KR20180116136A - Adhesive composition and film made of the composition - 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; R^1s each independently represent a hydrogen atom and the like; M^1s each independently represent a group selected from among X, Y, Z, and R^1; and a, b, c, and d each independently represent an integer of 0-100, wherein when a is 0, at least one of the M^1s is X, and c is an integer of 1 <= c <= 100; and when c is 0, at least one M^1 is Z, and a is an integer of 1 <= a <= 100.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a pressure-sensitive adhesive composition and a film using the pressure-

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

In the liquid crystal display, first, a liquid crystal cell is formed 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 retarder is attached to the surface of the liquid crystal cell through a pressure- Are manufactured through a process.

This liquid crystal display device has been widely used as a display device for a vehicle, an outdoor device, a personal computer, etc., and a display device such as a television. Further, according to the enlargement of this application, the environment in which the liquid crystal display device is used is complicated, and therefore, it is used in a very harsh environment, and the pressure-sensitive adhesive composition used in the production of a liquid crystal display device can also be adapted to harsh environments Performance is required.

Specifically, even when exposed to high temperature or high temperature and high humidity conditions, the characteristics (hereinafter referred to as &quot; durability &quot;) in which foaming occurs in the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition or in which the bonded optical functional film is not peeled off the substrate, .

On the other hand, in the manufacturing process, the optical functional film and the liquid crystal cell may need to be reattached. In this case, it is required that the optical functional film can be easily peeled without damaging 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, in the pressure-sensitive adhesive used for bonding the optically functional film and the liquid crystal cell, it is required that the reheat property at the time of bonding is good and that the pressure-sensitive adhesive is highly durable after being bonded.

As the pressure-sensitive adhesive used for such a purpose, a large amount of acrylic resin is used. For example, Patent Document 1 proposes a pressure-sensitive adhesive composition containing an epoxy group-containing coupling agent in an acrylic polymer.

The composition of Patent Document 1 exhibits high durability for an acrylic polymer of the type containing a carboxy group as a reactive group (hereinafter referred to as &quot; COOH-type acrylic polymer &quot;). However, there is a problem that durability can not be obtained with respect to an acrylic polymer of a type containing a hydroxyl group as a main group as a reactive group (hereinafter referred to as &quot; OH type acrylic polymer &quot;).

In Patent Documents 2 and 3, a pressure-sensitive adhesive composition containing an epoxy group-containing polyether-modified coupling agent in an acrylic polymer has been proposed. This composition is compatible with the reworkability and durability of the COOH-type acrylic polymer. However, there is a problem that durability can not be obtained with respect to the OH type acrylic polymer.

Further, Patent Document 4 describes a pressure-sensitive adhesive composition comprising a mercapto group-containing silane coupling agent for an acrylic polymer. This composition improves the durability of the OH type acrylic polymer, but is not a sufficient level.

Further, Patent Document 5 proposes a pressure-sensitive adhesive composition comprising an acryl-based polymer containing a polyether-modified coupling agent containing an acid anhydride group. This composition is compatible with OH-type acrylic polymer for reworkability and durability. However, in recent years, as the demand for the durability of the pressure sensitive adhesive increases, it is required to further improve the durability.

Japanese Patent No. 5826179 Japanese Patent No. 5891534 Japanese Patent No. 3498158 Japanese Patent No. 5544858 Japanese Patent No. 5,990,847

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a pressure-sensitive adhesive composition capable of improving durability while maintaining good reworkability when used for bonding an optically functional film and a liquid crystal cell, And a pressure-sensitive adhesive layer formed thereon.

As a result of intensive investigations 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 organosiloxane having at least one hydrolyzable silyl group and an acid anhydride group, When a composition comprising an organosiloxane having at least one hydrolysable silyl group, an acid anhydride group and a polyether group in the molecule or the molecule is used for bonding an optically functional film to a liquid crystal cell, It is possible to improve the durability while maintaining a satisfactory condition, and found that it is suitable as a pressure-sensitive adhesive composition, and the present invention has been completed.

That is,

1. A copolymer comprising a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylic acid ester monomer and an organosiloxane having at least one hydrolyzable silyl group and an acid anhydride group each represented by the following formula [1a] Wherein the pressure-sensitive adhesive composition comprises at least one of 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 hydrolyzable silyl group, R &lt; ¹ &gt; A hydrogen atom, or a monovalent hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom, M ¹ independently represents a group selected from X, Y, Z and R ¹ , c and d each represent an integer of 0? a? 100, 0? b? 100, 0? c? 100, 0? d? 100, provided that when a is 0, at least one of M ¹ is X 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. In parentheses a, b, c, The arrangement of each repeating unit may be random or block.

2. A copolymer comprising a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylic acid ester monomer and a copolymer having at least one hydrolyzable silyl group, acid anhydride group and polyether group represented by the following formula [1b] A pressure-sensitive adhesive composition comprising at least one of a non-siloxane 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 hydrolyzable silyl group, R &lt; ¹ &gt; A hydrogen atom, or a monovalent hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom, M ¹ independently represents a group selected from X, Y, Z and R ¹ , c and d each represent an integer 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 B and c are integers of ^1? B? 100, 1? C? 100, and when b is 0, at least one of M ¹ is Y, and a and c are 1? A? 100, 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? An array of each repeat unit in parentheses with b, c, and d May be a random block or a block.

Wherein X is a monovalent hydrocarbon group having an acid anhydride group represented by the following formula [2], Y is a monovalent hydrocarbon group having a polyether group represented by the following formula [3] 1 or 2, which is a monovalent hydrocarbon group having a hydrolyzable silyl group represented by the formula [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 of 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 independently represent 0 Wherein at least one of e and f is an integer of 1 or more.

