TW201900823A - Adhesive composition and film formed using the same - Google Patents

Abstract

The present invention provides an adhesive composition capable of improving durability while maintaining satisfactory reworkability when used in bonding an optical functional film and liquid cells. In particular, the adhesive composition comprises: a polymer of unsaturated polymerizable monomers containing (meth)acrylic ester monomers; organosiloxane represented by formula [1a]; and at least a portion of hydrolysates thereof. In the chemical formula [1a]: 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 hydrolysable silyl group; R1 each independently represent a hydrogen atom and the like; M1 each independently represent a group selected from among X, Y, Z, and R1; and a, b, c, and d each independently represent an integer of 0-100, wherein when a is 0, at least one of the M1 is X, and c is an integer of 1 ≤ c ≤ 100; and when c is 0, at least one M1 is Z, and a is an integer of 1 ≤ a ≤ 100.

Description

Adhesive composition and film made using the same

The present invention relates to an adhesive composition and a film formed using the composition, and if further detailed, the present invention relates to an adhesive composition used for bonding an optically functional film and a liquid crystal cell, and is formed using the composition. Layer of thin film.

A liquid crystal display device is made by first sandwiching a liquid crystal component between two glass substrates to produce a liquid crystal cell. Then, on the surface of the liquid crystal cell, a polarizing plate or a laminated body of a polarizing plate and a phase difference plate is attached through an adhesive layer. Optically functional film.

This liquid crystal display device is widely used as a display device such as a display for a vehicle, an outdoor meter, a personal computer, or a television. In addition, with the expansion of applications, the environment in which a liquid crystal display device is used is various, so it may be used in a very severe environment, and the adhesive composition used in the manufacture of a liquid crystal display device is also gradually required to be able to Performance in harsh environments. Specifically, even if exposed to a high temperature condition or a high temperature and high humidity condition, the adhesive layer formed of the adhesive composition does not foam, and the attached optically functional film does not peel off from the substrate (below) (Called "durability") is deemed necessary.

On the other hand, during the manufacturing process, the optically functional film and the liquid crystal cell may have to be reattached. In this case, it is necessary that the liquid crystal cell can be easily peeled without causing damage to the liquid crystal cell, and that the adhesive does not remain on the surface of the liquid crystal cell (hereinafter referred to as "reworkability"). That is, the adhesive used for bonding the optically functional film and the liquid crystal cell needs to have good reworkability during bonding and high durability after bonding.

Many of the adhesives used for this purpose are acrylic resins. For example, Patent Document 1 proposes an adhesive composition containing an epoxy group-containing coupling agent in an acrylic polymer.的 The composition of Patent Document 1 exhibits high durability with respect to an acrylic polymer (hereinafter referred to as "COOH-type acrylic polymer") of a type mainly containing a carboxyl group as a reactive group. However, there is a problem that durability cannot be obtained for an acrylic polymer of a type mainly containing a hydroxyl group as a reactive group (hereinafter referred to as "OH-type acrylic polymer"). In addition, Patent Documents 2 and 3 propose adhesive compositions containing an epoxy group-containing polyether modified coupling agent in an acrylic polymer. This composition can achieve both reworkability and durability for a COOH-type acrylic polymer. However, the OH-type acrylic polymer has a problem that durability cannot be obtained.

In addition, Patent Document 4 describes an adhesive composition containing a mercapto group-containing silane coupling agent in an acrylic polymer. Although this composition improves durability even with an OH-type acrylic polymer, it is not enough. In addition, Patent Document 5 proposes an adhesive composition containing an acid anhydride group-containing polyether modified coupling agent in an acrylic polymer. This composition can achieve reworkability and durability with respect to an OH-type acrylic polymer. However, in recent years, there has been a demand for further improvement in the durability of the sound waves for which the durability of the adhesive is required. [Prior Art Literature] [Patent Literature]

[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] Japan Patent No. 5990847

[Problems to be Solved by the Invention]

The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition which can maintain good reworkability and improve durability at the same time when used in the bonding of optically functional films and liquid crystal cells; A thin film of an adhesive layer made of this composition. [Means for solving problems]

In order to solve the above-mentioned problems, the present inventors conducted a review, and as a result, found a composition comprising a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer and a hydrolyzable silyl group in the molecule. And an organosiloxane having at least one each of an acid anhydride group or an organosiloxane having at least one each of a hydrolyzable silyl group, an acid anhydride group, and a polyether group in the molecule are used for the bonding of optically functional films and liquid crystal cells In the case, it is possible to maintain good reworkability and improve durability at the same time, and it is suitable as an adhesive composition, and completed the present invention.

That is, the present invention provides: 1. An adhesive composition characterized by comprising: a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, and a copolymer represented by the following formula [1a] At least one of an organosiloxane having a hydrolyzable silyl group and an acid anhydride group in the molecule, and at least one of its hydrolysates, (In the formula, 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 containing a hydrolyzable silyl group. R ^{1 is} independent of each other and represents a hydrogen atom, or A monovalent hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen atom, M ^{1 is} independent of each other, and represents a group selected from the foregoing X, Y, Z, and R ¹ ; a, b, c, and d each represent 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 100, 0 ≦ d ≦ 100, but when a is 0, at least one of M ¹ is X and c is an integer of 1 ≦ c ≦ 100, where c is In the case of 0, at least one of M ¹ is Z and a is an integer of 1 ≦ a ≦ 100, and the arrangement of the repeating units in the parentheses marked a, b, c, and d may be random or block). 2. An adhesive composition comprising a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylic acid ester monomer and a hydrolyzable silane in a molecule represented by the following formula [1b] At least one of an organosiloxane and at least one of each of an organic group, an acid anhydride group and a polyether group, and a hydrolyzate thereof, (In the formula, 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 containing a hydrolyzable silyl group. R ^{1 is} independent of each other and represents a hydrogen atom, or A monovalent hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen atom, M ^{1 is} independent of each other, and represents a group selected from the foregoing X, Y, Z, and R ¹ ; a, b, c, and d each represent 0 ≦ a ≦ 100, Integers of 0 ≦ b ≦ 100, 0 ≦ c ≦ 100, 0 ≦ d ≦ 100, but when a is 0, at least one of M ¹ is X and b and c are 1 ≦ b ≦ 100, 1 ≦ An integer of c ≦ 100, when b is 0, at least one of M ¹ is Y, and a and c are integers of 1 ≦ a ≦ 100, 1 ≦ c ≦ 100, respectively, and when c is 0, M ¹ At least one is Z and a and b are integers of 1 ≦ a ≦ 100, 1 ≦ b ≦ 100, and the arrangement of the repeating units in the brackets marked a, b, c, and d may be random or block). 3. The adhesive composition according to 1 or 2, wherein the X is a monovalent hydrocarbon group having an acid anhydride group represented by the following formula [2], and the Y is a polyether group having a polyether group represented by the following formula [3] A monovalent hydrocarbon group, wherein Z is a monovalent hydrocarbon group containing a hydrolyzable silyl group represented by the following formula [5], (Wherein A represents an alkylene group having 2 to 6 carbon atoms), (In the formula, R ² represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a group represented by the following formula [4], m represents an integer of 2 or more, e and f are independent of each other, and represent 0 or more. Integer, but at least one of e and f is an integer of 1 or more), (Wherein R ³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), (In the formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, R ⁵ represents a monovalent hydrocarbon group or fluorenyl 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. The adhesive composition according to any one of 1 to 3, wherein at least one of the aforementioned R ¹ is a monovalent hydrocarbon group having a perfluoroalkyl group, 5. The adhesive composition according to any one of 1 to 4, The equivalent of the anhydride group of the aforementioned organosiloxane and its hydrolyzate is 5,000 g / mol or less. 6. The adhesive composition according to any one of 1 to 5, wherein the aforementioned copolymer contains a structure derived from a carboxyl group-containing monomer. At least one of a unit and a structural unit derived from a hydroxyl-containing monomer, 7. The adhesive composition according to any one of 1 to 6, wherein the organosiloxane and the hydrolysis thereof are relative to 100 parts by mass of the copolymer. The blending amount of at least one of the substances is 0.001 to 5 parts by mass. 8. The adhesive composition according to any one of 1 to 7, which contains 0.01 to 40 parts by mass relative to 100 parts by mass of the aforementioned copolymer. Part, 9. The adhesive composition according to 8, wherein the aforementioned cross-linking agent is selected from the group consisting of isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal-based cross-linking agents, aziridine-based cross-linking agents, and peroxides. At least one type of cross-linking agent, 10. A film with an adhesive layer, characterized in that: And at least one side of this film is 1 to 9 using any one of the adhesive composition layer formed. [Effect of the invention]

