarbon group having an acid anhydride group, Y represents a monovalent hydrocarbon group having a polyether group, Z represents a monovalent hydrocarbon group having a hydrolyzable silyl group, R1Independently represent a hydrogen atom or a C1-20 monovalent hydrocarbon group which may be substituted with a halogen atom, M1Independently of one another represent a group selected from X, Y, Z and R1The group of (1).
In each of the above formulae, a, b, c and d each represent an integer of 0. ltoreq. a.ltoreq.100, 0. ltoreq. b.ltoreq.100, 0. ltoreq. c.ltoreq.100, 0. ltoreq. d.ltoreq.100, and the formula [1a ]]When a is 0, M1At least 1 of (a) is X, c is an integer of 1. ltoreq. c.ltoreq.100, and when c is 0, M1At least 1 of which is Z, a is an integer of 1. ltoreq. a.ltoreq.100, formula [1b]When a is 0, M1At least 1 of (a) is X, b and c are each an integer of 1. ltoreq. b.ltoreq.100, 1. ltoreq. c.ltoreq.100, when b is 0, M1At least 1 of which is Y, a and c are each an integer of 1. ltoreq. a.ltoreq.100, 1. ltoreq. c.ltoreq.100, and when c is 0, M1At least 1 of the groups is Z, and a and b are each an integer of 1. ltoreq. a.ltoreq.100 and 1. ltoreq. b.ltoreq.100.
In each of the above formulae, the arrangement of the repeating units in parentheses denoted by a, b, c, and d may be random or block.
As the above-mentioned R1Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include straight-chain, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-octyl, n-nonyl, n-decyl and n-octadecyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl.
Specific examples of the group in which some or all of the hydrogen atoms of the monovalent hydrocarbon group are substituted with a halogen atom include chloromethyl group, trifluoromethyl group, chloropropyl group and the like.
Among these, as R1Preferably, a methyl group or a monovalent hydrocarbon group having a perfluoroalkyl group is used, and more preferably, a methyl group or an alkyl group (fluoroalkyl group) substituted with a perfluoroalkyl group is used.
Specific examples of the fluoroalkyl group include CF3-C2H4-、CF3-C3H6-、C4F9-C2H4-、C4F9-C3H6-、C6F13-C2H4-、C6F13-C3H6-、C8F17-C2H4-、C8F17-C3H6A group represented by the formula (II) or the like.
The organosiloxane of the invention is prepared by introducing the above-mentioned monovalent hydrocarbon group as R1When the copolymer is used in admixture with the above copolymer as a matrix resin, the compatibility with the resin is improved, and phase separation or the like is less likely to occur, and therefore, it is preferable that each R is the above copolymer1At least 1 of (A) is a 1-valent hydrocarbon group, more preferably all are 1-valent hydrocarbon groups, and still more preferably all of R1Is methyl or a combination of methyl and a monovalent hydrocarbon group having a perfluoroalkyl group.
The organosiloxane used in the present invention has a monovalent hydrocarbon group X having an acid anhydride group, and when the organosiloxane is added to a base resin, the acid anhydride group of the monovalent hydrocarbon group X reacts with a reactive group (hydroxyl group, carboxyl group, or the like) of the base resin by the presence of the monovalent hydrocarbon group X, whereby the resin and the organosiloxane are integrated.
Examples of the monovalent hydrocarbon group in the monovalent hydrocarbon group having an acid anhydride group include the group R1The same groups as those exemplified in (1) above are preferred, and alkyl groups are more preferred.
Examples of the acid anhydride group include a succinic anhydride group and a maleic anhydride group.
Preferable examples of X include a group represented by the following formula [2 ].
[ CHEM 8]
Figure GDA0003112833360000111
A represents an alkylene group having 2 to 6 carbon atoms, and specific examples thereof include linear or branched alkylene groups such as ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene, and particularly trimethylene is preferable, and thus succinic anhydride propyl is preferable as X.
Further, the organosiloxane used in the present invention includes a monovalent hydrocarbon group Z having a hydrolyzable silyl group, and when an inorganic substrate such as glass is surface-treated with the organosiloxane by having the monovalent hydrocarbon group Z, the hydrolyzable silyl group reacts with an — OH group present on the surface of the inorganic substrate to form a chemical bond between the organosiloxane and the inorganic substrate.
Examples of the monovalent hydrocarbon group having a hydrolyzable silyl group include the group represented by the formula R1The same groups as those exemplified in (1) above are preferably alkyl groups, and more preferably linear alkyl groups.
Preferable examples of Z include a group represented by the following formula [5 ].
[ CHEM 9]
Figure GDA0003112833360000112
R is as defined above4Represents an alkyl group having 1 to 10 carbon atoms, R5Represents a monovalent hydrocarbon group or acyl group having 1 to 10 carbon atoms, n represents an integer of 2 or more, preferably an integer of 2 to 5, more preferably an integer of 2 or 3, and g represents an integer of 1 to 3, preferably 2 or 3, more preferably 3.
Specific examples of the alkyl group having 1 to 10 carbon atoms include the group R1Among the alkyl groups exemplified in (1) above, the same ones as those having 1 to 10 carbon atoms are preferably methyl and ethyl.
Specific examples of the monovalent hydrocarbon group include the groups represented by the formula R1The same groups as those exemplified in (1) above are preferably alkyl groups or aryl groups.
Specific examples of the acyl group include formyl group and acetyl group.
As a hydrolyzable silyl group (the above formula [5]]Does not include-CnH2nSpecific examples of the moiety-A) include trimethoxysilyl, methyldimethoxysilyl, dimethylmonomethoxysilyl, triethoxysilyl, methyldiethoxysilyl, dimethylmonoethoxysilyl, tripropoxysilyl, methyldipropoxysilyl, dimethylmonopropoxysilyl, triisopropenoxysilyl, methyldiisopropenyloxysilyl, dimethylisopropenyloxysilyl, triacyloxysilyl, methyldialkoxysilyl, dimethylmonoacyloxysilyl and the like, and at least 1 member selected from these groups can be used. Preferably trimethoxysilyl.
Furthermore, the number of hydrolyzable silyl groups and acid anhydride groups can be freely adjusted in the organosiloxane used in the present invention. Therefore, the balance of reactivity with the organic resin and reactivity with the inorganic base material can be freely controlled.