(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 an acyl group having 1 to 10 carbon atoms, n represents an integer of 2 or more, and g represents an integer of 1 to 3 Lt; / RTI &gt;

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

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

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

7. A pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the blending amount of at least one of the organosiloxane and the hydrolyzate thereof is 0.001 to 5 parts by mass relative to 100 parts by mass of the copolymer,

8. A pressure-sensitive adhesive composition according to any one of 1 to 7, which comprises 0.01 to 40 parts by mass of a crosslinking agent, based on 100 parts by mass of the copolymer,

9. A pressure-sensitive adhesive composition comprising at least one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, a metal crosslinking agent, an aziridine crosslinking agent and a peroxide crosslinking agent,

10. A pressure-sensitive adhesive sheet, which comprises a film and at least one surface of the film, wherein the pressure-sensitive adhesive layer has a layer comprising any one of the pressure-sensitive adhesive compositions 1 to 9

.

The pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive between an optically functional film and a liquid crystal cell in the production process of a liquid crystal display device, and although peeling is possible at the time of bonding, It is hard to rise or peel off.

The pressure-sensitive adhesive composition of the present invention having such properties can realize durability and reworkability, which are required to realize a high level in recent years. Therefore, the pressure-sensitive adhesive composition for a surface of a base material, the surface treatment agent for a fiber or a powder, It can be suitably used as a pressure-sensitive adhesive composition used for bonding an optically functional film in a process of manufacturing a liquid crystal display device.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

The pressure-sensitive adhesive composition according to the present invention comprises a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylic acid ester monomer and an organosiloxane represented by the above formula [1a] or [1b] and a hydrolyzate thereof Quot; or &quot; non-siloxane &quot;).

The copolymer of the polymerizable unsaturated monomer containing the (meth) acrylic acid ester monomer is a component which functions as a matrix resin in the pressure-sensitive adhesive composition, and is particularly limited as long as it is a copolymer of a polymerizable unsaturated monomer containing a (meth) acrylic acid ester monomer no.

Specific examples of the (meth) acrylic ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- butyl (meth) acrylate, isobutyl (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, Alkyl (meth) acrylates such as 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? -carboxyethyl acrylate; (Meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl Hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate; Caprolactone-modified (meth) acrylates; (Meth) acrylate such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. These monomers may be used alone or in combination of two kinds These may be used in combination.

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

Considering that the resin used for bonding the optically functional film and the liquid crystal cell has a pressure-sensitive adhesive property, the copolymer of the present invention contains at least one of a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a hydroxyl- Is preferably contained.

Specific examples of the monomer containing a carboxy group and / or a hydroxy group to provide such a structural unit include a carboxyl group such as a carboxyalkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate, a polyalkyleneglycol (meth) (Meth) acrylic acid and N- (2-hydroxyethyl) (meth) acrylamide. These monomers may be used alone or in combination of two or more.

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

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

Specific examples of other monomers include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptyl Styrene-based monomers such as styrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iododystyrene, nitrostyrene, acetylstyrene and methoxystyrene; 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 the repeating unit 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 the copolymer used in the present invention, there are no particular restrictions on the order of arrangement of the monomers therein, and random copolymers, block copolymers, and others may be used.

The weight average molecular weight of the copolymer is not particularly limited, but it is preferable that the cohesive force of the pressure-sensitive adhesive layer is increased and the foaming and peeling of the pressure-sensitive adhesive layer are suppressed to improve the durability and the viscosity of the pressure- It is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.

The weight average molecular weight is a polystyrene equivalent value determined 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 particularly preferable that the copolymer is produced by solution polymerization in which a copolymer is obtained as a solution , And thus the copolymer can be used as a solution to obtain the pressure-sensitive adhesive composition of the present invention.

As the solvent for the solution polymerization, an organic solvent is used, 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; And ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

The reaction solvent is preferably used in an amount of 50 to 300 parts by mass based on 100 parts by mass of the total amount of the monomers.

The polymerization initiator to be used in the polymerization may be appropriately selected from those known in the art, and specific examples thereof include di-tert-butylperoxide, benzoyl peroxide, lauryl peroxide, tert- butylperoxybenzoate, Oxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, tert-butylperoxy neodecanoate, tert-butylperoxy pivalate, (3,5,5-trimethylhexanoyl) peroxide, etc. Of peroxide; Azobisisobutyronitrile, azobisvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronite Azobis (2-methylpropionate), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) Azobis compounds such as azobis (2-hydroxymethylpropionitrile), and azo polymerization initiators. These may be used alone or in combination of two or more.

The reaction initiator is usually used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the monomers.

The polymerization reaction temperature is usually 50 to 90 占 폚, and the reaction time is usually 2 to 20 hours, 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 silicon skeleton different from that of a 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). In the compound described in Patent Document 5, the silicon skeleton has a three-dimensional structure, whereas the organosiloxane used in the present invention has a structure in which the silicon skeleton has a linear structure. As a result, when it is added to an acrylic resin, the transferability to the resin surface is improved, so that the functionality of the resin surface can be further improved. Also, due to the structural factors of the compound, the reactivity of an alkoxy group to an inorganic substrate such as glass is improved. Therefore, in the fusion of the optically functional film with the liquid crystal cell, the durability can be further improved.

Wherein X represents a monovalent hydrocarbon group having an acid anhydride group, Y represents a monovalent hydrocarbon group having a polyether group, Z represents a monovalent hydrocarbon group having a hydrolyzable silyl group, and R &lt; ¹ &gt; Represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom, and M ¹ independently represents a group selected from X, Y, Z and R ¹ .