The adhesive composition of the present invention is suitable for use as an adhesive between an optically functional film and a liquid crystal cell in the manufacturing steps of a liquid crystal display device. Although it is peelable during bonding, it can be used under high temperature and high humidity conditions after bonding. Swelling or peeling is also unlikely to occur. The adhesive composition of the present invention having such characteristics can achieve the durability and reworkability required in order to achieve a high level in recent years. Therefore, it is suitable to use the surface of a protective film forming agent, a surface of a fiber or a powder as a substrate surface. A processing agent, an adhesive between substrates, and the like are particularly adhesive compositions used for bonding optically functional films in the manufacturing process of a liquid crystal display device.

The present invention will be specifically described below. The adhesive composition related to the present invention includes a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, an organosiloxane represented by the above formula [1a] or [1b], and a copolymer thereof. At least one of a hydrolysate (hereinafter simply referred to as an organosiloxane).

The copolymer of the (meth) acrylate-containing polymerizable unsaturated monomer is a component that functions as a base resin in the adhesive composition, as long as it is a (meth) acrylate-containing monomer. The copolymer of a polymerizable unsaturated monomer is not particularly limited. Specific examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (methyl) (Isopropyl) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as lauryl acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate; methoxyethyl (meth) acrylate, ethoxylate (meth) acrylate (Meth) acrylic alkoxyalkyl esters such as methyl ethyl; (meth) acrylic aryl esters such as phenoxyethyl (meth) acrylate; (methyl) benzyl (meth) acrylates (meth) ) Aralkyl acrylate; (meth) propylene carboxyalkyl esters such as β-carboxyethyl acrylate; 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- (meth) acrylate Hydroxyheptyl, 8-hydroxyoctyl (meth) acrylate, etc. Hydroxyalkyl acrylate; caprolactone denatured (meth) acrylate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. ) Acrylate, etc., these monomers can be used alone or in combination of two or more.共聚物 The copolymer of the present invention preferably contains 60 to 100% by mass of the repeating unit derived from the (meth) acrylate monomer, and more preferably 80 to 100% by mass.

In addition, considering that the resin used for bonding the optically functional film and the liquid crystal cell has pressure-sensitive adhesiveness, the copolymer of the present invention includes a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer. At least one of them is better. Specific examples of the carboxyl group and / or hydroxyl group-containing monomer which generates such a structural unit include the carboxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and polyalkylene glycol (methyl ), And (meth) acrylic acid, N- (2-hydroxyethyl) (meth) acrylamide, etc. These monomers can be used alone or in combination of two or more. In particular, in the copolymer used in the present invention, the content of the repeating unit derived from a carboxyl group and / or hydroxyl group-containing monomer is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass.

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 other monomers include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, and propylstyrene. , Butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, nitrostyrene, ethylfluorenylbenzene Styrene monomers such as ethylene and methoxystyrene; vinylpyridine, vinylpyrrolidone, vinylcarbazole, divinylbenzene, vinyl acetate, acrylonitrile, butadiene, isoprene, chlorine Vinyl monomers such as butadiene, vinyl chloride, vinyl bromide, and vinylidene chloride. These monomers can be used alone or in combination of two or more.含量 In the copolymer used in the present invention, the content of the repeating unit derived from the other monomer is preferably 0 to 20% by mass, and more preferably 0 to 10% by mass.

In addition, the copolymer used in the present invention is not particularly limited in the arrangement rules of the monomers, and may be any of a random copolymer, a block copolymer, and the like. The weight average molecular weight of the above-mentioned copolymer is not particularly limited. If it is considered to improve the cohesive force of the adhesive layer, and to suppress foaming or peeling of the adhesive layer, to improve durability, while maintaining the viscosity of the adhesive composition in an appropriate range For better operability, 100,000 to 2,000,000 is better, and 300,000 to 1,500,000 is better. In addition, the weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC).

The copolymer used in the present invention can be produced by a known polymerization method such as solution polymerization, block polymerization, emulsion polymerization, or suspension polymerization, and is particularly preferably produced by solution polymerization in which the copolymer is obtained as a solution. In this way, the copolymer is obtained in the form of a solution and can be directly used in the manufacture of the adhesive composition of the present invention. Organic solvents can be used as the solvent for the solution polymerization. Specific examples include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane; esters such as ethyl acetate and butyl acetate; n-propanol , Isopropyl alcohol and other aliphatic alcohols; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones. 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.

The polymerization initiator used in the polymerization may be appropriately selected and used by a publicly known person. Specific examples thereof include di-tert-butyl peroxide, benzamidine peroxide, lauryl peroxide, Third butyl peroxybenzoate, cumene hydrogen peroxide, diisopropyl peroxy dicarbonate, dipropyl peroxy dicarbonate, third butyl peroxy neodecanoate, third Peroxides such as butylperoxyvalerate, (3,5,5-trimethylhexyl) peroxide; azobisisobutyronitrile, azobisvaleronitrile, 1,1'- Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl (4-methoxyvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-hydroxymethylpropionitrile), etc. Can be used alone or in combination of two or more. In addition, 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 ° C, and the reaction time is usually 2 to 20 hours, preferably 4 to 12 hours.

On the other hand, as described above, the organosiloxane used in the adhesive composition of the present invention is represented by the formula [1a] or [1b]. This organosiloxane is a compound having a polysiloxane structure different from the compound described in Patent Document 5 (Japanese Patent No. 5990847) having an alkoxy group, an acid anhydride group, and a polyether group in the molecule. . In contrast, the polysiloxane framework of the compound described in Patent Document 5 has a three-dimensional structure. In contrast, the organosiloxane used in the present invention has a polysiloxane framework having a linear structure. Thereby, when it is added to an acrylic resin for use, the transferability on the resin surface is improved, and thus the functionality of the resin surface can be further improved. In addition, due to the structure of the compound, the reactivity with an inorganic substrate such as an alkoxy glass is improved. Therefore, when the optically functional film is bonded to the liquid crystal cell, durability can be further improved.

In 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 containing a hydrolyzable silyl group, and R ^{1 is} independent of each other and represents a hydrogen atom, Or a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, M ^{1 is} independent of each other, and represents a group selected from the above-mentioned X, Y, Z, and R ¹ . In addition, in the above formulas, a, b, c, and d represent integers of 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 100, and 0 ≦ d ≦ 100, but in formula [1a] In the case where a is 0, at least one of M ¹ is X and c is an integer of 1 ≦ c ≦ 100, and when c is 0, at least one of M ¹ is Z and a is 1 ≦ a ≦ 100 Integer, in formula [1b], when a is 0, at least one of M ¹ is X, and b and c are integers of 1 ≦ b ≦ 100, 1 ≦ c ≦ 100, and when b is 0, At least one of M ¹ is an integer of Y and a and c are 1 ≦ a ≦ 100 and 1 ≦ c ≦ 100, respectively. When c is 0, at least one of M ¹ is Z and a and b are 1 ≦ a. An integer of ≦ 100 and 1 ≦ b ≦ 100. In addition, in the above formulas, the arrangement of the repeating units in the parentheses marked a, b, c, and d may be random or block.

Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-pentyl, Linear, branched or cyclic alkyl groups such as neopentyl, n-hexyl, cyclohexyl, n-octyl, n-nonyl, n-decyl, n-octadecyl; phenyl, tolyl, stubyl, Aryl groups such as naphthyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl. Specific examples of the monovalent hydrocarbon group in which a hydrogen atom is partially or entirely substituted with a halogen atom include chloromethyl, trifluoromethyl, and chloropropyl. Among these, R ^{1 is} preferably a methyl group or a monovalent hydrocarbon group having a perfluoroalkyl group, and more preferably a methyl group or an alkyl group (fluoroalkyl group) substituted with a perfluoroalkyl group. Specific examples of the fluoroalkyl group include CF ₃ -C ₂ H _4- , CF ₃ -C ₃ H _6- , C ₄ F ₉ -C ₂ H _4- , C ₄ F ₉ -C ₃ H _6- , The bases represented by C ₆ F ₁₃ -C ₂ H _4- , C ₆ F ₁₃ -C ₃ H _6- , C ₈ F ₁₇ -C ₂ H _4- , C ₈ F ₁₇ -C ₃ H _6- .

By introducing the above-mentioned monovalent hydrocarbon group as R ¹ in the organosiloxane of the present invention, when mixed with the above-mentioned copolymer of the base resin, the compatibility with the resin is improved, and phase separation and the like are unlikely to occur. Therefore, each of the above R ¹ At least one of them is preferably a monovalent hydrocarbon group, all of them are preferably monovalent hydrocarbon groups, and all of R ¹ is a methyl group, or a combination of a methyl group and a monovalent hydrocarbon group having a perfluoroalkyl group is more preferable.

In addition, the organosiloxane used in the present invention contains a monovalent hydrocarbon group X having an acid anhydride group, so that the monovalent hydrocarbon group X exists. When the organosiloxane is added to the base resin, the monovalent hydrocarbon group X has An acid anhydride group reacts with a reactive group (such as a hydroxyl group and a carboxyl group) of the base resin, thereby achieving integration of the resin and the organosiloxane. Examples of the monovalent hydrocarbon group among the monovalent hydrocarbon groups having an acid anhydride group include the same groups as those exemplified above for R ^{1. An} alkyl group is preferred, and a linear alkyl group is preferred. Examples of the acid anhydride group include a succinic anhydride group and a maleic anhydride group. Suitable X includes a group represented by the following formula [2].

The A represents an alkylene group having 2 to 6 carbon atoms, and specific examples thereof include straight or branched chains such as ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene. As the alkylene group, especially trimethylene is preferred, so X is preferably succinic anhydride propyl.

In addition, the organosiloxane used in the present invention has a monovalent hydrocarbon group Z containing a hydrolyzable silyl group. By having the monovalent hydrocarbon group Z, an inorganic substrate such as glass is surface-treated with the organosiloxane. In this case, the hydrolyzable silyl group reacts with the -OH group existing on the surface of the inorganic substrate, and a chemical bond is formed between the organic siloxane and the inorganic substrate. Examples of the monovalent hydrocarbon group containing a hydrolyzable monovalent hydrocarbon group include the same groups as those exemplified for R ¹ described above. An alkyl group is preferred, and a linear alkyl group is preferred. Suitable Z includes a group represented by the following formula [5].

The above R ⁴ represents an alkyl group having 1 to 10 carbon atoms, R ⁵ represents a monovalent hydrocarbon group or fluorenyl group having 1 to 10 carbon atoms, and n represents an integer of 2 or more, preferably an integer of 2 to 5, and preferably 2 Or an integer of 3, and g represents an integer of 1 to 3, preferably 2 or 3, and more preferably 3. Specific examples of the alkyl group having 1 to 10 carbon atoms include the same groups as the alkyl group having 1 to 10 carbon atoms among the alkyl groups exemplified in the above R ¹ , and a methyl group and an ethyl group are preferred. Specific examples of the monovalent hydrocarbon group include the same groups as those exemplified for R ¹ described above, and an alkyl group and an aromatic group are preferred. Specific examples of the fluorenyl group include methyl fluorenyl and ethenyl.

Specific examples of the hydrolyzable silyl group (except for -C _n H _2n -in the formula [5]) include trimethoxysilyl group, methyldimethoxysilyl group, and dimethyl group. Monomethoxysilyl, triethoxysilyl, methyldiethoxysilyl, dimethylmonoethoxysilyl, tripropoxysilyl, methyldipropoxy Methylsilyl, dimethylmonopropoxysilyl, triisopropenylsilyl, methyldiisopropenylsilyl, dimethylisopropenylsilyl, trioxo As a silyl group, a methyldimethoxysilyl group, a dimethylmonomethoxysilyl group, etc., at least 1 sort (s) selected from this group can be used. Preferably it is trimethoxysilyl.

In addition, 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 between the reactivity to the organic resin and the reactivity to the inorganic substrate 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. This polyether group has the effect of controlling the affinity of the organosiloxane with the surface of the inorganic substrate. That is, in an organosiloxane containing only a hydrolyzable silyl group and an acid anhydride group as an organic functional group, the acid anhydride group has a low hydrophilicity. Therefore, as the number thereof increases, the hydrophilicity of the entire molecule may be significantly reduced. Therefore, when this organosiloxane is coated on an inorganic substrate having a hydrophilic surface to form a hardened film, problems such as poor wettability and repulsion may occur, and a problem that a uniform coating film cannot be obtained may occur. However, by introducing a polyether group into the above-mentioned organosiloxane, the problem is solved, and a uniform organosiloxane hardened film can be formed on the inorganic substrate. In addition, by adjusting the type or introduction amount of the polyether group and controlling the reaction between the hydrolyzable silyl group and the inorganic substrate, the binding force between the substrate and the organosiloxane can be adjusted. With this, when an organosiloxane is used for the adhesion between an organic resin and an inorganic substrate, the adhesion force can be adjusted from microadhesion to strong adhesion according to the application.

Specific examples of the monovalent hydrocarbon group among the polyvalent group-containing monovalent hydrocarbon groups include the same groups as those exemplified for R ¹ described above. An alkyl group is preferred, and a linear alkyl group is preferred. Suitable Y includes a group represented by the following formula [3].

The R ² represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a group represented by the following formula [4].

(Wherein R ³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms)

Examples of the monovalent hydrocarbon group in the formulas [3] and [4] include groups in which the number of carbon atoms meets the conditions among the groups exemplified in the above R ¹ . R ² is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. e and f are independent of each other and represent an integer of 0 or more, preferably an integer in a range of 0 ≦ e ≦ 50, 0 ≦ f ≦ 50, and an integer in a range of 0 ≦ e ≦ 20, 0 ≦ f ≦ 20 good. However, at least one of e and f is 1 or more, and preferably an integer of 1 to 50. m represents an integer of 2 or more, and an integer of 2 to 6 is preferable.