The organosiloxane used in the present invention may contain a monovalent hydrocarbon group Y having a polyether group in addition to the hydrolyzable silyl group and the acid anhydride group.
The polyether group has the effect of controlling the affinity of the organosiloxane to the surface of the inorganic substrate.
That is, the organic functional group is an organic siloxane containing only a hydrolyzable silyl group and an acid anhydride group, and the hydrophilicity of the acid anhydride group is low, and therefore, the hydrophilicity of the entire molecule may be greatly reduced as the number of the groups increases. Therefore, when the organosiloxane is applied to an inorganic substrate having a hydrophilic surface to form a cured coating, the following problems may occur: poor wettability, generation of repulsion, etc., and uniform coating film was not obtained. However, by introducing a polyether group into the molecule of the organosiloxane, such a problem is solved, and a uniform cured film of the organosiloxane can be formed on an inorganic substrate.
Furthermore, by adjusting the type and the amount of polyether group to be incorporated, the reaction between the hydrolyzable silyl group and the inorganic base material can be controlled, and the bonding strength between the base material and the organosiloxane can be adjusted. Thus, when the organosiloxane is used for bonding an organic resin and an inorganic substrate, the adhesive strength can be adjusted from slight pressure bonding to strong bonding according to the application.
Specific examples of the monovalent hydrocarbon group in the monovalent hydrocarbon group containing a polyether group include the group R1The same groups as those exemplified in (1) above are preferably alkyl groups, and more preferably linear alkyl groups.
Preferable examples of Y include a group represented by the following formula [3 ].
[ CHEM 10]
-CmH2m-O(C2H4O)e(C3H6O)fR2 [3]
R is as defined above2Represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydrocarbon group represented by the following formula [ 4]]The group shown.
[ CHEM 11]
Figure GDA0003112833360000131
(in the formula, R3Represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. )
As formula [3]、[4]The monovalent hydrocarbon group in (1) includes the above-mentioned R1The monovalent hydrocarbon group having a carbon number corresponding to each of the groups shown in (1) above.
As R2The alkyl group having 1 to 4 carbon atoms is preferable, and the methyl group is more preferable.
e. f independently represents an integer of 0 or more, preferably an integer in the range of 0. ltoreq. e.ltoreq.50 or 0. ltoreq. f.ltoreq.50, more preferably an integer in the range of 0. ltoreq. e.ltoreq.20 or 0. ltoreq. f.ltoreq.20. However, at least 1 of e and f is an integer of 1 or more, preferably 1 to 50.
m represents an integer of 2 or more, preferably an integer of 2 to 6.
The polyether moiety may be of ethylene oxide type (hereinafter referred to as EO type), propylene oxide type (hereinafter referred to as PO type), or ethylene oxide-propylene oxide type (hereinafter referred to as EO-PO type), and in the case of EO-PO type, it may be random, block, or alternating.
In addition, moisture resistance can be improved by introducing a monovalent hydrocarbon group having a PO type polyether group into the organosiloxane used in the present invention.
The polyether group portion may be a fluoropolyether group in which at least a part of hydrogen atoms is substituted with fluorine. By containing fluorine, the migration of the organosiloxane used in the present invention to the resin surface can be improved, and the affinity of the resin surface with the adherend can be controlled.
The fluoropolyether group is not particularly limited, and preferably comprises at least 1 kind selected from the structural units shown below.
[ CHEM 12]
Figure GDA0003112833360000132
Specific examples of the monovalent hydrocarbon group having a fluoropolyether group include the following structures.
[ CHEM 13]
Figure GDA0003112833360000141
Preferred examples of the organosiloxane used in the present invention include those represented by the following formulae [12] and [13], but are not limited thereto. Further, the arrangement of the siloxane units in the organosiloxane of the following formulae [12] and [13] may be random or block.
[ CHEM 14]
Figure GDA0003112833360000142
The equivalent weight of the acid anhydride group of the organosiloxane used in the present invention is not particularly limited, but is preferably 5000g/mol or less, more preferably 2000g/mol or less, further preferably 1500g/mol or less, and further preferably 1000g/mol or less.
The organosiloxane described above can be produced by subjecting a hydrolyzable silyl group-containing compound having an aliphatic unsaturated bond, an acid anhydride group-containing compound having an aliphatic unsaturated bond, and optionally a polyether group-containing compound having an aliphatic unsaturated bond to a hydrosilylation reaction with an organohydrogensiloxane represented by the following formula [7] in the presence of a platinum catalyst.
[ CHEM 15]
Figure GDA0003112833360000151
Formula [7]In, R10M represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom2Represents a hydrogen atom or the above-mentioned R10. i. j each represents an integer of 1. ltoreq. i.ltoreq.300 or 0. ltoreq. j.ltoreq.100, preferably an integer of 1. ltoreq. i.ltoreq.150 or 0. ltoreq. j.ltoreq.50, more preferably an integer of 1. ltoreq. i.ltoreq.60 or 0. ltoreq. j.ltoreq.20. The arrangement of each repeating unit in parentheses denoted by i and j may be random or block.
In this case, examples of the hydrolyzable silyl group-containing compound having an aliphatic unsaturated bond include compounds represented by the following formula [8 ].
[ CHEM 16]
Figure GDA0003112833360000152
(wherein p represents an integer of 0 to 10, preferably 0 to 5. R4、R5And g represents the same meaning as described above. )
Specific examples of the hydrolyzable silyl group-containing compound having an unsaturated bond include vinyl group-containing alkoxysilane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane.
The reaction ratio in the hydrosilylation reaction is preferably 1 to 100mol, more preferably 1 to 50mol, and still more preferably 1 to 20mol, based on 1mol of organohydrogensiloxane.
Examples of the acid anhydride group-containing compound having an aliphatic unsaturated bond include compounds represented by the following formula [9 ].
[ CHEM 17]
Figure GDA0003112833360000161
(wherein p represents the same meaning as described above.)
Specific examples of the acid anhydride group-containing compound having an aliphatic unsaturated bond include the following compounds, and allyl succinic anhydride is particularly preferable.
