KR102492449B1 - Adhesive composition and film made of the composition - Google Patents

Abstract

(X는 산 무수물기를 갖는 1가 탄화수소기를, Y는 폴리에터기를 갖는 1가 탄화수소기를, Z는 가수분해성 실릴기를 갖는 1가 탄화수소기를, R¹은 서로 독립하여 수소 원자 등을, M¹은, 서로 독립하여, X, Y, Z 및 R¹로부터 선택되는 기를, a, b, c, d는, 각각, 0∼100의 정수를 나타내는데, a가 0인 경우, M¹의 적어도 1개가 X이고 c는 1≤c≤100의 정수이며, c가 0인 경우, M¹의 적어도 1개가 Z이고 a는 1≤a≤100의 정수이다.)[Problem] To provide an adhesive composition capable of improving durability while maintaining reworkability favorably when used for bonding between an optical functional film and a liquid crystal cell.
[Solution]
An adhesive composition containing at least one of a copolymer of a polymerizable unsaturated monomer containing a (meth)acrylic acid ester monomer, an organosiloxane represented by formula [1a], and a hydrolyzate thereof.

(X is a monovalent hydrocarbon group having an acid anhydride group, Y is a monovalent hydrocarbon group having a polyether group, Z is a monovalent hydrocarbon group having a hydrolyzable silyl group, R ¹ is independently a hydrogen atom, etc., M ¹ is , independently of each other, a group selected from X, Y, Z and R ¹ , a, b, c, and d each represent an integer from 0 to 100, and when 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 an integer of 1≤a≤100.)

Description

Adhesive composition and film formed using this composition {ADHESIVE COMPOSITION AND FILM MADE OF THE COMPOSITION}

The present invention relates to a pressure-sensitive adhesive composition and a film made using the composition, and more specifically, to a pressure-sensitive adhesive composition used for bonding an optical functional film and a liquid crystal cell, and a film having a layer formed using the composition will be.

In the liquid crystal display device, first, a liquid crystal cell is produced by sandwiching a liquid crystal component between two 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 through an adhesive layer. is manufactured through a process.

This liquid crystal display device has come to be widely used as a display device such as a display device for a vehicle, an outdoor instrument, a personal computer, and the like, and a television. In addition, with the expansion of this use, since the environment in which liquid crystal display devices are used is also complex, they may be used in very harsh environments, and also for the adhesive composition used in the manufacture of liquid crystal display devices, capable of responding to harsh environments performance was required.

Specifically, even when exposed to high-temperature conditions or high-temperature, high-humidity conditions, the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition does not foam or the adhered optical functional film does not peel off from the substrate (hereinafter referred to as "durability") this will be needed

On the other hand, in the manufacturing process, reattachment of the optical functional film and the liquid crystal cell may be necessary. In that 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 “reworkability”).

That is, the adhesive used for bonding the optical functional film and the liquid crystal cell is required to have good reworkability during bonding and high durability after bonding.

As the pressure-sensitive adhesive used for such applications, many acrylic resins are used. For example, in Patent Literature 1, an adhesive composition in which an epoxy group-containing coupling agent is contained in an acrylic polymer is proposed.

The composition of Patent Literature 1 exhibits high durability against a type of acrylic polymer (hereinafter referred to as "COOH-type acrylic polymer") containing a carboxyl group as the main reactive group. However, there is a problem that durability is not obtained for acrylic polymers of a type mainly containing a hydroxyl group as a reactive group (hereinafter referred to as "OH-type acrylic polymer").

Further, Patent Literatures 2 and 3 propose adhesive compositions in which an acrylic polymer contains an epoxy group-containing polyether-modified coupling agent. This composition achieves both reworkability and durability for COOH-type acrylic polymers. However, there is a problem that durability is not obtained for OH-type acrylic polymers.

Further, Patent Literature 4 describes an adhesive composition in which a mercapto group-containing silane coupling agent is incorporated in an acrylic polymer. Although this composition improves durability against OH-type acrylic polymers, it is not at a sufficient level.

Further, Patent Document 5 proposes an adhesive composition in which an acid anhydride group-containing polyether-modified coupling agent is contained in an acrylic polymer. This composition achieves both reworkability and durability with respect to the OH-type acrylic polymer. However, in recent years, while the demand for durability of pressure-sensitive adhesives has increased, further improvement in durability has been requested.

Japanese Patent No. 5826179 Japanese Patent No. 5891534 Japanese Patent No. 3498158 Japanese Patent No. 5544858 Japanese Patent No. 5990847

The present invention has been made in view of the above circumstances, and when used for bonding an optical functional film and a liquid crystal cell, a pressure-sensitive adhesive composition capable of improving durability while maintaining good reworkability, and using this composition It is an object of the present invention to provide a film having a pressure-sensitive adhesive layer formed thereon.

As a result of intensive studies to solve the above problems, the present inventors have found that a copolymer of a polymerizable unsaturated monomer containing a (meth)acrylic acid ester monomer and an organosilox having at least one hydrolyzable silyl group and acid anhydride group in the molecule, respectively. When a composition containing organosiloxane having at least one hydrolyzable silyl group, acid anhydride group, and polyether group in its molecule or at least one each is used for bonding an optical functional film and a liquid crystal cell, reworkability The present invention was completed by finding that it is possible to improve the durability and is suitable as an adhesive composition while maintaining it well.

That is, the present invention,

1. A copolymer of a polymerizable unsaturated monomer containing a (meth)acrylic acid ester monomer and an organosiloxane represented by the following formula [1a] having at least one hydrolyzable silyl group and at least one acid anhydride group in its molecule, respectively, and its A pressure-sensitive adhesive composition comprising at least one of a hydrolyzate,

(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 hydrolysable silyl group, R ¹ are independently of each other, Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and M ¹ is independently of each other a group selected from X, Y, Z and R ¹ , a, b, c and d respectively represent integers of 0≤a≤100, 0≤b≤100, 0≤c≤100, and 0≤d≤100, provided that when 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 an integer of 1≤a≤100. The arrangement of each repeating unit may be random or block.)

2. A copolymer of a polymerizable unsaturated monomer containing a (meth)acrylic acid ester monomer, and a five-group having at least one hydrolyzable silyl group, acid anhydride group, and polyether group in the molecule, each represented by the following formula [1b] A pressure-sensitive adhesive composition comprising at least one of nosiloxane and a hydrolyzate thereof;

(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 hydrolysable silyl group, R ¹ are independently of each other, Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and M ¹ is independently of each other a group selected from X, Y, Z and R ¹ , a, b, c and d represent integers of 0≤a≤100, 0≤b≤100, 0≤c≤100, and 0≤d≤100, respectively, provided that when a is 0, at least one of M ¹ is X And, b and c are integers of 1≤b≤100 and 1≤c≤100, respectively, and when b is 0, at least one of M ¹ is Y, and a and c are each 1≤a≤ It is an integer of 100 and 1≤c≤100, and when c is 0, at least one of M ¹ is Z, and a and b are integers of 1≤a≤100 and 1≤b≤100, respectively. The arrangement of each repeating unit in brackets with b, c and d may be random or block.)