In the above formulas, a, b, c and d each represent an integer of 0? A? 100, 0? B? 100, 0? C? 100, At least one of M ¹ is X and c is an integer of ^1? C? 100 when a is 0, and when c is 0, at least one of M ¹ is Z and a is 1? At least one of M ¹ is X and b and c are integers of 1? B? 100, 1? C? 100, and b is 0 when a is 0 in formula [1b] At least one of M ¹ is Y and a and c are integers of ^1? A? ¹⁰⁰ , ^1? C? 100, and when c is 0, at least one of M ¹ is Z and a, b is an integer of 1? a? 100, 1? b?

In the above formulas, the arrangement of each repeating unit in parentheses to which a, b, c and d are attached may be random or block.

Specific examples of the monovalent hydrocarbon group of 1 to 20 carbon atoms represented by R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, Straight, branched or cyclic alkyl groups such as cyclohexyl, n-octyl, n-nonyl, n-decyl, and n-octadecyl; Aryl groups such as phenyl, tolyl, xylyl and naphthyl groups; And aralkyl groups such as benzyl, phenylethyl and phenylpropyl groups.

Specific examples of the 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.

Of 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 A group represented by -C ₂ H ₄ -, C ₆ F ₁₃ -C ₃ H ₆ -, C ₈ F ₁₇ -C ₂ H ₄ -, or C ₈ F ₁₇ -C ₃ H ₆ -.

When the organosiloxane of the present invention is used in combination with the above-mentioned copolymer as a matrix resin by introducing the monovalent hydrocarbon group as R ¹ , the compatibility with the resin is improved and the phase separation becomes difficult to occur. At least one of R ¹ is preferably a monovalent hydrocarbon group, more preferably a monovalent hydrocarbon group, and all R ¹ is a methyl group, or a combination of a monovalent hydrocarbon group having a methyl group and a perfluoroalkyl group is further preferable .

Also, the organosiloxane used in the present invention has a monovalent hydrocarbon group X having an acid anhydride group, and when the organosiloxane is added to the matrix resin, the monovalent hydrocarbon group X is present, The acid anhydride group of X reacts with the reactive group (hydroxyl group, carboxyl group, etc.) of the matrix resin to integrate the resin and the organosiloxane.

The monovalent hydrocarbon group in the monovalent hydrocarbon group having an acid anhydride group may be the same as the group exemplified for R ¹ above, but an alkyl group is preferable, and a straight-chain alkyl group is more preferable.

Examples of the acid anhydride group include a maleic anhydride group and a maleic anhydride group.

Suitable X is a group represented by the following formula [2].

A is an alkylene group having 2 to 6 carbon atoms, and specific examples thereof include straight chain or branched alkylene groups such as ethylene, trimethylene, propylene, tetramethylene, pentamethylene and hexamethylene groups, , And a trimethylene group is preferable. Therefore, X is preferably an anhydrous succinic acid propyl group.

The organosiloxane used in the present invention has a monovalent hydrocarbon group Z having a hydrolyzable silyl group and has an univalent hydrocarbyl group Z so that an inorganic substrate such as glass is surface-treated with the organosiloxane , A hydrolyzable silyl group reacts with an -OH group present on the inorganic substrate surface, and a chemical bond is formed between the organosiloxane and the inorganic substrate.

The monovalent hydrocarbon group of the monovalent hydrocarbon group having a hydrolysable silyl group may be the same as the group exemplified for R ¹ above, but an alkyl group is preferable, and a linear alkyl group is more preferable.

Preferable examples of Z include those represented by the following formula [5].

R ⁴ represents an alkyl group having 1 to 10 carbon atoms, R ⁵ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or an acyl group, n is an integer of 2 or more, preferably an integer of 2 to 5, Preferably an integer of 2 or 3, and g represents an integer of 1 to 3, preferably 2 or 3, more preferably 3.

Specific examples of the alkyl group having 1 to 10 carbon atoms include the same alkyl groups as the alkyl groups having 1 to 10 carbon atoms among the alkyl groups exemplified for R ¹ above, but methyl group and 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.

Specific examples of the hydrolyzable silyl group (the part excluding -C _n H _2n - in the formula [5]) include trimethoxysilyl, methyldimethoxysilyl, dimethylmonomethoxysilyl, triethoxysilyl, methyl But are not limited to, diethoxysilyl, dimethylmonoethoxysilyl, tripropoxysilyl, methyldipropoxysilyl, dimethylmonopropoxysilyl, triisopropenoxysilyl, methyldiisopropeneoxysilyl, dimethylisopropene Oxysilyl, triacyloxysilyl, methyldiacyloxysilyl, dimethylmonoacyloxysilyl groups and the like, and at least one selected from these groups can be used. And is preferably a trimethoxysilyl group.

In the organosiloxane used in the present invention, the number of the hydrolyzable silyl group and the number of the acid anhydride groups can be freely adjusted. 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 acid anhydride group.

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

That is, the organosiloxane containing only the hydrolyzable silyl group and the acid anhydride group as the organic functional group has a low hydrophilicity of the acid anhydride group, and accordingly, the hydrophilicity of the entire molecule may be greatly lowered as the number of the organosiloxane is increased. For this reason, when the organosiloxane is applied onto an inorganic substrate having a hydrophilic surface to form a cured coating, problems such as a poor wettability and skipping, and a problem that a uniform coating film can not be obtained have. However, by introducing a polyether group into the molecule of the organosiloxane, such a problem is solved, and it becomes possible to form a uniform cured film of organosiloxane on the inorganic substrate.

It is also possible to adjust the binding force between the substrate and the organosiloxane by controlling the reaction between the hydrolyzable silyl group and the inorganic substrate by adjusting the type and amount of the polyether group. As a result, when the organosiloxane is used for bonding an organic resin and an inorganic substrate, the adhesive force can be adjusted depending on the application, from unadhesion to strong adhesion.