The reaction ratio in the hydrosilylation reaction is preferably 1 to 100mol, more preferably 1 to 50mol, and still more preferably 1 to 20mol, based on 1mol of organohydrogensiloxane.
[ CHEM 18]
Figure GDA0003112833360000162
Examples of the polyether group-containing compound having an aliphatic unsaturated bond include compounds represented by the following formula [10 ].
[ CHEM 19]
Figure GDA0003112833360000163
(wherein p and R are2E and f are as defined above. )
In particular, as the polyether group-containing compound having an unsaturated bond, allyl polyether represented by the following formula [11] is preferable.
The reaction ratio in the hydrosilylation reaction is preferably 1 to 100mol, more preferably 1 to 50mol, and still more preferably 1 to 20mol, based on 1mol of organohydrogensiloxane.
[ CHEM 20 ]
CH2＝CHGH2-O(C2H4O)e(C3H6O)tR2 [11]
(in the formula, R2E and f are as defined above. )
More specifically, for example, in the case of the compound represented by the above formula [12], it can be produced by subjecting 4mol of vinyltrimethoxysilane, 1mol of allyl polyether represented by the following formula [15] and 3mol of allyl succinic anhydride to a hydrosilylation reaction with respect to 1mol of methylhydrogensiloxane represented by the following formula [14] under a platinum catalyst.
[ CHEM 21 ]
Figure GDA0003112833360000171
In the case of the compound represented by the above formula [13], it can be produced by subjecting 4mol of vinyltrimethoxysilane and 4mol of allylsuccinic anhydride to a hydrosilylation reaction in the presence of a platinum catalyst with respect to 1mol of methylhydrogensiloxane represented by the following formula [16 ].
[ CHEM 22 ]
Figure GDA0003112833360000172
The alkoxysilane compound used in the present invention can be produced by a method other than the above-described method, and can be produced by, for example, a method of subjecting a succinic anhydride-modified alkoxysilane and a polyether-modified alkoxysilane to hydrolytic condensation.
However, this method has a problem that ring-opening reaction due to hydrolysis of succinic anhydride occurs simultaneously in the production stage because water is used.
As another method, for example, the following method can be used: vinyl trimethoxy silane, allyl polyether and allyl succinic anhydride were sequentially added to a cyclic organohydrogensiloxane represented by the following formula [17] under a platinum catalyst.
[ CHEM 23 ]
Figure GDA0003112833360000173
(wherein k represents an integer of 3 or more.)
However, among the cyclic organohydrogensiloxanes, an organohydrogensiloxane which is actually available at a low price and easily becomes a low molecular weight siloxane having a k of 3 to 5. In this case, the number of reaction Sites (SiH) present in a molecule is at most 5. When vinyltrimethoxysilane, allyl polyether, and allyl succinic anhydride are added to the cyclic organohydrogensiloxane in this order by a hydrosilylation reaction, the total amount of each compound to be introduced is at most 5, and the amount of each functional group to be freely introduced cannot be set.
The above-mentioned problems can be solved by the method for producing an organosiloxane of the present invention.
That is, the amount of vinyltrimethoxysilane, allyl polyether, or allyl succinic anhydride to be introduced can be freely set by adjusting the value of i of the organohydrogensiloxane represented by the above formula [7] used as a raw material.
The organosiloxane used in the present invention has a structure in which a group containing each functional group of an alkoxy group, an acid anhydride group, and a polyether group is bonded to a side chain of a linear siloxane skeleton.
In the pressure-sensitive adhesive composition of the present invention, the blending ratio of the copolymer to be the matrix resin and the alkoxysilane is not particularly limited, and the organosiloxane is preferably blended in an amount of 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and further preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the copolymer to be the matrix resin.
In addition, a crosslinking agent may be blended in the pressure-sensitive adhesive composition of the present invention.
The amount of the crosslinking agent is not particularly limited, and is preferably 0.01 to 40 parts by mass, more preferably 0.02 to 30 parts by mass, based on 100 parts by mass of the copolymer, in order to moderate the cohesive force of the pressure-sensitive adhesive composition, improve the durability, and effectively suppress peeling of the applied film.
The crosslinking agent is not particularly limited, and in the present invention, a crosslinking agent selected from an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a metal chelate crosslinking agent, and an aziridine-based crosslinking agent is preferably used.
More specifically, for example, a polyglycidyl compound having 2 or more glycidyl groups in 1 molecule, a polyisocyanate compound having 2 or more isocyanate groups in 1 molecule, a polyaziridine compound having 2 or more aziridine groups in 1 molecule, a metal chelate compound, a butylated melamine compound, or the like can be used, and these may be used alone or 2 or more kinds may be used in combination.
Specific examples of the polyglycidyl compounds include polyfunctional glycidyl compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, N' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, and diglycerol polyglycidyl ether, and these can be used alone or in combination of 2 or more kinds.
Specific examples of the polyisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and an adduct obtained by reacting a polyol such as glycerin or trimethylolpropane with these isocyanate compounds to convert the isocyanate compounds into a 2-mer or 3-mer product.
Specific examples of the polyaziridine compound include 1,1 '- (methylene-di-p-phenylene) bis-3, 3-aziridinylurea, 1' - (hexamethylene) bis-3, 3-aziridinylurea, ethylenebis- (2-aziridinylpropionate), tris (1-aziridinyl) phosphine oxide, 2,4, 6-triaziridinyl-1, 3, 5-triazine, trimethylolpropane-tris- (2-aziridinylpropionate), and the like, and these may be used alone or in combination of 2 or more.
Specific examples of the metal chelate compound include compounds in which acetylacetone and ethyl acetoacetate are added to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium, and these compounds may be used alone or in combination of 2 or more.
In addition, as a crosslinking mode, radiation (preferably ultraviolet rays) crosslinking is also effective, in which case a monomer having at least 2 polymerizable reactive double bonds and a photopolymerization initiator (including a sensitizer as well) can be added.
Specific examples of the monomer having at least 2 polymerizable double bonds include 2-functional (meth) acrylates such as polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol a diacrylate, tricyclodecane dimethanol diacrylate and 1, 9-nonanediol diacrylate; and polyfunctional (meth) acrylates such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, isocyanuric acid triacrylate, tris (2-acryloyloxyethyl) isocyanurate, and the like.