3. 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], and the Z is The pressure-sensitive adhesive composition of 1 or 2, which is a monovalent hydrocarbon group having a hydrolyzable silyl group represented by [5],

(In the formula, A represents an alkylene group having 2 to 6 carbon atoms.)

(Wherein, 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, and e and f are each independently 0 represents an integer above, at least one of e and f is an integer greater than or equal to 1.)

(In the formula, R ³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.)

(Wherein, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, R ⁵ represents a monovalent hydrocarbon group or acyl group having 1 to 10 carbon atoms, n represents an integer of 2 or greater, and g represents 1 to 3 represents the integer of .)

4. The pressure-sensitive adhesive composition of any one of 1 to 3, wherein at least one of R ¹ is a monovalent hydrocarbon group having a perfluoroalkyl group;

5. The pressure-sensitive adhesive composition of any one of 1 to 4, wherein the acid anhydride group equivalent of the organosiloxane and its hydrolyzate is 5,000 g/mol or less;

6. The pressure-sensitive adhesive composition of any one of 1 to 5, wherein the copolymer contains at least one of a structural unit derived from a carboxy group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer;

7. An adhesive composition of any one of 1 to 6, wherein the compounding amount of the organosiloxane and at least one of its hydrolyzate is 0.001 to 5 parts by mass, based on 100 parts by mass of the copolymer;

8. The adhesive composition of any one of 1-7 containing 0.01-40 mass parts of crosslinking agents with respect to 100 mass parts of said copolymers;

9. The pressure-sensitive adhesive composition of 8, wherein the crosslinking agent is at least one selected from isocyanate crosslinking agents, epoxy crosslinking agents, metal crosslinking agents, aziridine crosslinking agents, and peroxide crosslinking agents;

10. A film with an adhesive layer characterized by having a film and a layer comprising the adhesive composition of any one of 1 to 9 on at least one side of the film.

provides

The pressure-sensitive adhesive composition of the present invention can be suitably used as an adhesive between an optical functional film and a liquid crystal cell in the manufacturing process of a liquid crystal display device, and although it can be peeled off during bonding, it swells under high temperature and high humidity conditions after bonding. Raising and peeling are difficult to occur.

Since the pressure-sensitive adhesive composition of the present invention having these properties can realize durability and reworkability, which have recently been required to achieve a high level, a protective film forming agent for the surface of a substrate, a surface treatment agent for fibers or powders, and a point between substrates It can be used suitably as an adhesive etc., especially as an adhesive composition used for bonding of an optical functional film in the manufacturing process of a liquid crystal display device.

(Mode for implementing the invention)

Hereinafter, the present invention will be described in detail.

The pressure-sensitive adhesive composition according to the present invention is a copolymer of a polymerizable unsaturated monomer containing a (meth)acrylic acid ester monomer, an organosiloxane represented by the formula [1a] or [1b] and a hydrolyzate thereof (hereinafter, only five It is called nosiloxane) and contains at least one of them.

The copolymer of polymerizable unsaturated monomers containing the (meth)acrylic acid ester 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 polymerizable unsaturated monomers containing the (meth)acrylic acid ester monomer not.

Specific examples of the (meth)acrylic acid ester monomer include 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 Alkyl (meth)acrylates, such as late 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; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl ( hydroxyalkyl (meth)acrylates such as meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; caprolactone-modified (meth)acrylate; and polyalkylene glycol (meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate. You may use it in combination of more than one.

The copolymer of the present invention preferably contains 60 to 100% by mass, more preferably 80 to 100% by mass of the repeating unit derived from the (meth)acrylic acid ester monomer.

In addition, considering that the resin used for adhesion between the optical functional film and the liquid crystal cell has pressure-sensitive adhesiveness, the copolymer of the present invention has 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 It is preferable to contain.

Specific examples of the monomer containing a carboxy group and/or a hydroxy group providing such a structural unit include the above-mentioned carboxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, polyalkylene glycol (meth) acrylate and In addition, (meth)acrylic acid, N-(2-hydroxyethyl) (meth)acrylamide, etc. are mentioned, These monomers may be used independently or may be used in combination of 2 or more types.

In particular, the content of the repeating unit derived from the monomer containing a carboxy group and/or a hydroxyl group in the copolymer used in the present invention is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. .

In addition, the copolymer used in the present invention may contain repeating units derived from other monomers other than the above-mentioned monomers.

Specific examples of other monomers include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl Styrene-type monomers, such as styrene, octyl styrene, fluoro styrene, chloro styrene, bromo styrene, dibromo styrene, iodo styrene, nitro styrene, acetyl styrene, and methoxy styrene; Vinyl monomers such as vinylpyridine, vinylpyrrolidone, vinylcarbazole, divinylbenzene, vinyl acetate, acrylonitrile, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, and vinylidene chloride These monomers may be used alone or in combination of two or more.

The content of repeating units derived from the other monomers in the copolymer used in the present invention is preferably 0 to 20% by mass, 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 therein, and may be a random copolymer, a block copolymer, or any other copolymer.

The weight average molecular weight of the copolymer is not particularly limited, but increases the cohesive force of the pressure-sensitive adhesive layer, suppresses foaming and peeling of the pressure-sensitive adhesive layer to increase durability, and maintains the viscosity of the pressure-sensitive adhesive composition in an appropriate range for workability. 100,000 to 2,000,000 are preferable, and 300,000 to 1,500,000 are more preferable, considering making it good.

In addition, a weight average molecular weight is a polystyrene conversion value 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, but it is preferably produced by solution polymerization in which the copolymer is obtained as a solution. , By obtaining the copolymer as a solution in this way, it can be used as it is for the production of the pressure-sensitive adhesive composition of the present invention.

An organic solvent is used as a solvent for solution polymerization, 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-propyl alcohol and isopropyl alcohol; Ketones, such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, etc. are mentioned.

Further, 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 monomers.

In addition, as a polymerization initiator used for polymerization, it may be appropriately selected from known ones and used, and specific examples thereof include di-tert-butyl peroxide, benzoyl peroxide, lauryl peroxide, tert-butyl peroxybenzoate, and cumene hydroper. oxide, diisopropylperoxydicarbonate, dipropylperoxydicarbonate, tert-butylperoxyneodecanoate, tert-butylperoxypivalate, (3,5,5-trimethylhexanoyl) peroxide, etc. of peroxide; Azobisisobutyronitrile, azobisvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronite Lil), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2 azobis compounds such as '-azobis(2-hydroxymethylpropionitrile) or polymeric azo polymerization initiators are exemplified, and these may 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 monomers.