The polyether-based moiety may be of ethylene oxide type (hereinafter referred to as EO type), propylene oxide type (hereinafter referred to as PO type), ethylene oxide-propylene oxide type (hereinafter referred to as EO-PO type) In the case of the EO-PO type, any of) may be any of random, block, and interactive. In addition, by introducing a monovalent hydrocarbon group having a PO-type polyether group into the organosiloxane used in the present invention, moisture resistance can be improved.

The polyether group portion may be a fluorinated polyether group in which at least a part of a hydrogen atom is substituted with fluorine. By containing fluorine, the transferability of the organosiloxane used in the present invention on the resin surface can be improved, or the affinity between the resin surface and the coating body can be controlled. The fluorinated polyether group is not particularly limited, but is preferably composed of at least one selected from the structural units shown below.

Specific examples of the monovalent hydrocarbon group of the polyether group having fluorine include the following structures.

Suitable examples of the organosiloxane used in the present invention include the compounds represented by the following formulas [12] and [13], and are not limited thereto. In addition, the arrangement of each siloxane unit in the organosiloxane represented by the following formulas [12] and [13] may be random or block.

The acid anhydride group equivalent of the organosiloxane used in the present invention is not particularly limited, and is preferably 5,000 g / mol or less, more preferably 2,000 g / mol or less, even more preferably 1,500 g / mol or less, and 1,000 g / mol. The following is better.

The organosiloxane described above can be obtained by combining an organohydrosiloxane represented by the following formula [7] with a hydrolyzable silyl compound having an aliphatic unsaturated bond under a platinum catalyst, and having an aliphatic The unsaturated bond-containing compound containing an acid anhydride group and the polyether group-containing compound having an aliphatic unsaturated bond are subjected to a hydrosilylation reaction if necessary.

In the formula [7], R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and M ² represents a hydrogen atom or the aforementioned R ¹⁰ . i and j each represent an integer of 1 ≦ 1 ≦ 300, 0 ≦ j ≦ 100, and preferably an integer in the range of 1 ≦ i ≦ 150, 0 ≦ j ≦ 50, and preferably 1 ≦ i ≦ 60, 0 ≦ j ≦ 20 range integer. The arrangement of the repeating units in the parentheses marked with i and j may be random or block.

In this case, the hydrolyzable silyl group-containing compound having an aliphatic unsaturated bond includes, for example, a compound represented by the following formula [8].

(In the formula, p represents 0 to 10, preferably an integer of 0 to 5, and R ⁴ , R ⁵ and g have the same meanings as above.)

Specific examples of the hydrolyzable silyl-containing compound having the above-mentioned unsaturated bond include vinyl-containing alkoxysilane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane. The reaction ratio at the time of the hydrosilylation reaction is preferably 1 to 100 mol, more preferably 1 to 50 mol, and more preferably 1 to 20 mol relative to 1 mol of the organohydrosiloxane.

Examples of the acid anhydride group-containing compound having the above-mentioned aliphatic unsaturated bond include compounds represented by the following formula [9].

(In the formula, p represents the same meaning as 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 preferred. The reaction ratio at the time of the hydrosilylation reaction is preferably 1 to 100 mol, more preferably 1 to 50 mol, and more preferably 1 to 20 mol relative to 1 mol of the organohydrosiloxane.

Examples of the polyether group-containing compound having an aliphatic unsaturated bond include compounds represented by the following formula [10].

(In the formula, p, R ² , e, and f have the same meanings as described above.)

In particular, the polyether group-containing compound having an unsaturated bond is preferably an allyl polyether represented by the following formula [11]. The reaction ratio at the time of the hydrosilylation reaction is preferably 1 to 100 mol, more preferably 1 to 50 mol, and more preferably 1 to 20 mol relative to 1 mol of the organohydrosiloxane.

(Wherein R ² , e, and f have the same meanings as above)

More specifically, for example, in the case of the compound represented by the above formula [12], vinyl trimethoxy group can be made under a platinum catalyst with respect to 1 mol of methylhydrosiloxane represented by the following formula [14]. 4 mol of silane, 1 mol of allyl polyether represented by following formula [15], and 3 mol of allyl succinic anhydride were hydrosilylated to produce it.

In the case of the compound represented by the above formula [13], 4 mol of vinyltrimethoxysilane and olefin can be used in a platinum catalyst with respect to 1 mol of methylhydrosiloxane represented by the following formula [16]. 4 mol of propyl succinic anhydride was produced by hydrosilylation reaction.

The alkoxysilane compound used in the present invention can also be produced by a method other than the method described above. For example, the alkoxysilane compound can be hydrolyzed and condensed by succinic anhydride-denatured alkoxysilane and polyether-modified alkoxysilane Method to manufacture. However, since this method uses water, there is a problem of a ring-opening reaction caused by hydrolysis of succinic anhydride during the manufacturing stage. In addition, in another method, for example, vinyltrimethoxysilane, allyl polyether, and allyl succinic anhydride can be sequentially added to the following formula [17] under a platinum catalyst. Cyclic organohydrogen siloxane.

(Where k is an integer of 3 or more)

However, among the above-mentioned cyclic organic hydrosiloxanes, low-molecular-weight siloxanes having k = 3 to 5 are cheap and easily available in reality. In this case, the maximum number of reaction points (SiH) existing in the molecule is only five. When it is desired to sequentially add vinyl trimethoxysilane, allyl polyether, and allyl succinic anhydride to the cyclic organohydrosiloxane through the hydrosilylation reaction, the total introduction amount of each compound is only It can be up to five, and the introduction amount of each functional group cannot be freely set.

In contrast, the above-mentioned method for producing an organosiloxane according to the present invention can solve the above problems. That is, the introduction of vinyl trimethoxysilane, allyl polyether, and allyl succinic anhydride can be freely set by adjusting the i value of the organohydrosiloxane represented by the above-mentioned formula [7] used as a raw material. the amount.的 The organosiloxane used in the present invention has a structure in which a functional group containing an alkoxy group, an acid anhydride group, and a polyether group is bonded to a side chain of a linear siloxane skeleton.

In the adhesive composition of the present invention, the blending ratio of the copolymer as the base resin and the alkoxysilane is not particularly limited, and it is blended with respect to 100 parts by mass of the copolymer as the base resin. 0.001 to 5 parts by mass of organosiloxane is preferred, 0.01 to 3 parts by mass is preferred, and 0.1 to 2 parts by mass is more preferred.

In addition, a crosslinking agent may be blended in the adhesive composition of the present invention. The blending amount of the cross-linking agent is not particularly limited. If the cohesive force of the adhesive composition is considered to be moderate, the durability is improved, and the peeling of the adhered film is effectively suppressed, the ratio is based on 100 parts by mass of the copolymer. The blending crosslinking agent is preferably 0.01 to 40 parts by mass, and the blending agent is more preferably 0.02 to 30 parts by mass.

The crosslinking agent is not particularly limited. In the present invention, a group selected from the group consisting of an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a metal chelate crosslinking agent, and an aziridine-based crosslinking agent is suitably used. Crosslinking agent. More specifically, for example, a polyglycidyl compound having two or more glycidyl groups in one molecule, a polyisocyanate compound having two or more isocyanate groups in one molecule, and two or more aziridinyl groups in one molecule can be cited. Polyaziridine compounds, metal chelate compounds, or butylated melamine compounds, etc., these can be used alone or in combination of two or more.

Specific examples of the polyglycidyl compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, and neoglutaric acid. Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-di Polyfunctional glycidyl compounds, such as glycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, etc., These can be used individually or in combination of 2 or more types.

Specific examples of the polyisocyanate compound include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate. Isocyanates, naphthalene diisocyanates, triphenylmethane triisocyanates, etc., or adducts obtained by reacting these isocyanate compounds with polyols such as glycerol or trimethylolpropane, or the isocyanate compounds are made into dimers or trimers And the like, these can be used alone or in combination of two or more kinds.