Furthermore, if necessary, it is also possible to use known monomers having only 1 polymerizable reactive double bond in combination for controlling the crosslinking density.
As the photopolymerization initiator, a known photopolymerization initiator using radiation (ultraviolet rays) can be used, and examples thereof include amino ketone type, hydroxy ketone type, acylphosphine oxide type, benzildimethyl ketal type, benzophenone type, and trichloromethyl group-containing triazine derivative type photopolymerization initiators.
In addition, the pressure-sensitive adhesive composition of the present invention can further improve the durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention by adding a silane coupling agent and/or a hydrolysis condensate thereof (collectively referred to as a silane coupling agent) other than the above-mentioned essential organosiloxane.
The amount of the silane coupling agent added is preferably 0.01 to 5 parts by mass per 100 parts by mass of the copolymer.
Specific examples of the silane coupling agent include epoxy group-containing silane coupling agents such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropyltriethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and epoxy group-containing alkoxysilane oligomers; mercapto group-containing silane coupling agents such as γ -mercaptopropyltrimethoxysilane, γ -mercaptopropyltriethoxysilane, γ -mercaptopropylmethyldimethoxysilane, γ -mercaptopropylmethyldiethoxysilane, and mercapto group-containing alkoxysilane oligomers; amino group-containing silane coupling agents such as γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane and N-phenyl- γ -aminopropyltrimethoxysilane; and isocyanate group-containing silane coupling agents such as γ -isocyanatopropyltrimethoxysilane and γ -isocyanatopropyltriethoxysilane, which may be used alone or in combination of 2 or more.
Further, various additives may be blended in the pressure-sensitive adhesive composition of the present invention according to the required characteristics for the purpose of adjusting the adhesive force and the like within a range not to impair the effects of the present invention.
Examples of the additive include terpene-based, terpene-phenol-based, coumarone-indene-based, styrene-based, rosin-based, xylene-based, phenol-based, petroleum-based tackifying resins, antioxidants, ultraviolet absorbers, fillers, pigments, plasticizers, antistatic agents, and the like.
The film with an adhesive layer of the present invention has: and a layer comprising the pressure-sensitive adhesive composition of the present invention on at least one side of the film.
That is, a film (pressure-sensitive adhesive layer) made of the pressure-sensitive adhesive composition of the present invention having excellent "durability" and "reusability" is laminated on one or both sides of an optically functional film (hereinafter referred to as "original film") on which a pressure-sensitive adhesive layer is not formed.
Therefore, the film with an adhesive layer of the present invention has both: the pressure-sensitive adhesive layer has a property of not peeling from a glass substrate or the like constituting the liquid crystal cell at high temperature, high temperature and high humidity and not generating foaming in the pressure-sensitive adhesive layer (durability), and a property of being easily peeled even after a long period of time and not generating a residue on the substrate or the like after peeling (reusability).
The type of the original film is not particularly limited, and examples thereof include a light guide plate, an antireflection film, a conductive film, a viewing angle enlarging film, a retardation film, a polarizing plate, and a film obtained by combining these films.
In addition, in order to improve the adhesion of the film made of the pressure-sensitive adhesive composition of the present invention to the original film, the surface of the original film may be subjected to a surface treatment such as corona treatment.
The thickness of the original film is not particularly limited, and may be determined to be an appropriate thickness according to the application and purpose, and may be, for example, about 5 to 300 μm.
The film with an adhesive layer of the present invention is obtained by coating the pressure-sensitive adhesive composition of the present invention on one side or both sides of the above-mentioned original film by using a commonly used coating apparatus such as a roll coating apparatus, and drying the coated layer to form a film (pressure-sensitive adhesive layer). Further, the pressure-sensitive adhesive layer applied may be crosslinked by heating or cured by light such as ultraviolet rays to form a cured film, if necessary.
The pressure-sensitive adhesive layer-provided film of the present invention can also be obtained by first coating the pressure-sensitive adhesive composition of the present invention on a protective film such as a polyethylene terephthalate film (PET film) whose surface is coated with a release agent such as a silicone resin, drying the coating to form a pressure-sensitive adhesive layer, and then laminating the original film on the pressure-sensitive adhesive layer.
In all of the above cases, the thickness of the pressure-sensitive adhesive layer (film) after drying is preferably about 10 to 50 μm in terms of the amount of the pressure-sensitive adhesive composition applied. By setting the thickness of the pressure-sensitive adhesive layer within the above range, a film with an adhesive layer suitable as an optical functional film having a further balance of durability and reusability is obtained.
The adhesive layer-attached film of the present invention produced as described above can be attached to a glass substrate of a liquid crystal cell of a liquid crystal display device or the like by a commonly used means.
The film with an adhesive layer of the present invention may be further laminated on an optical functional film attached to a glass substrate.
Examples
The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples.
The apparatus used in the examples is as follows.
Infrared spectroscopy (FTIR): NICOLET6700 made by Thermo scientific
29Si-NMR: AVANCE400M manufactured by Bruker
GPC: HLC-8220GPC made by Tosoh
[1] Preparation of matrix resin
Synthesis examples 1-1]Preparation of copolymer solution-1
Nitrogen gas was introduced into a 1L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and the air in the apparatus was replaced with nitrogen gas. Next, 70.0g of n-Butyl Acrylate (BA), 30.0g of Methyl Acrylate (MA), 0.3g of Acrylic Acid (AA), 1.7g of 2-hydroxyethyl acrylate (2HEA), 0.1g of azobisisobutyronitrile and 100g of ethyl acetate were charged into the flask, and the mixture was reacted at 70 ℃ for 10 hours with stirring to obtain an acrylic copolymer solution-1. The weight average molecular weight of the copolymer obtained by GPC was 1500000.
Synthesis examples 1 to 2]Preparation of copolymer solution-2
A copolymer solution-2 was obtained in the same manner as in Synthesis example 1, except that Acrylic Acid (AA) was not used, 2.0g of 2-hydroxyethyl acrylate (2HEA) was used, and Acrylic Acid (AA) was not used. The weight average molecular weight of the copolymer obtained by GPC was 1500000.