The temperature of the polymerization reaction is usually 50 to 90°C, and the reaction time is usually 2 to 20 hours, but preferably 4 to 12 hours.

On the other hand, 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 has a structure of a silicone skeleton different from the compound having an alkoxy group, an acid anhydride group, and a polyether group in the molecule described in Patent Document 5 (Japanese Patent No. 5990847). The compound described in Patent Literature 5 has a three-dimensional silicon skeleton, whereas the organosiloxane used in the present invention has a linear silicon skeleton. As a result, since migration to the resin surface is improved when added to the acrylic resin and used, it becomes possible to further enhance the functionality of the resin surface. In addition, the reactivity of the alkoxy group to inorganic substrates such as glass is improved by structural factors of the compound. Therefore, in bonding the optical functional film and the liquid crystal cell, it becomes possible to further improve durability.

In each of the above formulas, 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, and R ¹ are independent of each other represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and M ¹ independently represents a group selected from X, Y, Z and R ¹ described above.

In each of the above formulas, a, b, c, and d represent integers of 0≤a≤100, 0≤b≤100, 0≤c≤100, and 0≤d≤100, respectively. In, when a is 0, at least one of M ¹ is X, c is an integer of 1≤c≤100, when c is 0, at least one of M ¹ is Z, and a is 1≤a≤100 In formula [1b], when a is 0, at least one of M ¹ is X, b and c are integers of 1≤b≤100 and 1≤c≤100, respectively, and b is 0. In this case, at least one of M ¹ is Y, a and c are integers of 1≤a≤100 and 1≤c≤100, respectively, and when c is 0, at least one of M ¹ is Z, a, b is an integer of 1≤a≤100 and 1≤b≤100, respectively.

Further, in each of the above formulas, the arrangement of each repeating unit in parentheses a, b, c and d may be random or block.

Specific examples of the monovalent hydrocarbon group of 1 to 20 carbon atoms for R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, linear, branched or cyclic alkyl groups such as cyclohexyl, n-octyl, n-nonyl, n-decyl, and n-octadecyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; Aralkyl groups, such as a benzyl, phenylethyl, and phenylpropyl group, etc. are mentioned.

Specific examples of groups in which some or all of the hydrogen atoms of these monovalent hydrocarbon groups are substituted with halogen atoms include chloromethyl, trifluoromethyl, and chloropropyl groups.

Among these, R ¹ is preferably a monovalent hydrocarbon group having a methyl group or a perfluoroalkyl group, and more preferably an alkyl group (fluoroalkyl group) substituted with a methyl group or 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 -, 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 monovalent hydrocarbon group as R ¹ , the organosiloxane of the present invention improves compatibility with the resin when used in combination with the copolymer as a matrix resin, making phase separation difficult to occur. It is preferable that at least one of each R ¹ is a monovalent hydrocarbon group, all of which are more preferably a monovalent hydrocarbon group, all R ¹ are methyl groups, or a combination of a methyl group and a monovalent hydrocarbon group having a perfluoroalkyl group is still more preferable. .

In addition, the organosiloxane used in the present invention has a monovalent hydrocarbon group X having an acid anhydride group, and when this organosiloxane is added to a matrix resin due to the existence of this monovalent hydrocarbon group X, a monovalent hydrocarbon group The acid anhydride group of X reacts with the reactive group (hydroxy group, carboxy group, etc.) of the matrix resin, and 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 same groups as those exemplified for R ¹ above, but an alkyl group is preferable and a straight-chain alkyl group is more preferable.

As an acid anhydride group, a succinic anhydride group, a maleic anhydride group, etc. are mentioned.

Suitable X includes groups represented by the following formula [2].

The above A represents an alkylene group having 2 to 6 carbon atoms, and specific examples thereof include linear or branched chain alkylene groups such as ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene groups. In particular, , a trimethylene group is preferable, and therefore, as X, a propyl succinic acid anhydride group is preferable.

In addition, the organosiloxane used in the present invention has a monovalent hydrocarbon group Z having a hydrolyzable silyl group, and by having this monovalent hydrocarbon group Z, inorganic substrates such as glass are surface-treated with the organosiloxane Then, the hydrolyzable silyl group reacts with the -OH group present on the surface of the inorganic substrate, and a chemical bond is formed between the organosiloxane and the inorganic substrate.

Examples of the monovalent hydrocarbon group of the monovalent hydrocarbon group having a hydrolyzable silyl group include the same groups as those exemplified for R ¹ above, but an alkyl group is preferable and a straight-chain alkyl group is more preferable.

As preferable Z, what is represented by following formula [5] is mentioned.

Said R ⁴ represents an alkyl group of 1 to 10 carbon atoms, R ⁵ represents a monovalent hydrocarbon group or acyl group of 1 to 10 carbon atoms, n is an integer of 2 or more, preferably an integer of 2 to 5, and more Preferably represents an integer of 2 or 3, 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 same ones as the alkyl groups having 1 to 10 carbon atoms among the alkyl groups exemplified for R ¹ above, but a methyl group and an ethyl group are preferable.

Specific examples of the monovalent hydrocarbon group include the same groups as those exemplified for R ¹ above, but an alkyl group and an aryl group are preferable.

Specific examples of the acyl group include formyl and acetyl groups.

As specific examples of the hydrolyzable silyl group (in the formula [5], the portion excluding -C _n H _2n -), trimethoxysilyl, methyldimethoxysilyl, dimethylmonomethoxysilyl, triethoxysilyl, methyl Diethoxysilyl, Dimethylmonoethoxysilyl, Tripropoxysilyl, Methyldipropoxysilyl, Dimethylmonopropoxysilyl, Triisopropenoxysilyl, Methyldiisopropeneoxysilyl, Dimethylisopropene oxysilyl, triacyloxysilyl, methyldiacyloxysilyl, dimethylmonoacyloxysilyl group, etc. are mentioned, and at least 1 sort(s) selected from these groups can be used. Preferably it is a trimethoxysilyl group.

In the organosiloxane used in the present invention, the number of hydrolyzable silyl groups and acid anhydride groups can be freely adjusted. For this reason, the balance of the reactivity to organic resins and the reactivity to inorganic substrates can be freely controlled.

In addition, the organosiloxane used in the present invention may contain a monovalent hydrocarbon group Y having a polyether group in addition to the hydrolysable silyl group and acid anhydride group.

This polyether group has an effect of controlling the affinity between the organosiloxane and the surface of the inorganic substrate.