Specific examples of the polyaziridine compound include 1,1 '-(methylene-di-p-phenylene) bis-3,3-aziridinyl urea, and 1,1'-(hexamethylene) Bis-3,3-aziridinyl urea, ethylene bis- (2-aziridinyl propionate), ginseng (1-aziridinyl) phosphine oxide, 2,4,6-triaziridine -1,3,5-triazine, trimethylolpropane-shen- (2-aziridinylpropionate), etc. These can be used alone or in combination of two or more. Specific examples of the metal chelate compound include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Ester compounds and the like can be used alone or in combination of two or more kinds.

In addition, regarding the cross-linking form, radiation (preferably ultraviolet) cross-linking is also effective. In this case, a monomer having at least two polymerizable reactive double bonds and a photopolymerization initiator (including a sensitizer may also be added). ). Specific examples of the monomer having at least two polymerizable double bonds include polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, and tricyclodecane dimethanol diacrylate. , 1, 9-monononanediol diacrylate, and other bifunctional (meth) acrylates; trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, isotrimeric cyanate Polyfunctional (meth) acrylates such as acrylate, ginseng (2-propenyloxyethyl) isocyanurate, and the like. In addition, if necessary, a known monomer having only one polymerizable reactive double bond may be used in combination to control the crosslinking density. As the photopolymerization initiator, a photopolymerization initiator using a known radiation (ultraviolet rays) can be used, and examples thereof include amine ketone, hydroxy ketone, fluorenyl phosphine oxide, benzyl dimethyl ketal, and diphenyl Ketone-based, trichloromethyl-containing triazine derivative-based photopolymerization initiators, and the like.

In addition, in the adhesive composition of the present invention, a silane coupling agent and / or a hydrolyzed condensate thereof (combinedly referred to as a silane coupling agent) other than the above-mentioned essential organosiloxane may be added, thereby further improving Durability of the adhesive layer formed from the adhesive composition. The addition amount of the hydrazine coupling agent is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the copolymer.

Specific examples of the silane coupling agent include γ-glycidyletheroxypropyltrimethoxysilane, γ-glycidyletheroxypropyltriethoxysilane, and γ-glycidyletheroxypropylmethyldi Methoxysilane, γ-glycidyl etheroxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, epoxy-containing alkoxysilane Epoxy-containing silane coupling agents such as oligomers; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Mercaptopropylmethyldiethoxysilane, mercapto-containing alkoxysilane oligomers and other mercapto-containing silane coupling agents; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (amineethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl ) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and other amine-containing silane coupling agents; γ-isocyanatepropyltrimethoxysilane, γ -Isocyanatepropyltriethoxysilane Silane coupling agent, isocyanate groups, these may be used alone or in combination of two or more thereof.

In addition, various additives may be blended in the adhesive composition of the present invention in order to adjust the adhesion and the like, in accordance with necessary characteristics, so long as the effect of the present invention is not impaired. Examples of the additives include terpene-based, terpene-phenol-based, coumarone-indene-based, styrene-based, turpentine-based, xylene-based, phenol-based, petroleum-based adhesion-imparting resins, antioxidants, ultraviolet absorbers, Fillers, pigments, plasticizers, antistatic agents, etc.

The film with an adhesive layer of the present invention includes a film and a layer formed by using the adhesive composition of the present invention on at least one side of the film. That is, a single-sided or double-sided laminate of an optically functional film (hereinafter referred to as a "raw material film") on which an adhesive layer is not formed is excellent in the "durability" and "reworkability" of the present invention. An article made of a film (adhesive layer) made of an adhesive composition. Therefore, the film with an adhesive layer of the present invention has the characteristics that it does not peel off from the glass substrate or the like constituting the liquid crystal cell even under high temperature or high humidity, and does not cause foaming in the adhesive layer (durable) Properties) and easy peeling even after a long period of time. In addition, after peeling, there is no property (reworkability) of the substrate or the like.

The type of the raw material film is not particularly limited, and examples thereof include a thin film light guide plate, an anti-reflection film, a conductive film, a viewing angle magnifying film, a phase difference film, a polarizing plate, and a combination of these films. In addition, in order to improve the adhesion of the film made of the adhesive composition of the present invention to the original thin film, a surface treatment such as corona treatment may be performed on the surface of the original thin film. The thickness of the raw material film is not particularly limited, as long as it is set to an appropriate thickness according to the use or purpose, for example, it may be set to about 5 to 300 μm.

The film with an adhesive layer of the present invention can be applied on one or both sides of the raw material film by using a commonly used coating device, such as a roll coating device, so that the coating can be applied. The layer was dried to form a film (adhesive layer). In addition, if necessary, the applied adhesive layer can be hardened by heating light such as cross-linking or ultraviolet rays to form a cured film. In addition, in the film with an adhesive layer of the present invention, first, a protective film such as a polyethylene terephthalate film (PET film) coated with a release agent such as silicone resin is applied on the surface to apply the adhesive of the present invention. After the composition is dried to form an adhesive layer, a raw material film is pasted on the adhesive layer to obtain the composition. In any of the above cases, the coating amount of the adhesive composition is preferably such that the thickness of the dried adhesive layer (film) is about 10 to 50 μm. By setting the thickness of the adhesive layer within the above range, it becomes a film with an adhesive layer suitable as an optically functional film and more balanced with durability and reworkability.

The film with an adhesive layer of the present invention produced as described above can be attached to a glass substrate of a liquid crystal cell such as a liquid crystal display device by a commonly used method. In addition, the film with an adhesive layer of the present invention may be further laminated and attached to an optically functional film attached to a glass substrate. [Example]

Examples and comparative examples are given below to explain the present invention more specifically, but the present invention is not limited to these examples. Examples of the apparatus used in the examples are as follows. Infrared Spectroscopy (FTIR): NICOLET6700 ²⁹ Si-NMR manufactured by Thermo Sientific: AVANCE400M GPC manufactured by Bruker: HLC-8220GPC manufactured by Tosoh

[1] Preparation of base resin [Synthesis Example-1] Preparation of copolymer solution-1 In a 1-liter separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, nitrogen was introduced to replace the air in the device. For nitrogen. Next, the flask was charged with 70.0 g of n-butyl acrylate (BA), 30.0 g of methacrylate (MA), 0.3 g of acrylic acid (AA), 1.7 g of 2-hydroxyethyl acrylate (2HEA), and azo. 0.1 g of bisisobutyronitrile and 100 g of ethyl acetate were stirred and reacted at 70 ° C for 10 hours to obtain an acrylic copolymer solution-1. The weight average molecular weight of the copolymer measured by GPC was 1,500,000.

[Synthesis Example 1-2] The copolymer solution-2 was prepared in the same manner as in Synthesis Example 1 except that acrylic acid (AA) was not used, 2.0 g of 2-hydroxyethyl acrylate (2HEA) was not used, and acrylic acid (AA) was not used. To obtain a copolymer solution-2. The weight average molecular weight of the copolymer measured by GPC was 1,500,000.