[2] Synthesis of organosiloxanes
[ Synthesis examples 2-1]
100g (0.192mol) of organohydrogensiloxane represented by the following formula [18] and 114g of toluene were charged in a 1 liter 3-neck flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 1.00g of a vinylsiloxane-coordinated Pt toluene solution was added thereto under stirring. Subsequently, the temperature was raised to 80 ℃ and 56.7g (0.383mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
[ CHEM 24 ]
Figure GDA0003112833360000231
The reaction rate of vinyltrimethoxysilane used in the above reaction was measured as follows.
First, the ≡ SiH content in 1g of each sample before and after the reaction was measured by the following method.
10g of butanol was heated to 1g of each sample before and after the reaction, and 20g of a 20 mass% NaOH aqueous solution was added thereto with stirring. From the hydrogen produced at this time (. ident.SiH + H)2O→≡SiOH+H2≡ SiH content was calculated for each of the amounts ≡ SiH).
Next, the amount of vinyltrimethoxysilane actually reacted in 1g of the sample was calculated from the following formula. The results are shown in table 1.
Reaction amount (mol) — [ ≡ SiH content (mol) before reaction) ] - [ ≡ SiH content (mol) after reaction ]
[ TABLE 1]
Figure GDA0003112833360000232
In 1g of sample before reaction, 1.41X 10 times as the starting material charged vinyltrimethoxysilane was present-3And (mol). From the reaction amount obtained above and the amount charged as the raw material, the reaction rate of vinyltrimethoxysilane was calculated as described below and found to be 99.3%.
[ reaction Rate ═ 1.40X 10%-3(mol)/1.41×10-3(mol)×100＝99.3(％)]
From the above, it was confirmed that: by the hydrosilylation reaction, 99% or more of vinyltrimethoxysilane charged as a raw material is reacted with methylhydrogensiloxane.
Next, an operation for reacting allyl succinic anhydride with the remaining ≡ Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00g of a vinylsiloxane-coordinated Pt toluene solution (Pt concentration: 0.5 mass%) was added under stirring, and the temperature was raised to 110 ℃. Subsequently, 120g (0.857mol) of allyl succinic anhydride was added dropwise, and then, the mixture was aged at 115 ℃ for 10 hours.
Here, the reaction rate of allyl succinic anhydride was measured. First, the ≡ SiH content in 1g of a sample before and after the reaction is measured by the same method as described above, and the amount of allyl succinic anhydride actually reacted is calculated. The results are shown in table 2.
[ TABLE 2]
Figure GDA0003112833360000241
The amount of hydrogen gas produced after the completion of the reaction was a value approximately close to 0 ml. It is considered that substantially all of ≡ SiH remaining in methylhydrogensiloxane has reacted with allyl succinic anhydride by the hydrosilylation reaction.
In sample 1g before the reaction, allyl succinic anhydride 2.17X 10 charged as a raw material was present-3And (mol). From the reaction amount obtained above and the amount charged as the raw material, the reaction rate of allyl succinic anhydride was calculated as follows, and found to be 87.6%.
[1.90×10-3(mol)/2.17×10-3(mol)×100＝87.6(％)]
About 88% of the allyl succinic anhydride charged as a raw material was reacted with methylhydrogensiloxane, and the remaining about 12% remained as the remaining portion.
Finally, an operation for removing the residual allyl succinic anhydride was performed. The Dimroth condenser was connected to the exhaust line in the manner of changing the pressure, and after the pressure in the system was reduced to 10mmHg, the system was heated at 150 ℃ for 20 hours under nitrogen bubbling. After the heating under reduced pressure was completed, the temperature was cooled to room temperature and the pressure was returned to normal pressure, and then the obtained liquid was purified by filtration to obtain 246g of product-1.
Here, as the product-1, GPC measurement in a THF solvent was carried out. As a result, a broad product peak was observed at a position where the retention time was 21 to 32 minutes. Since the peak of the raw material allyl succinic anhydride was not present in the vicinity of the retention time of 36 to 37 minutes, it was considered that the remaining part of the allyl succinic anhydride was almost completely removed by the final reduced-pressure heating.
Next, as the product-1, an acid anhydride group was assigned by infrared spectroscopy (FTIR). The result was 1863cm-1、1785cm-1Absorption due to carbonyl stretching vibration of the succinic anhydride group was observed. Furthermore, at 1735cm-1No absorption due to stretching vibration of the carboxyl group caused by ring opening of the succinic anhydride group was observed. Since the product-1 is produced in a completely nonaqueous system, the ring-opening of the succinic anhydride group is sufficiently suppressed without mixing active hydrogen-containing compounds (e.g., water, alcohol, etc.) in the production stage.
Next, in order to analyze the structure of product-1, the following steps were carried out29Si-NMR measurement. As a result, 1 peak suggesting the existence of the structure shown below was first confirmed in the vicinity of 7.2 ppm.
[ CHEM 25 ]
Figure GDA0003112833360000251
In addition, in the vicinity of-22 ppm, 1 peak suggesting the existence of the structure shown below was confirmed.
[ CHEM 26 ]
Figure GDA0003112833360000252
Wherein R represents any one of the following groups.
[ CHEM 27 ]
Figure GDA0003112833360000261
In addition, in the vicinity of-42 ppm, 1 peak suggesting the existence of the group shown below was confirmed.
[ CHEM 28 ]
Figure GDA0003112833360000262
From the above results, it is estimated that: the product-1 is a structure in which a monovalent hydrocarbon group containing a trimethoxysilyl group and a monovalent hydrocarbon group containing a succinic anhydride group are bonded to the side chain of a linear siloxane.
Here, the number (average value) of trimethoxysilyl groups and succinic anhydride groups introduced by reaction of 1mol with respect to methylhydrogensiloxane was calculated from the measurement results of the feed amounts of the respective raw materials of methylhydrogensiloxane, vinyltrimethoxysilane and allylsuccinic anhydride and the above reaction rate. The introduced amount of each functional group and the acid anhydride group equivalent are shown in table 3.