That is, organosiloxanes containing only hydrolyzable silyl groups and acid anhydride groups as organic functional groups have low hydrophilicity of the acid anhydride groups, and therefore, the hydrophilicity of the entire molecule may significantly decrease as the number of organic functional groups increases. For this reason, when this organosiloxane is applied on an inorganic substrate having a hydrophilic surface to form a cured film, problems such as poor wettability, repelling, etc., and inability to obtain a uniform coating film may occur. there is. However, by introducing a polyether group into the molecule of the organosiloxane, this problem is solved, and it becomes possible to form a uniform cured film of organosiloxane on an inorganic substrate.

In addition, by adjusting the type and amount of the polyether group introduced, it is possible to control the reaction between the hydrolyzable silyl group and the inorganic substrate and adjust the bonding strength between the substrate and the organosiloxane. As a result, when organosiloxane is used for adhesion between an organic resin and an inorganic substrate, it becomes possible to adjust the adhesive strength from slight adhesion to strong adhesion depending on the application.

Specific examples of the monovalent hydrocarbon group in the monovalent hydrocarbon group containing a polyether group include the same groups as those exemplified for R ¹ above, but an alkyl group is preferable and a straight-chain alkyl group is more preferable.

As suitable Y, group represented by following formula [3] is mentioned.

The above 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].

(In the formula, R ³ represents a monovalent hydrocarbon group of 1 to 4 carbon atoms, preferably an alkyl group of 1 to 4 carbon atoms.)

As a monovalent hydrocarbon group in Formula [3] and [4], the thing of the corresponding number of carbon atoms can be mentioned among the groups illustrated by said R< ¹ >, respectively.

As R ² , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable.

e and f represent integers greater than or equal to 0 independently of each other, preferably integers in the range of 0≤e≤50 and 0≤f≤50, and more preferably integers in the range of 0≤e≤20 and 0≤f≤20. Do. However, at least 1 of e and f is 1 or more, Preferably it is an integer of 1-50.

Although m represents an integer of 2 or more, an integer of 2 to 6 is preferable.

The polyether group portion is 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) .) may be used, and in the case of the EO-PO type, any of random, block and alternating may be used.

Moisture resistance can be improved by introducing a monovalent hydrocarbon group having a PO 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 are substituted with fluorine. By containing fluorine, it becomes possible to improve the transferability of the organosiloxane used in the present invention to the resin surface or to control the affinity between the resin surface and the adherend.

The fluoropolyether group is not particularly limited, but is preferably composed of at least one selected from structural units shown below.

Specific examples of the monovalent hydrocarbon group having a fluoropolyether group include the following structures.

Although what is represented by the following formula [12] and [13] as a suitable example of organosiloxane used by this invention is mentioned, It is not limited to these. In addition, the arrangement|sequence of each siloxane unit in organosiloxane represented by following formula [12] and [13] may be random or a block may be sufficient as it.

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

The organosiloxane described above contains a hydrolyzable silyl group-containing compound having an aliphatic unsaturated bond and an acid anhydride group having an aliphatic unsaturated bond in an organohydrogensiloxane represented by the following formula [7] under a platinum catalyst. It can manufacture by carrying out the hydrosilylation reaction of a compound and the polyether group containing compound which has an aliphatic unsaturated bond as needed.

In 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 above R ¹⁰ . i and j represent integers of 1≤i≤300 and 0≤j≤100, respectively, preferably integers in the range of 1≤i≤150 and 0≤j≤50, more preferably 1≤i≤ 60, an integer in the range of 0≤j≤20. The arrangement of each repeating unit in parentheses with 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 those represented by the following formula [8].

(In the formula, p represents an integer of 0 to 10, preferably 0 to 5. R ⁴ , R ⁵ and g represent the same meaning as 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 during the hydrosilylation reaction is preferably 1 to 100 mol, more preferably 1 to 50 mol, and still more preferably 1 to 20 mol, relative to 1 mol of organohydrogensiloxane.

As an acid anhydride group containing compound which has the said aliphatic unsaturated bond, what is represented by following formula [9] is mentioned, for example.

(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 preferable.

The reaction ratio during the hydrosilylation reaction is preferably 1 to 100 mol, more preferably 1 to 50 mol, and even more preferably 1 to 20 mol, per 1 mol of organohydrogensiloxane.

As a polyether group containing compound which has the said aliphatic unsaturated bond, what is represented by following formula [10] is mentioned, for example.

(In the formula, p, R ² , e, f represent the same meaning as above.)

In particular, as the polyether group-containing compound having an unsaturated bond, an allylpolyether represented by the following formula [11] is preferable.

The reaction ratio in the hydrosilylation reaction is preferably 1 to 100 mol, more preferably 1 to 50 mol, and still more preferably 1 to 20 mol, per 1 mol of organohydrogensiloxane.

(In the formula, R ² , e and f represent the same meaning as above.)

More specifically, for example, in the case of the compound represented by the formula [12], 4 mol of vinyltrimethoxysilane and 4 mol of vinyltrimethoxysilane per 1 mol of methylhydrogensiloxane represented by the following formula [14] under a platinum catalyst. , 1 mol of allyl polyether represented by the following formula [15] and 3 mol of allyl succinic anhydride are subjected to a hydrosilylation reaction, and can be manufactured.

In addition, in the case of the compound represented by the formula [13], 4 mol of vinyltrimethoxysilane and 4 mol of allyl succinic anhydride were hydrolyzed with respect to 1 mol of methylhydrogensiloxane represented by the following formula [16] under a platinum catalyst. It can be produced by silylation reaction.

In addition, the alkoxysilane compound used in the present invention can be produced by a method other than the method described above, for example, by hydrolytic condensation of succinic anhydride-modified alkoxysilane and polyether-modified alkoxysilane. It can also be manufactured by this method.

However, since this method uses water, there is a problem that a ring-opening reaction due to hydrolysis of succinic anhydride occurs together in the production step.

As another method, for example, vinyl trimethoxysilane, allyl polyether, and allyl succinic anhydride are sequentially added to a cyclic organohydrogensiloxane represented by the following formula [17] under a platinum catalyst. It can also be manufactured in the same way.

(In the formula, k represents an integer of 3 or greater.)

However, among the above-mentioned cyclic organohydrogensiloxanes, low-molecular-weight siloxanes having k = 3 to 5 are practically inexpensive and easily available. In that case, the number of reaction sites (SiH) present in the molecule is at most five. When adding vinyl trimethoxysilane, allyl polyether, and allyl succinic anhydride sequentially to this cyclic organohydrogensiloxane through a hydrosilylation reaction, the total amount of each compound introduced is up to five. Therefore, it is not possible to freely set the introduction amount of each functional group.

In contrast, the method for producing organosiloxane of the present invention described above can solve the above problems.

That is, by adjusting the i-value of the organohydrogensiloxane represented by the above formula [7] used as a raw material, the introduction amount of vinyl trimethoxysilane, allyl polyether, and allyl succinic anhydride can be freely set. .