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.

Suitable Y is a group represented by the following formula [3].

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 having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.)

Examples of the monovalent hydrocarbon groups represented by the formulas [3] and [4] include those corresponding to the corresponding carbon atoms among the groups exemplified for R ¹ above.

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

e and f independently represent an integer of 0 or more, preferably 0? e? 50, 0? f? 50, more preferably 0? e? 20 and 0? f? Do. Provided that at least one of e and f is an integer of 1 or more, preferably 1 to 50. [

m represents an integer of 2 or more, preferably an integer of 2 to 6.

The polyether group portion is described as an ethylene oxide type (hereinafter referred to as EO type), a propylene oxide type (hereinafter referred to as PO type), an ethylene oxide-propylene oxide type . In the case of the EO-PO type, any of random, block, and alternate may be used.

Further, by introducing a monovalent hydrocarbon group having a polyether group of PO type into the organosiloxane used in the present invention, moisture resistance can be improved.

The polyether group portion may be a fluoropolyether group in which at least a part of the hydrogen atoms are substituted with fluorine. By containing fluorine, it becomes possible to increase 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 member selected from the following structural units.

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

Suitable examples of the organosiloxane used in the present invention include those represented by the following formulas [12] and [13], but are not limited thereto. In addition, the arrangement of each siloxane unit among the organosiloxanes 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, but is preferably 5,000 g / mol or less, more preferably 2,000 g / mol or less, still more preferably 1,500 g / mol or less, More preferably 1,000 g / mol or less.

The organosiloxane described above can be synthesized by reacting an organohydrogensiloxane represented by the following formula [7] with a hydrolyzable silyl group-containing compound having an aliphatic unsaturated bond and an acid anhydride group having an aliphatic unsaturated bond A compound and a polyether group-containing compound having an aliphatic unsaturated bond, if necessary, may be subjected to a hydrosilylation reaction.

In formula [7], R ¹⁰ represents a monovalent hydrocarbon group of 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 each represent an integer of 1? i? 300 and 0? j? 100, preferably an integer in the range of 1? i? 150 and 0? j? 50, 60, 0? J? 20. The arrangement of each repeating unit in parentheses to which i and j are attached may be a random or a 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].

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

Specific examples of the hydrolyzable silyl group-containing compound having an unsaturated bond include a vinyl group-containing alkoxysilane compound such as vinyltrimethoxysilane and vinyltriethoxysilane.

The reaction rate in the hydrosilylation reaction is preferably from 1 to 100 mol, more preferably from 1 to 50 mol, and still more preferably from 1 to 20 mol, based on 1 mol of the organohydrogensiloxane.

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

(Wherein p has the same meaning as defined above.)

Specific examples of the acid anhydride group-containing compound having an aliphatic unsaturated bond include the following compounds, and allylhydrosuccinic acid is particularly preferable.

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

The polyether group-containing compound having an aliphatic unsaturated bond includes, for example, those represented by the following formula [10].

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

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

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

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

More specifically, for example, in the case of the compound represented by the above formula [12], 4 mol of vinyltrimethoxysilane and 1 mol of vinyltrimethoxysilane are reacted with 1 mol of methylhydrogensiloxane represented by the following formula [14] , 1 mole of allyl polyether represented by the following formula [15], and 3 moles of allylhydrosicylic acid are subjected to a hydrosilylation reaction.

In the case of the compound represented by the above formula [13], 4 mol of vinyltrimethoxysilane and 4 mol of allylhydrosuccinic acid are reacted with 1 mol of methylhydrogensiloxane represented by the following formula [16] Followed by silylation 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 may be produced by hydrolysis and condensation of succinic anhydride-modified alkoxysilane and polyether-modified alkoxysilane Method. &Lt; / RTI &gt;

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

Further, as another method, for example, a method in which a cyclic organohydrogensiloxane represented by the following formula [17], a vinyltrimethoxysilane, an allyl polyether and an allylsuccinic anhydride are sequentially added And the like.

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

However, among the above-mentioned cyclic organohydrogensiloxanes, what is practically inexpensive and readily available is a low-molecular siloxane having k = 3 to 5. In this case, the number of reaction sites (SiH) present in the molecule may be up to five. When the cyclic organohydrogensiloxane is to be added by the hydrosilylation reaction in order of vinyltrimethoxysilane, allyl polyether and allylhydrous succinic acid, the total introduction amount of each compound is up to 5 So that it is not possible to set the free introduction amount of each functional group.

On the other hand, the above-described method for producing an organosiloxane of the present invention can solve the above problems.

That is, the introduction amount of vinyltrimethoxysilane, allyl polyether, and allylnaphosuccinic acid can be freely set by adjusting the i value of the organohydrogensiloxane represented by the above formula [7] used as a raw material .

The organosiloxane used in the present invention has a structure in which a group containing an alkoxy group, an acid anhydride group and 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 compounding ratio of the copolymer to be the matrix resin and the alkoxysilane is not particularly limited. However, it is preferable that the ratio of the organosiloxane to the organosiloxane More preferably from 0.01 to 3 parts by mass, and even more preferably from 0.1 to 2 parts by mass.

A crosslinking agent may be added to the pressure-sensitive adhesive composition of the present invention.

The blending amount of the crosslinking agent is not particularly limited. However, considering that the cohesive force of the pressure-sensitive adhesive composition is suitably adjusted to improve the durability and effectively suppress the film peeling, the crosslinking agent is preferably used in an amount of 0.01 to 40 Is preferably incorporated in an amount of 0.02 to 30 parts by mass.