[2] Synthesis of organosiloxane [Synthesis Example 2-1] (1) A 1-liter three-necked flask equipped with a stirrer, a thermometer, and a Dairy condenser was charged with 100 g of organohydrosiloxane represented by the following formula [18] (0.192 mol) and 114 g of toluene, and then 1.00 g of a toluene solution of a vinylsiloxane coordinated Pt was added with stirring. Next, the temperature was raised to 80 ° C, and 567 g (0.383 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Here, the reaction rate of the vinyltrimethoxysilane used for the said reaction was measured as follows. First, the ≡SiH content in 1 g of the sample before and after the reaction was measured by the following method. 10 g of butanol were added to 1 g of the sample before and after the reaction, and 20 g of a 20% by mass NaOH aqueous solution was further added with stirring. From this, the amount of hydrogen gas (≡SiH + H ₂ O → ≡SiOH + H ₂ ↑) was used to calculate the content of ≡SiH. Next, the amount of vinyltrimethoxysilane actually reacted in 1 g of the sample was calculated according to the following formula. The results are shown in Table 1. Reaction amount (mol) = [≡SiH content (mol) before reaction]-[≡SiH content (mol) after reaction]

In 1 g of the sample before the reaction, 1.41 × 10 ^-3 mol of vinyltrimethoxysilane was charged as a raw material. From the previously obtained reaction amount and the amount charged as a raw material, the reaction rate of vinyltrimethoxysilane was calculated as follows, and it was 99.3%. [Reaction rate = 1.40 × 10 ^-3 (mol) /1.41×10 ^-3 (mol) × 100 = 99.3 (%)] From the above calculations, it was confirmed that the vinyl group charged as a raw material through the hydrosilylation reaction More than 99% of trimethoxysilane reacts with methylhydrosilane.

Next, an operation for reacting allyl succinic anhydride with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane complex with Pt was added under stirring, and the temperature was raised to 110 ° C. Next, 120 g (0.857 mol) of allyl succinic anhydride was added dropwise, and then aging was performed at 115 ° C for 10 hours. Here, the reaction rate of allyl succinic anhydride was measured. First, the ≡SiH content in 1 g of the sample before and after the reaction was measured by the same method as above, and the amount of the allyl succinic anhydride actually reacted was calculated. The results are shown in Table 2.

After the completion of the reaction, the amount of hydrogen generated was approximately close to 0 ml. From this, it can be considered that almost all of ≡SiH remaining in methylhydrosiloxane is reacted with allylsuccinic anhydride by the hydrosilylation reaction. In 1 g of the sample before the reaction, 2.17 × 10 ^-3 mol of allylsuccinic anhydride charged as a raw material was present. From the previously obtained reaction amount and the amount charged as a raw material, the reaction rate of allyl succinic anhydride was calculated as follows, and it was 87.6%. [1.90 × 10 ^-3 (mol) /2.17×10 ^-3 (mol) × 100 = 87.6 (%)] Approximately 88% of allyl succinic anhydride charged as a raw material reacts with methyl hydrosiloxane, and the rest About 12% remained as the remainder.

Finally, an operation for removing residual allylsuccinic anhydride was performed. The Dessert condenser was connected to an exhaust pipe, and the pressure in the system was reduced to 10 mmHg, and then heated under a bubble of nitrogen and heating at 150 ° C for 20 hours. 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 filtered and purified to obtain 246 g of product-1. Here, GPC measurement was performed on Product-1 in a THF solvent. As a result, a broad product peak was confirmed at a position with a retention time of 21 to 32 minutes. The peak of the allyl succinic anhydride did not exist near the retention time of 36 to 37 minutes. Therefore, it was considered that the remaining fraction of the allyl succinic anhydride was almost completely removed by the final reduced-pressure heating.

Next, for product-1, the assignment of an acid anhydride group was performed by infrared spectroscopy (FTIR). As a result, absorption by carbonyl stretching vibration of the succinic anhydride group was observed at 1863 cm ^-1 and 1785 cm ^-1 . In addition, absorption at 1735 cm ^-1 due to carbonyl stretching vibration of the carboxyl group due to ring opening of the succinic anhydride group was not observed. Product-1 is manufactured in a completely non-aqueous system. Therefore, during the manufacturing stage, compounds containing active hydrogen (eg, water or alcohol) are not mixed, and ring opening of the succinic anhydride group is sufficiently suppressed.

Next, in order to analyze the structure of Product-1, a ²⁹ Si-NMR measurement was performed. As a result, at first around 7.2 ppm, one peak suggesting the existence of the structure shown below was confirmed.

In addition, around -22 ppm, one peak suggesting the existence of the structure shown below was confirmed.

In the formula, R represents any one of the following groups.

In addition, one peak suggesting the presence of a group shown below was confirmed near -42 ppm.

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 a side chain of a linear siloxane. Here, from the charged amount of each raw material of methylhydrosiloxane, vinyltrimethoxysilane and allylsuccinic anhydride, and the measurement result of the above reaction rate, 1 mol relative to methylhydrosiloxane is calculated. Number of trimethoxysilyl groups and succinic anhydride groups introduced in the reaction (average value). Table 3 shows the amount of each functional group introduced and the equivalent of the acid anhydride group.

[Synthesis Example 2-2] In the same manner as in Synthesis Example 2-1, 100 g (0.0371 mol) of methylhydrosiloxane represented by the following formula [19] and 114 g of toluene were charged, and then vinyl silicon was added with stirring. 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of an oxane complex of Pt. Next, the temperature was raised to 80 ° C., and 55.0 g (0.371 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Next, an operation for reacting allyl succinic anhydride with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane coordinated Pt was added under stirring, and the temperature was raised to 110 ° C. Next, 62.3 g (0.445 mol) of allyl succinic anhydride was added dropwise, and then aging was performed at 115 ° C for 10 hours. Finally, in the same manner as in Synthesis Example 2-1, an operation for removing residual allyl succinic anhydride was performed, and the resulting liquid was filtered and purified to obtain 178 g of product-2. Here, in the same manner as in Synthesis Example 2-1, the number (average value) of trimethoxysilyl groups and succinic anhydride groups introduced into the reaction was calculated with respect to 1 mol of methylhydrosiloxane. Table 3 shows the amount of each functional group introduced and the equivalent of the acid anhydride group.

[Synthesis Example 2-3] In the same manner as in Synthesis Example 2-1, 100 g (0.0371 mol) of methyl hydrosiloxane represented by the above formula [19] and 114 g of toluene were charged, and then vinyl siloxane was added with stirring. 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of an alkane complex with Pt. Next, the temperature was raised to 80 ° C., and 55.0 g (0.371 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours. Next, an operation for reacting 3- (perfluorohexyl) -1-propene with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. The temperature of the reaction solution obtained above was raised to 100 ° C, and 26.7 g (0.0742 mol) of 3- (perfluorohexyl) -1-propene was added dropwise, followed by further aging for 5 hours.

Next, an operation for reacting allyl succinic anhydride with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane coordinated Pt was added under stirring, and the temperature was raised to 110 ° C. Next, 62.3 g (0.445 mol) of allyl succinic anhydride was added dropwise, and then aging was performed at 115 ° C for 10 hours. Finally, in the same manner as in Synthesis Example 2-1, an operation for removing residual allyl succinic anhydride was performed, and the obtained liquid was filtered and purified to obtain 199 g of product-3. Here, in the same manner as in Synthesis Example 2-1, the number of trimethoxysilyl groups, perfluorohexyl groups, and succinic anhydride groups (average value) introduced in the reaction was calculated with respect to 1 mol of methylhydrosiloxane. Table 3 shows the amount of each functional group introduced and the equivalent of the acid anhydride group.