The organosiloxane used in the present invention has a structure in which a group containing each functional group, such as an alkoxy group, an acid anhydride group, or a polyether group, is bonded to the side chain of the linear siloxane skeleton.

In the pressure-sensitive adhesive composition of the present invention, the blending ratio of the above-mentioned copolymer serving as the matrix resin and the alkoxysilane is not particularly limited, but 0.001 to 0.001 to 0.001 of organosiloxane based on 100 parts by mass of the copolymer serving as the matrix resin. It is preferably blended at 5 parts by mass, more preferably blended at 0.01 to 3 parts by mass, and even more preferably blended at 0.1 to 2 parts by mass.

In addition, you may mix|blend a crosslinking agent with the adhesive composition of this invention.

The amount of the crosslinking agent is not particularly limited, but considering that the cohesive force of the pressure-sensitive adhesive composition is appropriate, the durability is improved, and peeling of the film to be adhered is effectively suppressed, the crosslinking agent is 0.01 to 40 parts per 100 parts by mass of the copolymer. It is preferable to mix by mass part, and it is more preferable to blend 0.02 to 30 mass parts.

The crosslinking agent is not particularly limited, but in the present invention, one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, a metal chelate crosslinking agent and an aziridine crosslinking agent is suitably used.

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 aziridine in one molecule. A polyaziridine compound, a metal chelate compound, a butylated melamine compound, etc. which have two or more groups are mentioned, These may be used individually or may be used in combination of 2 or more types.

Specific examples of the polyglycidyl compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, N, N, N', N'-tetragly Lycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycy Polyfunctional glycidyl compounds, such as dil ether, are mentioned, These may be used independently or may be used in combination of 2 or more types.

Specific examples of the polyisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and hydrogenated xylene diisocyanate. , diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc., and these isocyanate compounds, adducts obtained by reacting polyols such as glycerol and trimethylolpropane, and compounds obtained by making isocyanate compounds into dimers, trimers, etc. are exemplified; even if these are used alone, two or more You may use them in combination.

Specific examples of the polyaziridine compound include 1,1'-(methylene-di-p-phenylene)bis-3,3-aziridyl urea and 1,1'-(hexamethylene) bis-3,3-aziridyl urea. , Ethylenebis-(2-aziridinylpropionate), tris(1-aziridinyl)phosphine oxide, 2,4,6-triaziridinyl-1,3,5-triazine, trimethylolpropane- Tris-(2-aziridinyl propionate) etc. are mentioned, These may be used independently or may be used in combination of 2 or more types.

Specific examples of the metal chelate compound include compounds in which acetylacetone or ethyl acetoacetate is coordinated with a multivalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. and these may be used alone or in combination of two or more.

Radiation (preferably ultraviolet) crosslinking is also effective as a form of crosslinking, in which case a monomer having at least two polymerizable reactive double bonds and a photopolymerization initiator (including a sensitizer) can be added.

Specific examples of the monomer having at least two polymerizable double bonds include polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, and 1,9-nonanediol. bifunctional (meth)acrylates such as diacrylate; Polyfunctionals such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, isocyanuric acid triacrylate, and tris(2-acryloxyethyl)isocyanurate ( meta) acrylate; and the like.

Further, 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 known photopolymerization initiator by radiation (ultraviolet rays) can be used, for example, an amino ketone system, a hydroketone system, an acylphosphine oxide system, a benzyldimethyl ketal system, a benzophenone system, and a trichloromethyl group-containing triazine derivative-based photopolymerization initiators; and the like.

In addition, the pressure-sensitive adhesive composition of the present invention can add a silane coupling agent other than the above-mentioned essential organosiloxane and/or a hydrolytic condensate thereof (also referred to as a silane coupling agent), whereby the present invention The durability of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition can be further improved.

The addition amount of the silane coupling agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the copolymer.

Specific examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glucin. epoxy group-containing silane coupling agents such as lysedoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and epoxy group-containing alkoxysilane oligomers; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercapto group-containing alkoxy mercapto group-containing silane coupling agents such as silane oligomers; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ- amino group-containing silane coupling agents such as aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; Isocyanate group containing silane coupling agents, such as γ-isocyanate propyl trimethoxysilane and γ-isocyanate propyl triethoxysilane, etc. are mentioned, Even if these are used independently, You may use in combination of 2 or more types.

Further, the pressure-sensitive adhesive composition of the present invention may be formulated with various additives depending on required properties such as the purpose of adjusting the adhesive strength, within a range not impairing the effects of the present invention.

As additives, terpene-based, terpene-phenolic, cumarone-indene-based, styrene-based, rosin-based, xylene-based, phenolic, petroleum-based tackifying resins, antioxidants, ultraviolet absorbers, fillers, pigments, plasticizers, electrification An inhibitor etc. are mentioned.

The film with an adhesive layer of the present invention is provided with a film and a layer formed by using the above-described adhesive composition of the present invention on at least one side of the film.

That is, a film made of the pressure-sensitive adhesive composition of the present invention excellent in both "durability" and "reworkability" on one side or both sides of an optical functional film (hereinafter referred to as "raw material film") on which no pressure-sensitive adhesive layer is formed ( pressure-sensitive adhesive layer).

For this reason, the film with an adhesive layer of the present invention has characteristics (durability) that it does not peel off from the glass substrate constituting the liquid crystal cell even under high temperature and high humidity, and foaming does not occur in the adhesive layer, and it is easy even after a long period of time. It can be easily peeled off, and also has a characteristic (rework property) that no residue is formed on the substrate or the like after peeling.

The type of the raw material film is not particularly limited, and examples thereof include a film light guide plate, an antireflection film, a conductive film, a viewing angle expansion film, a retardation film, a polarizing plate, and a combination thereof.

Further, in order to improve the adhesion of the film made of the pressure-sensitive adhesive composition of the present invention to the raw material film, the surface of the raw material film may be subjected to surface treatment such as corona treatment.

The thickness of the raw material film is not particularly limited, and may be, for example, about 5 to 300 μm, although it may be an appropriate thickness depending on the use or purpose.

The film with an adhesive layer of the present invention is formed by coating the adhesive composition of the present invention on one or both surfaces of the raw material film using a commonly used coating device, for example, a roll coating device, and drying the coated layer. It is obtained by forming (adhesive layer). Further, if necessary, the coated pressure-sensitive adhesive layer may be cured by heat crosslinking or by light such as ultraviolet rays to form a cured film.

In the film with an adhesive layer of the present invention, first, the adhesive composition of the present invention is coated on a protective film such as a polyethylene terephthalate film (PET film) coated with a release agent such as a silicone resin on the surface, and dried to form an adhesive layer. It can also be obtained by bonding a raw material film on an adhesive layer after forming.