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

More specifically, for example, polyglycidyl compounds having two or more glycidyl groups in one molecule, polyisocyanate compounds having two or more isocyanate groups in one molecule, aziridine A metal chelate compound or a butylated melamine compound having two or more diaries, and these may be used alone or in combination of two or more.

Specific examples of the polyglycidyl compound include ethylene glycol diglycidylether, polyethylene glycol diglycidylether, propylene glycol diglycidylether, polypropylene glycol diglycidyl Ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, N, N, N ', N'-tetra Lysidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl And polyfunctional glycidyl compounds such as diethers. These may be used alone or in combination of two or more.

Specific examples of the polyisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophoronediisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate , Diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like, and to these isocyanate compounds, An adduct in which a polyol such as glycerol or trimethylolpropane is reacted, or an isocyanate compound in which the isocyanate compound is a dimer, a trimer or the like. These may be used alone or in combination of two or more They may be used in combination.

Specific examples of the polyaziridine compound include 1,1 '- (methylene-di-p-phenylene) bis-3,3-aziridylurea, 1,1' - (hexamethylene) , Ethylene bis- (2-aziridinyl propionate), tris (1-aziridinyl) phosphine oxide, 2,4,6-triaziridinyl-1,3,5-triazine, Tris- (2-aziridinyl propionate), etc. These may be used alone or in combination of two or more kinds.

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

Radiation (preferably ultraviolet ray) crosslinking is also effective as a crosslinked form. At this time, a monomer having at least two polymerizable reactive double bonds and a photopolymerization initiator (including a sensitization system) may 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, 1,9-nonene diol Bifunctional (meth) acrylates such as diacrylate; (Such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, isocyanuric acid triacrylate, and tris (2-acryloxyethyl) isocyanurate. Methacrylate, and the like.

In addition, crosslinking density control may be performed by using a known monomer having only one reactive double bond capable of polymerization as needed.

As the photopolymerization initiator, a photopolymerization initiator based on a known radiation (ultraviolet ray) can be used. Examples of the photopolymerization initiator include an aminoketone type, hydro ketone type, acylphosphine oxide type, benzyldimethylketal type, benzophenone type, Triazine-derived photopolymerization initiator, and the like.

In addition, the pressure-sensitive adhesive composition of the present invention can further comprise a silane coupling agent other than the above-mentioned essential organosiloxane and / or a hydrolyzed condensate thereof (also referred to as a silane coupling agent) 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 relative to 100 parts by mass of the copolymer.

Specific examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Epoxy group-containing silane coupling agents such as ricidoxypropylmethyldiethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and epoxy group-containing alkoxysilane oligomer; ? -mercaptopropyltrimethoxysilane,? -mercaptopropyltriethoxysilane,? -mercaptopropylmethyldimethoxysilane,? -mercaptopropylmethyldiethoxysilane, a mercapto group-containing alkoxy A mercapto group-containing silane coupling agent such as a silane oligomer; ? - (aminoethyl) -? - aminopropyltrimethoxysilane, N-? - (aminoethyl) -γ-aminopropyltrimethoxysilane,? -aminopropyltriethoxysilane, N- Amino group-containing silane coupling agents such as aminopropyltriethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane and N-phenyl-? -Aminopropyltrimethoxysilane; and isocyanate group-containing silane coupling agents such as? -isocyanate propyltrimethoxysilane and? -isocyanate propyltriethoxysilane, and these may be used singly, Two or more kinds may be used in combination.

The pressure-sensitive adhesive composition of the present invention may be blended with various additives within a range that does not impair the effect of the present invention, depending on the necessary properties such as the purpose of adjusting the adhesive strength.

Examples of the additives include adhesion-imparting resins such as terpene, terpene-phenol, coumarone-indene, styrene, rosin, xylene, phenol and petroleum, antioxidants, ultraviolet absorbers, fillers, pigments, plasticizers, And the like.

The adhesive layer-adhering film of the present invention comprises a film and a layer formed by using the pressure-sensitive adhesive composition of the present invention described above on at least one surface of the film.

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

Therefore, the pressure-sensitive adhesive layer-bearing film of the present invention is excellent in properties (durability) that the pressure-sensitive adhesive layer does not peel from the glass substrate or the like constituting the liquid crystal cell even at high temperature but high temperature and high humidity, (Reworkability) that does not cause residues on the substrate or the like even after peeling off.

The kind 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 film obtained by combining them.

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 set to a suitable thickness depending on the application or purpose, but may be, for example, about 5 to 300 m.

The adhesive layer-adhering film of the present invention can be produced by applying the pressure-sensitive adhesive composition of the present invention to one side or both sides of the raw material film using a commonly used coating device, such as a roll coating device, (Pressure-sensitive adhesive layer). If necessary, the applied pressure-sensitive adhesive layer may be cured by heat crosslinking or light such as ultraviolet rays to form a cured film.

The pressure-sensitive adhesive layer-bearing film of the present invention is obtained by first coating a pressure-sensitive adhesive composition of the present invention on a protective film such as a polyethylene terephthalate film (PET film) coated with a releasing agent such as a silicone resin, And then, a raw material film is laminated on the pressure-sensitive adhesive layer.

In any of the above cases, the coating amount of the pressure-sensitive adhesive composition is preferably such that the thickness of the pressure-sensitive adhesive layer (film) after drying becomes 10 to 50 占 퐉. By setting the thickness of the pressure-sensitive adhesive layer within the above-mentioned range, a pressure-sensitive adhesive layer-attached film which is suitable as an optically functional film and has a balance of durability and reworkability can be obtained.

The adhesive layer-adhering film of the present invention produced in the above-described manner can be adhered onto a glass substrate of a liquid crystal cell such as a liquid crystal display device by a commonly used means.