[Synthesis Example 2-4] In the same manner as in Synthesis Example 2-1, 100 g (0.192 mol) of methyl hydrosiloxane represented by the above formula [18] and 114 g of toluene were charged, and then vinyl siloxane was added with stirring. 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of an alkane complex with Pt. Next, the temperature was raised to 80 ° C, and 56.9 g (0.384 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours. Next, an operation for reacting an allyl polyether with a part of the ≡Si-H group remaining in methylhydrosiloxane is performed. 81.4 g (0.192 mol) of allyl polyether represented by CH ₂ = CH-CH ₂ -O (CH ₂ CH ₂ O) ₈ CH ₃ was added dropwise while the reaction solution was maintained at 80 ° C. After that, aging was performed for 3 hours. Next, an operation for reacting allyl succinic anhydride with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. The temperature of the reaction solution was raised to 110 ° C., and 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane coordinated Pt was added under stirring, and 121 g (0.864 mol) of allylsuccinic anhydride was further added dropwise. It was aged at 115 ° C for 10 hours. Finally, in order to remove the residual allyl succinic anhydride, the pressure was reduced to 10 mmHg in the same manner as in Synthesis Example 2-1, and then the mixture was heated under nitrogen bubbling and at 120 ° C for 20 hours. 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 filtered and purified to obtain 271 g of product-4. Here, in the same manner as in Synthesis Example 2-1, the number (average value) of trimethoxysilyl groups, polyether groups, and succinic anhydride groups introduced in the reaction was calculated with respect to 1 mol of methylhydrosiloxane. Table 3 shows the amount of each functional group introduced and the equivalent of the acid anhydride group.

[Synthesis Example 2-5] In the same manner as in Synthesis Example 2-1, 100 g (0.0371 mol) of methyl hydrosiloxane represented by the above formula [19] and 114 g of toluene were charged, and then vinyl siloxy was added with stirring. 1.00 g of a toluene solution (Pt concentration; 0.5% by mass) of an alkane complex with Pt. Next, the temperature was raised to 80 ° C., 16.5 g (0.111 mol) of vinyltrimethoxysilane was added dropwise, and the mixture was aged for 2 hours. Next, an operation for reacting the allyl polyether with the remaining ≡Si-H group contained in the methylhydrosiloxane is performed. While maintaining the reaction solution at 80 ° C, 271 g of allyl polyether represented by CH ₂ = CH-CH ₂ -O (CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ was added dropwise with stirring ( After 0.335 mol), aging was performed for 3 hours. Next, an operation for reacting allyl succinic anhydride with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration; 0.5% by mass) of a vinylsiloxane coordinated Pt was added under stirring, and the temperature was raised to 110 ° C. Next, 62.3 g (0.445 mol) of allyl succinic anhydride was added dropwise, and then aging was performed at 115 ° C for 10 hours. Finally, in the same manner as in Synthesis Example 2-4, an operation for removing residual allyl succinic anhydride was performed, and the obtained liquid was filtered and purified to obtain 367 g of product-5. Here, in the same manner as in Synthesis Example 2-1, the number (average value) of trimethoxysilyl groups, polyether groups, and succinic anhydride groups introduced in the reaction was calculated with respect to 1 mol of methylhydrosiloxane. Table 3 shows the amount of each functional group introduced and the equivalent of the acid anhydride group.

[Synthesis Example 2-6] In the same manner as in Synthesis Example 2-1, 100 g (0.0371 mol) of methyl hydrosiloxane represented by the above formula [19] and 114 g of toluene were charged, and then vinyl siloxane was added with stirring. 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of an alkane complex with Pt. Next, the temperature was raised to 80 ° C., 16.5 g (0.111 mol) of vinyltrimethoxysilane was added dropwise, and the mixture was aged for 2 hours. Next, an operation for reacting the allyl polyether with the remaining ≡Si-H group contained in the methylhydrosiloxane is performed. While the reaction solution was maintained at 80 ° C, 420 g of allyl polyether represented by CH ₂ = CH-CH ₂ -O (CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ was added dropwise with stirring ( After 0.519 mol), aging was performed for 3 hours. Next, an operation for reacting allyl succinic anhydride with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane coordinated Pt was added under stirring, and the temperature was raised to 110 ° C. Next, 23.4 g (0.167 mol) of allyl succinic anhydride was added dropwise, and then aging was performed at 115 ° C for 10 hours. Finally, in the same manner as in Synthesis Example 2-4, an operation for removing residual allylsuccinic anhydride was performed, and the obtained liquid was filtered and purified to obtain 475 g of product-6. Here, in the same manner as in Synthesis Example 2-1, the number (average value) of trimethoxysilyl groups, polyether groups, and succinic anhydride groups introduced in the reaction was calculated with respect to 1 mol of methylhydrosiloxane. Table 3 shows the amount of each functional group introduced and the equivalent of the acid anhydride group.

[Synthesis Example 2-7] In the same manner as in Synthesis Example 2-1, 100 g (0.0371 mol) of methyl hydrosiloxane represented by the above formula [19] and 114 g of toluene were charged, and then vinyl siloxane was added with stirring. 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of an alkane complex with Pt. Next, the temperature was raised to 80 ° C., and 55.0 g (0.371 mo 1) 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 methylhydrosiloxane is performed. While maintaining the reaction solution at 80 ° C., 60.1 g of an allyl polyether represented by CH ₂ = CH-CH ₂ -O (CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ was added dropwise with stirring. After (0.0742 mol), aging was performed for 3 hours. Next, an operation for reacting 3- (perfluorohexyl) -1-propene with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. To the obtained reaction solution, 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane complex Pt was added under stirring, and the temperature was raised to 100 ° C. Next, 26.7 g (0.0741 mol) of 3- (perfluorohexyl) -1-propene was added dropwise, followed by aging for 5 hours. Further, an operation for reacting allyl succinic anhydride with a residual ≡Si-H group contained in methylhydrosilane was performed. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane coordinated Pt was added under stirring, and the temperature was raised to 110 ° C. Next, 46.8 g (0.334 mol) of allyl succinic anhydride was added dropwise, and then aging was performed at 115 ° C for 10 hours. Finally, in the same manner as in Synthesis Example 2-4, an operation for removing residual allyl succinic anhydride was performed, and the obtained liquid was purified by filtration to obtain 230 g of product-7. Here, in the same manner as in Synthesis Example 2-1, the number of trimethoxysilyl groups, polyether groups, perfluorohexyl groups, and succinic anhydride groups (averaged) introduced with respect to 1 mol of methylhydrosiloxane was calculated. value). Table 3 shows the amount of each functional group introduced and the equivalent of the acid anhydride group.

[Synthesis Example 2-8] A 1-liter three-necked flask equipped with a stirrer, a thermometer, and a Dessert condenser was charged with 100 g (0.0371 mol) of methyl hydrosiloxane represented by the above formula [19] and 114 g of toluene. With stirring, 1.00 g of a toluene solution (Pt concentration: 0.5% by mass) of a vinylsiloxane-coordinated Pt was added. Next, the temperature was raised to 80 ° C., and 55.0 g (0.371 mol) 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 methylhydrosiloxane is performed. While maintaining the reaction solution at 80 ° C, 60.1 g of an allyl polyether represented by CH ₂ = CH-CH ₂ -O (CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ was added dropwise with stirring. After (0.0742 mol), aging was performed for 3 hours. Next, an operation for reacting allyl glycidyl ether with the remaining ≡Si-H group contained in methylhydrosiloxane is performed. After 50.7 g (0.445 mol) of allyl glycidyl ether was added dropwise to the reaction solution obtained above, aging was performed for 10 hours. Finally, in order to remove the residual allyl glycidyl ether, it was reduced to 10 mmHg in the same manner as in Synthesis Example 2-1, and then heated under nitrogen bubbling and at 120 ° C. for 5 hours. After completion of the reduced-pressure heating, the temperature was cooled to room temperature, and the pressure was returned to normal pressure, and then the obtained liquid was filtered and purified to obtain 219 g of product-8. Here, in the same manner as in Synthesis Example 2-1, the number of trimethoxysilyl groups, polyether groups, and epoxy groups (average value) introduced in the reaction was calculated with respect to 1 mol of methylhydrosiloxane. Table 4 shows the amount of each functional group introduced and the epoxy equivalent.