[ Synthesis examples 2-2]
100g (0.0371mol) of methylhydrogensiloxane represented by the following formula [19] and 114g of toluene were charged in the same manner as in Synthesis example 2-1, and 1.00g of a toluene solution (Pt concentration: 0.5 mass%) containing vinylsiloxane-coordinated Pt was added thereto under stirring. Then, the temperature was raised to 80 ℃ and 55.0g (0.371mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
[ CHEM 29 ]
Figure GDA0003112833360000271
Next, an operation for reacting allyl succinic anhydride with the remaining ≡ Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00g of a vinylsiloxane-coordinated Pt toluene solution (Pt concentration: 0.5 mass%) was added under stirring, and the temperature was raised to 110 ℃. Then, 62.3g (0.445mol) of allyl succinic anhydride was added dropwise thereto, followed by aging at 115 ℃ for 10 hours.
Finally, the same procedure as in Synthesis example 2-1 was carried out to remove the remaining allyl succinic anhydride, and the resulting liquid was purified by filtration to obtain 178g of product-2.
Here, the number (average value) of trimethoxysilyl groups and succinic anhydride groups introduced by the reaction was calculated for 1mol of methylhydrogensiloxane in the same manner as in Synthesis example 2-1. The introduced amount of each functional group and the acid anhydride group equivalent are shown in table 3.
Synthesis examples 2 to 3
In the same manner as in Synthesis example 2-1, 100g (0.0371mol) of methylhydrogensiloxane represented by the above formula [19] and 114g of toluene were charged, and 1.00g of a toluene solution (Pt concentration: 0.5 mass%) containing vinylsiloxane-coordinated Pt was added thereto under stirring. Then, the temperature was raised to 80 ℃ and 55.0g (0.371mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
Subsequently, an operation for reacting 3- (perfluorohexyl) -1-propene with the remaining ≡ Si-H group contained in the methylhydrogensiloxane was performed. The temperature of the reaction solution thus obtained was raised to 100 ℃ and 26.7g (0.0742mol) of 3- (perfluorohexyl) -1-propene were added dropwise thereto, followed by aging for 5 hours.
Next, an operation for reacting allyl succinic anhydride with the remaining ≡ Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00g of a vinylsiloxane-coordinated Pt toluene solution (Pt concentration: 0.5 mass%) was added under stirring, and the temperature was raised to 110 ℃. Then, 62.3g (0.445mol) of allyl succinic anhydride was added dropwise thereto, followed by aging at 115 ℃ for 10 hours.
Finally, the same procedure as in Synthesis example 2-1 was carried out to remove the remaining allyl succinic anhydride, and the resulting liquid was purified by filtration to give 199g of product-3.
Here, the number (average value) of trimethoxysilyl group, perfluorohexyl group and succinic anhydride group introduced by the reaction was calculated for 1mol of methylhydrogensiloxane in the same manner as in Synthesis example 2-1. The introduced amount of each functional group and the acid anhydride group equivalent are shown in table 3.
Synthesis examples 2 to 4
100g (0.192mol) of methylhydrogensiloxane represented by the above formula [18] and 114g of toluene were charged in the same manner as in Synthesis example 2-1, and 1.00g of a toluene solution (Pt concentration: 0.5 mass%) containing vinylsiloxane-coordinated Pt was added thereto under stirring. Subsequently, the temperature was raised to 80 ℃ and 56.9g (0.384mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
Next, an operation for reacting the allyl polyether with a part of the residual ≡ Si-H groups in the methylhydrogensiloxane was performed. While maintaining the reaction solution at 80 ℃, CH was added dropwise under stirring2＝CH-CH2-O(CH2CH2O)8CH3After 81.4g (0.192mol) of the allyl polyether shown, aging was carried out for 3 hours.
Next, an operation for reacting allyl succinic anhydride with the remaining ≡ Si-H groups contained in methylhydrogensiloxane was performed. The temperature of the reaction solution was raised to 110 ℃, 1.00g of a vinyl siloxane Pt complex toluene solution (Pt concentration: 0.5 mass%) was added under stirring, 121g (0.864mol) of allyl succinic anhydride was added dropwise thereto, and then aging was carried out at 115 ℃ for 10 hours.
Finally, in order to remove the remaining allyl succinic anhydride, the pressure was reduced to 10mmHg in the same manner as in Synthesis example 2-1, and then the mixture was heated at 120 ℃ for 20 hours under nitrogen bubbling. After the heating under reduced pressure was completed, the temperature was cooled to room temperature, the pressure was returned to normal pressure, and the obtained liquid was purified by filtration to obtain 271g of product-4.
Here, the number (average value) of trimethoxysilyl groups, polyether groups and succinic anhydride groups introduced by the reaction was calculated for 1mol of methylhydrogensiloxane in the same manner as in Synthesis example 2-1. The introduced amount of each functional group and the acid anhydride group equivalent are shown in table 3.
Synthesis examples 2 to 5
100g (0.0371mol) of methylhydrogensiloxane represented by the above formula [19] and 114g of toluene were charged in the same manner as in Synthesis example 2-1, and 1.00g of a toluene solution (Pt concentration: 0.5 mass%) containing vinylsiloxane-coordinated Pt was added thereto under stirring. Then, the temperature was raised to 80 ℃ and 16.5g (0.111mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
Next, an operation for reacting the allyl polyether with the remaining ≡ Si-H group contained in the methylhydrogensiloxane was performed. While maintaining the reaction solution at 80 ℃, CH was added dropwise under stirring2＝CH-CH2-O(CH2CH2CH2O)12C4H9271g (0.335mol) of the allyl polyether was then aged for 3 hours.
Next, an operation for reacting allyl succinic anhydride with the remaining ≡ Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00g of a vinylsiloxane-coordinated Pt toluene solution (Pt concentration: 0.5 mass%) was added under stirring, and the temperature was raised to 110 ℃. Then, 62.3g (0.445mol) of allyl succinic anhydride was added dropwise thereto, followed by aging at 115 ℃ for 10 hours.
Finally, the same procedure as in Synthesis example 2-4 was carried out to remove the remaining residual allyl succinic anhydride, and the resulting liquid was purified by filtration to give 367g of product-5.
Here, the number (average value) of trimethoxysilyl groups, polyether groups and succinic anhydride groups introduced by the reaction was calculated for 1mol of methylhydrogensiloxane in the same manner as in Synthesis example 2-1. The introduced amount of each functional group and the acid anhydride group equivalent are shown in table 3.