The adhesive layer-adhering film of the present invention may also be laminated and adhered onto an optical functional film adhered on a glass substrate.

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The apparatuses used in the examples are as follows.

Infrared Spectroscopy (FTIR): Thermo sientific NICOLET6700

²⁹ Si-NMR: Bruker's AVANCE400M

GPC: Topical agent 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, a reflux condenser, a dropping funnel and a thermometer, and air in the apparatus was replaced with nitrogen gas. Then, 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) 0.1 g of nitrile and 100 g of ethyl acetate were charged and reacted at 70 DEG 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 obtained 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) . The weight average molecular weight of the copolymer by GPC was 1,500,000.

[2] Synthesis of organosiloxane

[Synthesis Example 2-1]

100 g (0.192 mol) of the organohydrogensiloxane shown in the following formula [18] and 114 g of toluene were charged into a 1-liter three-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser cooling tube, Siloxane coordination 1.00 g of a toluene solution of Pt was added with stirring. Then, the temperature was raised to 80 占 폚, and 56.7 g (0.383 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Here, the reaction rate of the vinyltrimethoxysilane used in the above reaction was measured in the following manner.

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 was added to 1 g of the sample before and after the reaction, and 20 g of a 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 equation. The results are shown in Table 1.

Reaction amount (mol) = [? SiH content (mol) before reaction] - [? SiH content (mol)

In 1 g of the sample before the reaction, 1.41 × 10 ^-3 mol of vinyltrimethoxysilane charged as a raw material was present. From the amount of the reaction previously obtained and the amount charged as the raw material, the reaction rate of vinyltrimethoxysilane is calculated to be 99.3% as described below.

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

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

Next, an operation was performed to react allylhydrosuccinic acid with the remaining ≡Si-H groups contained in the methylhydrogensiloxane. 1.00 g of a toluene solution (Pt concentration: 0.5 mass%) of Pt in a vinylsiloxane coordination state was added to the reaction solution obtained above with stirring, and the temperature was raised to 110 캜. Subsequently, 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 allylhydrous succinic acid 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 allylhydrous succinic acid actually reacted was calculated. The results are shown in Table 2.

The amount of hydrogen gas generated after the completion of the reaction was close to 0 ml. From this, it is considered that the ≡SiH remaining in the methylhydrogensiloxane reacted with the allyl anhydridesuccinic acid by virtue of the hydrosilylation reaction.

In 1 g of the sample before the reaction, 2.17 x 10 &lt; ^-3 &gt; mol of allylhydrous succinic acid charged as a raw material was present. From the amount of the reaction previously obtained and the amount charged as the raw material, the reaction rate of allylhydrous succinic acid is calculated as described below to be 87.6%.

^{[1.90 × 10 -3 (mol)} /2.17×10 -3 (mol) × 100 = 87.6 (%)]

About 88% of the allyl anhydride succinic acid charged as the raw material reacted with methylhydrogensiloxane, and the remaining about 12% remained as surplus.

Finally, an operation was performed to remove residual surplus allyl anhydridesic acid. The dimox cooler cooling tube was connected to an exhaust gas pipe, and the pressure in the system was reduced to 10 mmHg, followed by heating at 150 DEG C for 20 hours under nitrogen gas bubbling. After completion of the reduced-pressure heating, the temperature was cooled to room temperature, the pressure was returned to normal pressure, and the obtained liquid was filtrated and purified to obtain 246 g of the product-1.

Here, regarding the product-1, GPC measurement was carried out in a THF solvent. As a result, a broad peak of the product was observed at a holding time of 21 to 32 minutes. It is considered that the excess of allylhydrosic succinic acid was almost completely removed by the last decompression heating in that the peak of allylphthalic anhydride was not present in the vicinity of the retention time of 36 to 37 minutes.

Next, regarding the product-1, attachment of an acid anhydride group was carried out by infrared spectroscopy (FTIR). As a result, absorption at 1863 cm ^-1 and 1785 cm ^-1 was observed by the stretching vibration of the carbon monoxide anhydride group. Absorption by carboxy stretching vibration of the carboxy group resulting from the ring opening of the anhydride group was not observed at 1735 cm ^-1 . Since the production of product-1 is carried out completely in the non-aqueous system, the active hydrogen-containing compound (such as water or alcohol) is not incorporated in the production step, and the conversion of the anhydride group is sufficiently inhibited.

Next, ²⁹ Si-NMR measurement was carried out to analyze the structure-1 structure. As a result, at first about 7.2 ppm, one peak indicating the existence of the structure shown below was confirmed.

In addition, near the -22 ppm, one peak indicating the presence of the structure shown below was confirmed.

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

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

From the above results, it is presumed that the product-1 is a structure in which a monovalent hydrocarbon group containing a trimethoxysilyl group and a monovalent hydrocarbon group containing a succinic anhydride group are bonded to the side chain of the linear siloxane.

From the measurement results of the amounts of each raw material of methylhydrogensiloxane, vinyltrimethoxysilane, and allylhydrous succinic acid, and the reaction rate, it was confirmed from the measurement results that the amount of trimethoxysilyl introduced into 1 mole of methylhydrogensiloxane (Average value) of the anhydride groups and the anhydride groups were calculated. Table 3 shows the amount of each functional group introduced and the acid anhydride group equivalent.