In any of the above cases, it is preferable that the coating amount of the pressure-sensitive adhesive composition is such that the thickness of the pressure-sensitive adhesive layer (film) after drying is 10 to 50 μm. By setting the thickness of the pressure-sensitive adhesive layer within the above range, the film with the pressure-sensitive adhesive layer is more well-balanced in durability and reworkability, suitable as an optical functional film.

The film with an adhesion layer of the present invention produced as described above can be adhered onto a glass substrate of a liquid crystal cell such as a liquid crystal display device by means normally used.

Further, the film with an adhesive layer of the present invention may be further laminated and adhered onto an optical functional film adhered onto a glass substrate.

(Example)

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to these Examples.

In addition, the apparatus used in the Example is as follows.

Infrared spectroscopy (FTIR): NICOLET6700 from Thermo sientific

²⁹ Si-NMR: AVANCE400M from Bruker

GPC: Toso HLC-8220 GPC

[1] Preparation of matrix resin

[Synthesis Example 1-1] Preparation of Copolymer Solution-1

Nitrogen gas was introduced into a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, and the air in the apparatus was substituted with nitrogen gas. Next, in the flask, 70.0 g of n-butyl acrylate (BA), 30.0 g of methyl acrylate (MA), 0.3 g of acrylic acid (AA), 1.7 g of 2-hydroxyethyl acrylate (2HEA), and azobisisobutyro 0.1 g of nitrile and 100 g of ethyl acetate were charged, and the mixture was reacted at 70°C for 10 hours while stirring to obtain an acrylic copolymer solution-1. The weight average molecular weight of the copolymer by GPC was 1,500,000.

[Synthesis Example 1-2] Preparation of Copolymer Solution-2

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 used, and acrylic acid (AA) was not used. got it The weight average molecular weight of the copolymer by GPC was 1,500,000.

[2] Synthesis of organosiloxanes

[Synthesis Example 2-1]

After charging 100 g (0.192 mol) of organohydrogensiloxane represented by the following formula [18] and 114 g of toluene to a 1 liter three-necked flask equipped with a stirrer, a thermometer, and a dimroth condenser condenser, vinyl 1.00 g of a toluene solution of siloxane-coordinated Pt was added with stirring. Next, the temperature was raised to 80°C, and 56.7 g (0.383 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Here, the reaction rate of vinyltrimethoxysilane used in the above 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, respectively.

10 g of butanol was added to 1 g of the sample before and after the reaction, respectively, and 20 g of 20 mass% NaOH aqueous solution was added while stirring. The content of ≡SiH was calculated from the amount of hydrogen gas (≡SiH+H ₂ O→≡SiOH+H ₂ ↑) generated at this time.

Next, the amount of vinyltrimethoxysilane actually reacted in 1 g of the sample was calculated by 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 x 10 ^-3 mol of vinyltrimethoxysilane charged as a raw material was present. When the reaction rate of vinyltrimethoxysilane is calculated as follows from the reaction amount obtained previously and the amount charged as a raw material, it is 99.3%.

[Reaction rate = 1.40 × 10 ^-3 (mol) / 1.41 × 10 ^-3 (mol) × 100 = 99.3 (%)]

From the above, it was confirmed that 99% or more of vinyltrimethoxysilane charged as a raw material reacted with methylhydrogensiloxane by the hydrosilylation reaction.

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, 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while stirring, and the temperature was raised to 110°C. Next, 120 g (0.857 mol) of allyl succinic anhydride was added dropwise, followed by aging at 115°C for 10 hours.

Here, the reaction rate of allyl succinic anhydride was measured. First, by the same method as above, the content of ≡SiH in 1 g of the sample before and after the reaction was measured, and the amount of allyl succinic anhydride actually reacted was calculated. The results are shown in Table 2.

The amount of hydrogen gas generated after completion of the reaction was a value close to 0 ml. From this, it is considered that almost all of the ?SiH remaining in methylhydrogensiloxane reacted with allyl succinic anhydride by the hydrosilylation reaction.

In 1 g of the sample before the reaction, 2.17 x 10 ^-3 mol of allyl succinic anhydride charged as a raw material was present. When the reaction rate of allyl succinic anhydride is calculated as follows from the reaction amount obtained above and the amount charged as a raw material, it is 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 reacted with methylhydrogensiloxane, and the remaining about 12% remained as an excess.

Finally, an operation was performed to remove the remaining surplus allyl succinic anhydride. The cooling pipe of the Dimroth condenser was replaced with an exhaust gas pipe, and after reducing the pressure in the system to 10 mmHg, heating was performed at 150° C. for 20 hours under nitrogen gas bubbling. After completion of heating under reduced pressure, the temperature was cooled to room temperature and the pressure was restored to normal pressure, and then the obtained liquid was purified by filtration to obtain 246 g of Product-1.

Here, for Product-1, GPC measurement was performed under a THF solvent. As a result, a broad product peak was confirmed at a holding time of 21 to 32 minutes. Since the peak of raw material allyl succinic anhydride does not exist in the vicinity of the holding time of 36 to 37 minutes, it is considered that the excess of allyl succinic anhydride was almost completely removed by the last reduced-pressure heating.

Next, the acid anhydride group was assigned to Product-1 by infrared spectroscopy (FTIR). As a result, absorption by the carbonyl stretching vibration of the anhydride succinic acid group was observed at 1863 cm ^-1 and 1785 cm ^-1 . Further, at 1735 cm ⁻¹ , absorption due to stretching vibration of the carbonyl group of the carboxy group caused by ring-opening of an anhydride succinic acid group was not observed. Since Product-1 was produced in a completely non-aqueous system, active hydrogen-containing compounds (eg, water, alcohol, etc.) were not incorporated in the production step, and ring opening of the succinic anhydride group was sufficiently suppressed.

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

Furthermore, one peak suggesting the presence of a structure shown below was confirmed around -22 ppm.

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

Furthermore, one peak suggesting the presence of a group shown below was confirmed around -42 ppm.

From the above results, it is estimated that 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, from the measurement results of the respective raw material loading amounts of methylhydrogensiloxane, vinyltrimethoxysilane, and allyl succinic anhydride, and the reaction rate, trimethoxysilyl introduced by reacting with respect to 1 mol of methylhydrogensiloxane The number of groups and anhydrous succinic acid groups (average value) was calculated. Table 3 shows the amount of each functional group introduced and the equivalent weight of the acid anhydride group.

[Synthesis Example 2-2]

In the same manner as in Synthesis Example 2-1, after charging 100 g (0.0371 mol) of methylhydrogensiloxane represented by the following formula [19] and 114 g of toluene, a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 mass %) 1.00 g was added while stirring. 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 groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while stirring, and the temperature was raised to 110°C. Next, 62.3 g (0.445 mol) of allyl succinic anhydride was added dropwise, followed by aging at 115°C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-1, an operation for removing the remaining surplus allyl succinic anhydride was carried out, and the obtained liquid was purified by filtration to obtain 178 g of Product-2.