[2] Preparation of Adhesive Composition [Examples and Comparative Examples] 下 With respect to 100 parts by mass of the solid content of the copolymer solution containing the (A) acrylate obtained in Synthesis Examples 1-1 and 1-2, blended Each component described in Tables 5 and 6 was prepared in each of Examples 1-1 to 1-7, 2-1 to 2-7, and Comparative Examples 1-1 to 1-4, and 2-1 to 2-4. Adhesive composition.

TDI: Trimethylolpropane toluene diisocyanate adduct

TDI: Trimethylolpropane toluene diisocyanate adduct X-24-1056: manufactured by Shin-Etsu Chemical Industry Co., Ltd., epoxy alkoxy oligomer X-41-1810: manufactured by Shin-Etsu Chemical Industry Co., Ltd. Methyl mercapto-based alkoxy oligomer X-12-641: manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silane

The adhesive composition obtained by each said Example and the comparative example was apply | coated to PET film (releasable base material), and it dried, and the uniform adhesive layer of 25 micrometers was formed. The side on which the adhesive layer was formed was bonded to an iodine-based polarizing plate having a thickness of 185 μm. After being matured in a gas environment at 25 ° C. and 50% RH for 7 days, the obtained polarizing plate was cut into an appropriate size. The disclosed method evaluates reworkability and durability. The results are shown in Tables 7 and 8.

(1) Reworkability: The polarizing plate coated with an adhesive was cut into a size of 90 mm × 170 mm, and the PET film was peeled off and bonded to a glass substrate, and then held at 50 ° C. and 0.5 MPa for 20 minutes. A test specimen is prepared. After standing at 25 ° C and 60% RH for 1 hour, it was further matured at 70 ° C for 20 hours and allowed to cool to 25 ° C. Next, the polarizing plate was peeled from the glass, and it was confirmed whether the polarizing plate or the glass plate can be peeled off without leaving the adhesive on the glass surface, and evaluated according to the following criteria. The results are shown in Tables 7 and 8. ◎: Easy to peel (light peeling force) ○: Peelable (medium peeling force) △: Slightly difficult to peel off, adhesive remaining on glass surface (heavy peeling force): Unable to peel, glass or polarizer breakage (heavy peeling force)

(2) Durability The polarizing plate coated with an adhesive was cut into a size of 90 mm × 170 mm, and the PET film was peeled off and bonded to a glass substrate, and then subjected to an autoclave treatment at 50 ° C and 0.5 MPa for 20 minutes to The polarizing plate is adhered to the glass. Next, after being left in a gas environment at 80 ° C (DRY) and a gas environment at 60 ° C / 90% RH for 1,000 hours, the presence or absence of bubbles formation or peeling was confirmed, and evaluated according to the following criteria. The results are shown in Tables 7 and 8. In addition, before evaluating the state of the test piece, it was left to stand at room temperature (23 ° C / 60% RH) for 24 hours. ◎: There are no changes in appearance such as peeling. ○: Some peeling, but practically no problem. ×: There is significant peeling, and there are practical problems.

As shown in Tables 7 and 8, it was confirmed that the adhesive composition of each example had good reworkability and durability, and was significantly superior to the adhesive composition of the comparative example. When the OH-type acrylic resin mainly containing a hydroxyl group as a functional group is used as the adhesive composition of the present invention, it also exhibits excellent durability and can also take into consideration reworkability.

Claims (10)

An adhesive composition comprising a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylic acid ester monomer, and a hydrolyzable silyl group in a molecule represented by the following formula [1a]. At least one of organosiloxane and at least one hydrolysate of each acid anhydride group, (In the formula, 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 containing a hydrolyzable silyl group. R ^{1 is} independent of each other and represents a hydrogen atom, or A monovalent hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen atom, M ^{1 is} independent of each other, and represents a group selected from the foregoing X, Y, Z, and R ¹ ; a, b, c, and d each represent 0 ≦ a ≦ 100, 0 ≦ b ≦ 100, 0 ≦ c ≦ 100, 0 ≦ d ≦ 100, but when a is 0, at least one of M ¹ is X and c is an integer of 1 ≦ c ≦ 100, where c is In the case of 0, at least one of M ¹ is Z and a is an integer of 1 ≦ a ≦ 100, and the arrangement of the repeating units in the parentheses marked a, b, c, and d may be random or block). An adhesive composition comprising a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylate monomer, and a hydrolyzable silyl group in a molecule represented by the following formula [1b], At least one of an organosiloxane and at least one of an acid anhydride group and a polyether group, and a hydrolyzate thereof, (In the formula, 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 containing a hydrolyzable silyl group. R ^{1 is} independent of each other and represents a hydrogen atom, or A monovalent hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen atom, M ^{1 is} independent of each other, and represents a group selected from the foregoing X, Y, Z, and R ¹ ; a, b, c, and d each represent 0 ≦ a ≦ 100, Integers of 0 ≦ b ≦ 100, 0 ≦ c ≦ 100, 0 ≦ d ≦ 100, but when a is 0, at least one of M ¹ is X and b and c are 1 ≦ b ≦ 100, 1 An integer of ≦ c ≦ 100. When b is 0, at least one of M ¹ is Y and a and c are integers of 1 ≦ a ≦ 100 and 1 ≦ c ≦ 100, respectively. When c is 0, M At least one of ¹ is Z and a and b are integers of 1 ≦ a ≦ 100, 1 ≦ b ≦ 100, and the arrangement of the repeating units in the brackets marked a, b, c, and d may be random or embedded. segment). The adhesive composition according to claim 1 or 2, wherein X is a monovalent hydrocarbon group having an acid anhydride group represented by the following formula [2], and Y is a polyether group having a polyether group represented by the following formula [3]. A monovalent hydrocarbon group, wherein Z is a monovalent hydrocarbon group containing a hydrolyzable silyl group represented by the following formula [5], (Wherein A represents an alkylene group having 2 to 6 carbon atoms), (In the formula, R ² represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a group represented by the following formula [4], m represents an integer of 2 or more, e and f are independent of each other, and represent 0 or more. Integer, but at least one of e and f is an integer of 1 or more), (Wherein R ³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), (In the formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, R ⁵ represents a monovalent hydrocarbon group or fluorenyl group having 1 to 10 carbon atoms, n represents an integer of 2 or more, and g represents an integer of 1 to 3). The adhesive composition according to any one of claims 1 to 3, wherein at least one of the aforementioned R ¹ is a monovalent hydrocarbon group having a perfluoroalkyl group. The adhesive composition according to any one of claims 1 to 4, wherein the acid anhydride group equivalent of the organosiloxane and the hydrolyzate thereof is 5,000 g / mol or less. The adhesive composition according to any one of claims 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. The adhesive composition according to any one of claims 1 to 6, wherein the blending amount of at least one of the organosiloxane and its hydrolysate is 0.001 to 5 parts by mass based on 100 parts by mass of the copolymer. The adhesive composition according to any one of claims 1 to 7, which contains 0.01 to 40 parts by mass of a crosslinking agent with respect to 100 parts by mass of the aforementioned copolymer. The adhesive composition according to claim 8, wherein the crosslinking agent is 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. At least one combination. A film with an adhesive layer, comprising: a film; and a layer formed by using the adhesive composition according to any one of claims 1 to 9 on at least one side of the film.