Synthesis examples 2 to 6
100g (0.0371mol) of methylhydrogensiloxane represented by the above formula [19] and 114g of toluene were charged in the same manner as in Synthesis example 2-1, and 1.00g of a toluene solution (Pt concentration: 0.5 mass%) containing vinylsiloxane-coordinated Pt was added thereto under stirring. Then, the temperature was raised to 80 ℃ and 16.5g (0.111mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
Subsequently, an operation for reacting the allyl polyether with the remaining ≡ Si-H group contained in the methylhydrogensiloxane was performed. While maintaining the reaction solution at 80 ℃, CH was added dropwise under stirring2＝CH-CH2-O(CH2CH2CH2O)12C4H9420g (0.519mol) of the allyl polyether was then aged for 3 hours.
Next, an operation for reacting allyl succinic anhydride with the remaining ≡ Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00g of a vinylsiloxane-coordinated Pt toluene solution (Pt concentration: 0.5 mass%) was added under stirring, and the temperature was raised to 110 ℃. Subsequently, 23.4g (0.167mol) of allyl succinic anhydride was added dropwise thereto, and then, the mixture was aged at 115 ℃ for 10 hours.
Finally, the same procedure as in Synthesis example 2-4 was carried out to remove the remaining residual allyl succinic anhydride, and the resulting liquid was purified by filtration to give 475g of product-6.
Here, the number (average value) of trimethoxysilyl groups, polyether groups and succinic anhydride groups introduced by the reaction was calculated for 1mol of methylhydrogensiloxane in the same manner as in Synthesis example 2-1. The introduced amount of each functional group and the acid anhydride group equivalent are shown in table 3.
Synthesis examples 2 to 7
100g (0.0371mol) of methylhydrogensiloxane represented by the above formula [19] and 114g of toluene were charged in the same manner as in Synthesis example 2-1, and 1.00g of a toluene solution (Pt concentration: 0.5 mass%) containing vinylsiloxane-coordinated Pt was added thereto under stirring. Then, the temperature was raised to 80 ℃ and 55.0g (0.371mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
Subsequently, an operation for reacting the allyl polyether with the remaining ≡ Si-H group contained in the methylhydrogensiloxane was performed. While maintaining the reaction solution at 80 ℃, CH was added dropwise under stirring2＝CH-CH2-O(CH2CH2CH2O)12C4H960.1g (0.0742mol) of the allyl polyether was then aged for 3 hours.
Next, an operation for reacting 3- (perfluorohexyl) -1-propene with the remaining ≡ Si-H group contained in the methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00g of a vinylsiloxane-coordinated Pt toluene solution (Pt concentration: 0.5 mass%) was added under stirring, and the temperature was raised to 100 ℃. Subsequently, 26.7g (0.0741mol) of 3- (perfluorohexyl) -1-propene was added dropwise thereto, and then, the mixture was aged for 5 hours.
Furthermore, an operation for reacting allyl succinic anhydride with the remaining ≡ Si-H group contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00g of a vinylsiloxane-coordinated Pt toluene solution (Pt concentration: 0.5 mass%) was added under stirring, and the temperature was raised to 110 ℃. Subsequently, 46.8g (0.334mol) of allyl succinic anhydride was added dropwise thereto, and then, the mixture was aged at 115 ℃ for 10 hours.
Finally, the same procedure as in Synthesis example 2-4 was carried out to remove the remaining residual allyl succinic anhydride, and the obtained liquid was purified by filtration to obtain 230g of product-7.
Here, the number (average value) of trimethoxysilyl group, polyether group, perfluorohexyl group and succinic anhydride group introduced by the reaction was calculated for 1mol of methylhydrogensiloxane in the same manner as in Synthesis example 2-1. The introduced amount of each functional group and the acid anhydride group equivalent are shown in table 3.
[ TABLE 3]
Figure GDA0003112833360000311
Synthesis examples 2 to 8
100g (0.0371mol) of methylhydrogensiloxane represented by the above formula [19] and 114g of toluene were charged in a 1 liter 3-neck flask equipped with a stirrer, a thermometer and a Dimroth condenser, and then 1.00g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 mass%) was added thereto under stirring. Then, the temperature was raised to 80 ℃ and 55.0g (0.371mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.
Subsequently, an operation for reacting the allyl polyether with the remaining ≡ Si-H group contained in the methylhydrogensiloxane was performed. While maintaining the reaction solution at 80 ℃, CH was added dropwise under stirring2＝CH-CH2-O(CH2CH2CH2O)12C4H960.1g (0.0742mol) of the allyl polyether was then aged for 3 hours.
Next, an operation for reacting allyl glycidyl ether with the remaining ≡ Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 50.7g (0.445mol) of allyl glycidyl ether was added dropwise, followed by aging for 10 hours.
Finally, in order to remove the remaining allyl glycidyl ether, the pressure was reduced to 10mmHg in the same manner as in Synthesis example 2-1, and then the mixture was heated at 120 ℃ for 5 hours under nitrogen bubbling. After the completion of the vacuum heating, the temperature was cooled to room temperature and the pressure was returned to normal pressure, and the obtained liquid was purified by filtration to obtain 219g of product-8.
Here, the number (average value) of trimethoxysilyl groups, polyether groups, and epoxy groups introduced by the reaction was calculated for 1mol of methylhydrogensiloxane in the same manner as in Synthesis example 2-1. The introduced amount of each functional group and the epoxy equivalent are shown in table 4.
[ TABLE 4]
Figure GDA0003112833360000321
[2] Preparation of pressure sensitive adhesive composition
[ examples and comparative examples ]
The pressure-sensitive adhesive compositions of examples 1-1 to 1-7 and 2-1 to 2-7 and comparative examples 1-1 to 1-4 and 2-1 to 2-4 were prepared by mixing the components described in tables 5 and 6 below with respect to 100 parts by mass of the solid content of the (a) acrylic ester-containing copolymer solution obtained in synthesis examples 1-1 and 1-2.