Here, in the same manner as in Synthesis Example 2-1, the number of reacted and introduced trimethoxysilyl groups and succinic anhydride groups (average value) was calculated with respect to 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the equivalent weight of the acid anhydride group.

[Synthesis Example 2-3]

In the same manner as in Synthesis Example 2-1, after charging 100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene, a toluene solution of Pt coordinated with vinylsiloxane (Pt concentration: 0.5 mass %) 1.00 g was added while stirring. 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.

Subsequently, an operation for reacting 3-(perfluorohexyl)-1-propene with the remaining ≡Si-H groups contained in methylhydrogensiloxane was 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 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, 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while stirring, and the temperature was raised to 110°C. Next, 62.3 g (0.445 mol) of allyl succinic anhydride was added dropwise, followed by aging at 115°C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-1, an operation for removing remaining surplus allyl succinic anhydride was carried out, and the resulting liquid was purified by filtration to obtain 199 g of Product-3.

Here, in the same manner as in Synthesis Example 2-1, the number (average value) of trimethoxysilyl groups, perfluorohexyl groups, and succinic anhydride groups introduced by the reaction was calculated with respect to 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the equivalent weight of the acid anhydride group.

[Synthesis Example 2-4]

In the same manner as in Synthesis Example 2-1, after charging 100 g (0.192 mol) of methylhydrogensiloxane represented by the above formula [18] and 114 g of toluene, a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 mass %) 1.00 g was added while stirring. 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.

Subsequently, an operation for reacting allyl polyether with a part of the ?Si-H groups remaining in methylhydrogensiloxane was performed. 81.4 g (0.192 mol) of an allyl polyether represented by CH ₂ =CH-CH ₂ -O(CH ₂ CH ₂ O) ₈ CH ₃ was added dropwise while stirring the reaction solution at 80°C. After that, aging was performed 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 ° C., and 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while stirring, and further, 121 g (0.864 mol) of allyl succinic anhydride was added dropwise. After that, aging was performed at 115°C for 10 hours.

Finally, in order to remove the remaining surplus allyl succinic anhydride, in the same manner as in Synthesis Example 2-1, after reducing the pressure to 10 mmHg, heating was performed at 120° C. for 20 hours under nitrogen gas bubbling. After completion of heating under reduced pressure, the temperature was cooled to room temperature, and the pressure was restored to normal pressure, and then the resulting liquid was purified by filtration 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 by the reaction was calculated with respect to 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the equivalent weight of the acid anhydride group.

[Synthesis Example 2-5]

In the same manner as in Synthesis Example 2-1, after charging 100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene, a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 mass %) 1.00 g was added while stirring. Next, the temperature was raised to 80°C, and 16.5 g (0.111 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Subsequently, an operation for reacting allylpolyether with the remaining ≡Si-H groups contained in methylhydrogensiloxane was performed. While the reaction solution was maintained at 80 ° C., 271 g (0.335 mol) of allyl polyether represented by CH ₂ =CH-CH ₂ -O (CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ was stirred. After dropwise addition, aging was performed 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, 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while stirring, and the temperature was raised to 110°C. Next, 62.3 g (0.445 mol) of allyl succinic anhydride was added dropwise, followed by aging at 115°C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-4, an operation for removing the remaining surplus allyl succinic anhydride was carried out, and the obtained liquid was purified by filtration 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 by the reaction was calculated with respect to 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the equivalent weight of the acid anhydride group.

[Synthesis Example 2-6]

In the same manner as in Synthesis Example 2-1, after charging 100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene, a toluene solution of Pt coordinated with vinylsiloxane (Pt concentration: 0.5 mass %) 1.00 g was added while stirring. Next, the temperature was raised to 80°C, and 16.5 g (0.111 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Subsequently, an operation for reacting allylpolyether with the remaining ≡Si-H groups contained in methylhydrogensiloxane was performed. 420 g (0.519 mol) of allyl polyether represented by CH ₂ =CH-CH ₂ -O(CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ while stirring the reaction solution at 80 ° C. After dropwise addition, aging was performed 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, 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while stirring, and the temperature was raised to 110°C. Next, 23.4 g (0.167 mol) of allyl succinic anhydride was added dropwise, followed by aging at 115°C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-4, an operation for removing remaining surplus allyl succinic anhydride was carried out, and the resulting liquid was purified by filtration 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 by the reaction was calculated with respect to 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the equivalent weight of the acid anhydride group.

[Synthesis Example 2-7]

In the same manner as in Synthesis Example 2-1, after charging 100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene, a toluene solution of Pt coordinated with vinylsiloxane (Pt concentration: 0.5 mass %) 1.00 g was added while stirring. 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.

Subsequently, an operation for reacting allylpolyether with the remaining ≡Si-H groups contained in methylhydrogensiloxane was performed. While the reaction solution was maintained at 80°C, 60.1 g (0.0742 mol) 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 while stirring. ) After adding dropwise, aging was performed for 3 hours.

Next, an operation for reacting 3-(perfluorohexyl)-1-propene with the remaining ≡Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while 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.

In addition, an operation for reacting allyl succinic anhydride with the remaining ≡Si-H groups contained in methylhydrogensiloxane was performed. To the reaction solution obtained above, 1.00 g of a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5% by mass) was added while stirring, and the temperature was raised to 110°C. Next, 46.8 g (0.334 mol) of allyl succinic anhydride was added dropwise, followed by aging at 115°C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-4, an operation for removing remaining surplus allyl succinic anhydride was carried out, and the resulting 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 (average value) of trimethoxysilyl groups, polyether groups, perfluorohexyl groups and succinic anhydride groups introduced by the reaction with respect to 1 mol of methylhydrogensiloxane Calculated. Table 3 shows the amount of each functional group introduced and the equivalent weight of the acid anhydride group.

[Synthesis Example 2-8]

After charging 100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene to a 1 liter three-necked flask equipped with a stirrer, a thermometer and a dimroth condenser cooling pipe, vinylsiloxane 1.00 g of a toluene solution of coordinating Pt (Pt concentration: 0.5% by mass) was added while stirring. 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.

Subsequently, an operation for reacting allylpolyether with the remaining ≡Si-H groups contained in methylhydrogensiloxane was performed. While the reaction solution was maintained at 80 ° C., 60.1 g (0.0742 mol) of allyl polyether represented by CH ₂ =CH-CH ₂ -O (CH ₂ CH ₂ CH 2 _O ) ₁₂ C ₄ H ₉ was stirred. After dropwise addition, aging was performed for 3 hours.