[Synthesis Example 2-2]

100 g (0.0371 mol) of methylhydrogensiloxane represented by the following formula [19] and 114 g of toluene were charged in the same manner as in Synthesis Example 2-1, and a toluene solution of vinyl siloxane-coordinated Pt (Pt concentration: 0.5 Mass%) was added with stirring. Then, the temperature was raised to 80 DEG C, and 55.0 g (0.371 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Then, the remaining ≡Si-H group contained in the methylhydrogensiloxane was subjected to an operation for reacting allylhydrosuccinic acid. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5 mass%) of Pt in a vinyl siloxane coordination state was added with stirring, and the temperature was raised to 110 캜. Subsequently, 62.3 g (0.445 mol) of allyl-succinic anhydride was added dropwise and aged at 115 ° C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-1, an operation for removing residual surplus allylphthalic anhydrosuccinic acid was carried out, and the resulting liquid was subjected to filtration purification to obtain 178 g of Product-2.

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

[Synthesis Example 2-3]

100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene were charged in the same manner as in Synthesis Example 2-1, and a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 Mass%) was added with stirring. Then, the temperature was raised to 80 DEG C, and 55.0 g (0.371 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Then, the remaining ≡Si-H group contained in the methylhydrogensiloxane was subjected to an operation for reacting 3- (perfluorohexyl) -1-propene. The temperature of the reaction solution obtained above was raised to 100 占 폚, and 26.7 g (0.0742 mol) of 3- (perfluorohexyl) -1-propene was added dropwise, followed by further aging for 5 hours.

Then, the remaining ≡Si-H group contained in the methylhydrogensiloxane was subjected to an operation for reacting allylhydrosuccinic acid. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5 mass%) of Pt in a vinyl siloxane coordination state was added with stirring, and the temperature was raised to 110 캜. Subsequently, 62.3 g (0.445 mol) of allyl-succinic anhydride was added dropwise and aged at 115 ° C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-1, an operation for removing residual surplus allylphthalic anhydrosaric acid was carried out, and the obtained liquid was subjected to filtration purification to obtain 199 g of Product-3.

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

[Synthesis Example 2-4]

100 g (0.192 mol) of methylhydrogensiloxane shown in the above formula [18] and 114 g of toluene were charged in the same manner as in Synthesis Example 2-1, and then a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 Mass%) was added with stirring. Then, the temperature was raised to 80 ° C, 56.9 g (0.384 mol) of vinyltrimethoxysilane was added dropwise, and the mixture was aged for 2 hours.

Subsequently, an operation for reacting the allyl polyether with a part of the? Si-H groups remaining in the methylhydrogensiloxane was carried out. The reaction solution was maintained in a state in 80 ℃, _{stirring, CH 2 = CH-CH 2} -O (CH 2 CH 2 O) 8 CH 3 by dropwise addition of emitter 81.4g (0.192mol) in allyl poly represented by And then aged for 3 hours.

Then, the remaining ≡Si-H group contained in the methylhydrogensiloxane was subjected to an operation for reacting allylhydrosuccinic acid. The temperature of the reaction solution was raised to 110 占 폚 and 1.00 g of a toluene solution of Pt siloxane-coordinated Pt (Pt concentration: 0.5 mass%) was added with stirring, and 121 g (0.864 mol) of allylhydrous succinic acid was added dropwise And then aged at 115 ° C for 10 hours.

Finally, in order to remove residual surplus allylhydrosic succinic acid, the pressure was reduced to 10 mmHg in the same manner as in Synthesis Example 2-1, followed by heating at 120 캜 for 20 hours under nitrogen gas bubbling. After completion of the reduced-pressure heating, the temperature was cooled to room temperature, the pressure was returned to normal pressure, and the obtained liquid was filtrated 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 the reaction-introduced trimethoxysilyl group, polyether group and anhydride group was calculated for 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the acid anhydride group equivalent.

[Synthesis Example 2-5]

100 g (0.0371 mol) of methylhydrogensiloxane shown in the above formula [19] and 114 g of toluene were charged in the same manner as in Synthesis Example 2-1, and a toluene solution of vinylsiloxane coordination Pt (Pt concentration: 0.5 Mass%) was added with stirring. Then, the temperature was raised to 80 占 폚, and 16.5 g (0.111 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Subsequently, the remaining ≡Si-H groups contained in the methylhydrogensiloxane were subjected to an operation for reacting the allyl polyether. 271 g (0.335 mol) 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 thereto while stirring at 80 ° C., After the dropwise addition, aging was carried out for 3 hours.

Then, the remaining ≡Si-H group contained in the methylhydrogensiloxane was subjected to an operation for reacting allylhydrosuccinic acid. 1.00 g of a toluene solution (Pt concentration: 0.5 mass%) of Pt in a vinylsiloxane coordination state was added to the reaction solution obtained above with stirring, and the temperature was raised to 110 캜. Subsequently, 62.3 g (0.445 mol) of allyl-succinic anhydride was added dropwise and aged at 115 ° C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-4, an operation for removing residual surplus allylphthalic anhydrosuccinic acid was carried out, and the resulting liquid was filtrated and purified to obtain 367 g of the product-5.

Here, in the same manner as in Synthesis Example 2-1, the number (average value) of the reaction-introduced trimethoxysilyl group, polyether group and anhydride group was calculated for 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the acid anhydride group equivalent.

[Synthesis Example 2-6]

100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene were charged in the same manner as in Synthesis Example 2-1, and a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 Mass%) was added with stirring. Then, the temperature was raised to 80 占 폚, and 16.5 g (0.111 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Subsequently, the remaining ≡Si-H groups contained in the methylhydrogensiloxane were subjected to an operation for reacting the allyl polyether. (0.519 mol) of an allyl polyether represented by CH ₂ = CH-CH ₂ -O (CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ under stirring while maintaining the reaction liquid at 80 ° C, After the dropwise addition, aging was carried out for 3 hours.