[ TABLE 5]
Figure GDA0003112833360000331
TDI: trimethylolpropane toluene diisocyanate adduct
[ TABLE 6]
Figure GDA0003112833360000332
TDI: trimethylolpropane toluene diisocyanate adduct
X-24-1056: epoxy alkoxy oligomer manufactured by shin-Etsu chemical industry Co., Ltd
X-41-1810: methylmercapto alkoxy oligomer manufactured by shin-Etsu chemical industry Co., Ltd
X-12-641: polyether-modified silane produced by shin-Etsu chemical industry Co., Ltd
By applying the pressure-sensitive adhesive compositions obtained in the above-described examples and comparative examples to a PET film (releasable substrate) and drying, a uniform pressure-sensitive adhesive layer of 25 μm was formed. An iodine polarizing plate having a thickness of 185 μm was attached to the surface on which the pressure-sensitive adhesive layer was formed, and after maintaining the pressure-sensitive adhesive layer at 25 ℃ and 50% RH for 7 days, the obtained polarizing plate was cut into an appropriate size, and reusability and durability were evaluated by the following methods. The results are shown in tables 7 and 8.
(1) Reusability
The polarizing plate coated with the pressure-sensitive adhesive was cut into a size of 90mm × 170mm, and the PET film was peeled off and bonded to a glass substrate, and then the glass substrate was held at 50 ℃ and 0.5MPa for 20 minutes to bond the two to prepare a sample for testing. After being left at 25 ℃ and 60% RH for 1 hour, the mixture was aged at 70 ℃ for 20 hours and then cooled to 25 ℃.
Next, the polarizing plate was peeled from the glass, and it was confirmed whether or not the polarizing plate and the glass plate could be peeled without breaking and without leaving an adhesive on the glass surface, and evaluation was made based on the following criteria. The results are shown in tables 7 and 8.
Very good: can be easily peeled (light peeling)
O: strippable (middle stripping)
And (delta): peeling was slightly difficult, and the pressure-sensitive adhesive remained on the glass surface (heavy peeling)
X: non-peelable property, breakage of glass or polarizing plate (heavy peeling)
(2) Durability
The pressure-sensitive adhesive-coated polarizing plate was cut into a size of 90mm × 170mm, and the PET film was peeled off and bonded to a glass substrate, and then, the polarizing plate was subjected to autoclave treatment at 50 ℃ and 0.5MPa for 20 minutes to adhere the polarizing plate to the glass. Next, after leaving in an atmosphere of 80 ℃ (dry) and an atmosphere of 60 ℃/90% RH for 1000 hours, the presence or absence of bubble formation and peeling was confirmed, and evaluated based on the following criteria. The results are shown in tables 7 and 8. Further, the test piece was left to stand at room temperature (23 ℃ C./60% RH) for 24 hours before the evaluation of the state of the test piece.
Very good: there was no change in appearance such as peeling.
O: there was slight peeling, but there was no practical problem.
X: the peeling was remarkable, and there was a problem in practical use.
[ TABLE 7]
Figure GDA0003112833360000351
[ TABLE 8]
Figure GDA0003112833360000352
As shown in tables 7 and 8, it was confirmed that the pressure-sensitive adhesive compositions of the examples were good in both reusability and durability and were significantly superior to the pressure-sensitive adhesive compositions of the comparative examples. The pressure-sensitive adhesive composition of the present invention exhibits excellent durability even when an OH-type acrylic resin mainly containing a hydroxyl group as a functional group is used, and can achieve compatibility with reusability.

Claims (9)

1. A pressure sensitive adhesive composition characterized by comprising: a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, and at least one of an organosiloxane having at least 1 hydrolyzable silyl group and at least 1 acid anhydride group in the molecule represented by the following formula [1a ] and a hydrolysate thereof, the copolymer containing a structural unit derived from a hydroxyl group-containing monomer,
Figure FDA0003112833350000011
wherein X represents a monovalent hydrocarbon group having an acid anhydride group, Y represents a monovalent hydrocarbon group having a polyether group, Z represents a monovalent hydrocarbon group having a hydrolyzable silyl group, and R represents1Independently represents a hydrogen atom or a C1-20 monovalent hydrocarbon group which may be substituted with a halogen atom, M1Independently of one another represent a group selected from X, Z and R1Wherein a, b, c and d each represent an integer of 0. ltoreq. a.ltoreq.100, b 0, 0. ltoreq. c.ltoreq.100, 0. ltoreq. d.ltoreq.100; wherein, when a is 0, at least 1M1Is X, c is an integer of 1 to 100, and when c is 0, at least 1M1Is Z, a is an integer which is more than or equal to 1 and less than or equal to 100; the arrangement of the repeating units in parentheses denoted by a, b, c and d may be random or block.
2. The pressure-sensitive adhesive composition according to claim 1, wherein X is a monovalent hydrocarbon group having an acid anhydride group represented by the following formula [2], Z is a monovalent hydrocarbon group having a hydrolyzable silyl group represented by the following formula [5],
Figure FDA0003112833350000012
wherein A represents an alkylene group having 2 to 6 carbon atoms,
Figure FDA0003112833350000021
in the formula, R4Represents an alkyl group having 1 to 10 carbon atoms, R5Represents a monovalent hydrocarbon group or acyl group having 1 to 10 carbon atoms, n represents an integer of 2 or more, and g represents an integer of 1 to 3.
3. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein R is1At least 1 of (a) is a monovalent hydrocarbon group having a perfluoroalkyl group.
4. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the equivalent weight of the acid anhydride group of the organosiloxane and the hydrolysate thereof is 5000g/mol or less.
5. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the copolymer further contains a structural unit derived from a carboxyl group-containing monomer.
6. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the amount of at least one of the organosiloxane and the hydrolysate thereof is 0.001 to 5 parts by mass based on 100 parts by mass of the copolymer.
7. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the crosslinking agent is contained in an amount of 0.01 to 40 parts by mass based on 100 parts by mass of the copolymer.
8. The pressure-sensitive adhesive composition according to claim 7, wherein the crosslinking agent is at least 1 selected from the group consisting of an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a metal-based crosslinking agent, an aziridine-based crosslinking agent, and a peroxide-based crosslinking agent.
9. A film with an adhesive layer, comprising: a film and a layer formed by using the pressure-sensitive adhesive composition according to any one of claims 1 to 8 on at least one side of the film.
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