Next, an operation for reacting allylglycidyl ether with the remaining ≡Si-H groups contained in methylhydrogensiloxane was performed. After adding 50.7 g (0.445 mol) of allylglycidyl ether dropwise to the reaction solution obtained above, aging was performed for 10 hours.

Finally, in order to remove the remaining surplus allylglycidyl ether, in the same manner as in Synthesis Example 2-1, after reducing the pressure to 10 mmHg, heating was performed at 120°C for 5 hours under nitrogen gas bubbling. After completion of heating under reduced pressure, the temperature was cooled to room temperature and the pressure was restored to normal pressure, and then the obtained liquid was purified by filtration to obtain 219 g of Product-8.

Here, in the same manner as in Synthesis Example 2-1, the number (average value) of trimethoxysilyl groups, polyether groups, and epoxy groups introduced by reaction was calculated with respect to 1 mol of methylhydrogensiloxane. The amount of each functional group introduced and the epoxy equivalent are shown in Table 4.

[2] Preparation of pressure-sensitive adhesive composition

[Examples and Comparative Examples]

With respect to 100 parts by mass of the solid content of the copolymer solution containing (A) acrylic acid ester obtained in Synthesis Examples 1-1 and 1-2, each component shown in Tables 5 and 6 below was blended, and Examples 1-1 to 1 -7, 2-1 to 2-7, and Comparative Examples 1-1 to 1-4, and each adhesive composition of 2-1 to 2-4 were prepared.

TDI: trimethylolpropanetolylenediisocyanate adduct

TDI: trimethylolpropanetolylenediisocyanate adduct

X-24-1056: manufactured by Shin-Etsu Chemical Co., Ltd., epoxy-based alkoxy oligomer

X-41-1810: Shin-Etsu Chemical Industry Co., Ltd., methyl mercapto alkoxy oligomer

X-12-641: Polyether-modified silane, manufactured by Shin-Etsu Chemical Co., Ltd.

A uniform pressure-sensitive adhesive layer of 25 µm was formed by coating the pressure-sensitive adhesive composition obtained in each of the above Examples and Comparative Examples on a PET film (releasable substrate) and drying. An iodine-based polarizing plate having a thickness of 185 μm was bonded to the surface on which this pressure-sensitive adhesive layer was formed, and after curing for 7 days in an atmosphere of 25 ° C. and 50% RH, the obtained polarizing plate was cut into appropriate sizes, and the method shown below Thus, reworkability and durability were evaluated. The results are shown in Tables 7 and 8.

(1) Reworkability

A polarizing plate coated with an adhesive was cut to a size of 90 mm × 170 mm, the PET film was peeled off, bonded to a glass substrate, held at 50 ° C. and 0.5 MPa for 20 minutes to adhere, and a test sample was prepared. After leaving it at 25°C and 60% RH for 1 hour, it was further aged 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 or not it could be peeled without destroying the polarizing plate or the glass plate and without leaving an adhesive material on the glass surface, and evaluated based on the following criteria. The results are shown in Tables 7 and 8.

◎: Easy peeling (light peeling)

○: Peelable (heavy peeling)

△: Peeling is slightly difficult, the adhesive remains on the glass surface (heavy peeling)

×: Impossible to peel, broken glass or polarizing plate (heavy peeling)

(2) durability

A polarizing plate coated with an adhesive was cut to a size of 90 mm × 170 mm, the PET film was peeled off, bonded to a glass substrate, and then autoclave treatment was performed at 50 ° C. and 0.5 MPa for 20 minutes to adhere the polarizing plate to the glass. Next, after leaving it to stand for 1000 hours in an atmosphere of 80° C. (DRY) and an atmosphere of 60° C./90% RH, respectively, the presence or absence of bubble generation or peeling was confirmed and evaluated based on 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 still at room temperature (23 degreeC/60%RH) for 24 hours.

◎: No change in appearance such as peeling at all.

○: There is slight peeling, but there is no problem in practical use.

x: There is remarkable peeling, and there is a problem in practical use.

As shown in Tables 7 and 8, it was confirmed that the pressure-sensitive adhesive compositions of each example had good reworkability and durability, and were clearly superior to the pressure-sensitive adhesive compositions of comparative examples. The pressure-sensitive adhesive composition of the present invention exhibits excellent durability and is compatible with reworkability even when an OH-type acrylic resin containing a hydroxyl group as a main functional group is used.

Claims (10)

A copolymer of a polymerizable unsaturated monomer containing a (meth)acrylic acid ester monomer and an organosiloxane represented by the following formula [1a] having at least one hydrolyzable silyl group and at least one acid anhydride group in its molecule, and a hydrolyzate thereof A pressure-sensitive adhesive composition comprising at least one of

(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 hydrolysable silyl group, R ¹ are independently of each other, Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and M ¹ independently represents a group selected from the above X, Z and R ¹ , and a, b, c and d represents an integer of 0≤a≤100, b=0, 0≤c≤100, and 0≤d≤100, provided, however, that when a is 0, at least one of M ¹ is X, and c is It is an integer of 1≤c≤100, and when c is 0, at least one of M ¹ is Z, and a is an integer of 1≤a≤100. The array may be random or block.) The method according to claim 1, wherein X is a monovalent hydrocarbon group having an acid anhydride group represented by the following formula [2], and Z is a monovalent hydrocarbon group having a hydrolysable silyl group represented by the following formula [5]. A pressure-sensitive adhesive composition.

(In the formula, A represents an alkylene group having 2 to 6 carbon atoms.)

(Wherein, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, R ⁵ represents a monovalent hydrocarbon group or acyl group having 1 to 10 carbon atoms, n represents an integer of 2 or greater, and g represents 1 to 3 represents the integer of .) The pressure-sensitive adhesive composition according to claim 1, wherein at least one of R ¹ is a monovalent hydrocarbon group having a perfluoroalkyl group. The pressure-sensitive adhesive composition according to claim 1, wherein the organosiloxane and its hydrolyzate have an acid anhydride group equivalent of 5,000 g/mol or less. The pressure-sensitive adhesive composition according to claim 1, wherein the copolymer contains at least one of a structural unit derived from a carboxy group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer. The adhesive composition according to claim 1, wherein the compounding amount of the organosiloxane and at least one of its hydrolyzate is 0.001 to 5 parts by mass with respect to 100 parts by mass of the copolymer. The pressure-sensitive adhesive composition according to claim 1, wherein the copolymer contains 0.01 to 40 parts by mass of a crosslinking agent based on 100 parts by mass of the copolymer. The pressure-sensitive adhesive composition according to claim 7, wherein the crosslinking agent is at least one selected from isocyanate-based crosslinking agents, epoxy-based crosslinking agents, metal-based crosslinking agents, aziridine-based crosslinking agents, and peroxide-based crosslinking agents. A film with an adhesion layer characterized by having 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 surface of the film. delete