Then, the remaining ≡Si-H group contained in the methylhydrogensiloxane was subjected to an operation for reacting allylhydrosuccinic acid. 1.00 g of a toluene solution (Pt concentration: 0.5 mass%) of Pt in a vinylsiloxane coordination state was added to the reaction solution obtained above with stirring, and the temperature was raised to 110 캜. Then, 23.4 g (0.167 mol) of allylhydrous succinic acid was added dropwise, followed by aging at 115 DEG C for 10 hours.

Finally, in the same manner as in Synthesis Example 2-4, an operation for removing residual surplus allylphthalic anhydrosuccinic acid was carried out, and the obtained liquid was filtrated and purified to obtain 475 g of the product-6.

Here, in the same manner as in Synthesis Example 2-1, the number (average value) of the reaction-introduced trimethoxysilyl group, polyether group and anhydride group was calculated for 1 mol of methylhydrogensiloxane. Table 3 shows the amount of each functional group introduced and the acid anhydride group equivalent.

[Synthesis Example 2-7]

100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene were charged in the same manner as in Synthesis Example 2-1, and a toluene solution of vinylsiloxane-coordinated Pt (Pt concentration: 0.5 Mass%) was added with stirring. Then, the temperature was raised to 80 DEG C, and 55.0 g (0.371 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Subsequently, the remaining ≡Si-H groups contained in the methylhydrogensiloxane were subjected to an operation for reacting the allyl polyether. While maintaining the reaction solution at 80 占 폚, 60.1 g (0.0742 mol) of an allyl polyether represented by CH ₂ = CH-CH ₂ -O (CH ₂ CH ₂ CH ₂ O) ₁₂ C ₄ H ₉ ), Followed by aging for 3 hours.

Then, the remaining ≡Si-H groups contained in the methylhydrogensiloxane were subjected to an operation for reacting 3- (perfluorohexyl) -1-propene. To the reaction solution obtained above, 1.00 g of a toluene solution of Pt siloxane-coordinated Pt (Pt concentration: 0.5 mass%) was added with stirring, and the temperature was raised to 100 캜. Then, 26.7 g (0.0741 mol) of 3- (perfluorohexyl) -1-propene was added dropwise and aged for 5 hours.

Further, an operation for reacting allylhydrosuccinic acid with the remaining ≡Si-H groups contained in the methylhydrogensiloxane was carried out. To the reaction solution obtained above, 1.00 g of a toluene solution (Pt concentration: 0.5 mass%) of Pt in a vinyl siloxane coordination state was added with stirring, and the temperature was raised to 110 캜. Subsequently, 46.8 g (0.334 mol) of allylphthalic 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 residual surplus allylphthalic anhydrosuccinic acid was carried out, and the obtained liquid was filtrated and purified to obtain 230 g of Product-7.

Here, in the same manner as in Synthesis Example 2-1, the number (average value) of the reaction-introduced trimethoxysilyl group, polyether group, perfluorohexyl group, and anhydrous succinic acid groups, relative to 1 mol of methylhydrogensiloxane, Respectively. Table 3 shows the amount of each functional group introduced and the acid anhydride group equivalent.

[Synthesis Example 2-8]

100 g (0.0371 mol) of methylhydrogensiloxane represented by the above formula [19] and 114 g of toluene were charged into a 1-liter three-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser cooling tube, 1.00 g of a toluene solution of coordination Pt (Pt concentration: 0.5% by mass) was added with stirring. Then, the temperature was raised to 80 DEG C, and 55.0 g (0.371 mol) of vinyltrimethoxysilane was added dropwise, followed by aging for 2 hours.

Subsequently, the remaining ≡Si-H groups contained in the methylhydrogensiloxane were subjected to an operation for reacting the allyl polyether. 60.1 g (0.0742 mol) 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 thereto while stirring at 80 ° C., After the dropwise addition, aging was carried out for 3 hours.

Next, the remaining ≡Si-H groups contained in the methylhydrogensiloxane were reacted with allyl glycidyl ether. To the reaction solution obtained above, 50.7 g (0.445 mol) of allyl glycidyl ether was added dropwise, followed by aging for 10 hours.

Finally, to remove residual surplus allyl glycidyl ether, the pressure was reduced to 10 mmHg in the same manner as in Synthesis Example 2-1, followed by heating at 120 캜 for 5 hours under nitrogen gas bubbling. After completion of the reduced-pressure heating, the temperature was cooled to room temperature, the pressure was returned to normal pressure, and the obtained liquid was filtrated and purified to obtain 219 g of product-8.

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

[2] Preparation of pressure-sensitive adhesive composition

[Examples and Comparative Examples]

Each of the components described in Tables 5 and 6 was blended with 100 parts by mass of the solid content of the copolymer solution containing the acrylic acid ester (A) obtained in Synthesis Examples 1-1 and 1-2, -7, 2-1 to 2-7, and Comparative Examples 1-1 to 1-4 and 2-1 to 2-4 were prepared.

TDI: Trimethylol propane tallylene diisocyanate adduct

TDI: Trimethylol propane tallylene diisocyanate adduct

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

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

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

The pressure-sensitive adhesive compositions obtained in the above Examples and Comparative Examples were coated on a PET film (releasable substrate) and dried to form a uniform pressure-sensitive adhesive layer of 25 탆. An iodine polarizing plate having a thickness of 185 mu m was laminated on the surface on which the pressure-sensitive adhesive layer was formed and cured for 7 days under an atmosphere of 25 DEG C and 50% RH. The obtained polarizing plate was cut into an appropriate size, , The reworkability and durability were evaluated. The results are shown in Tables 7 and 8.

(1) Re-workability

The polarizer coated with the pressure-sensitive adhesive was cut into a size of 90 mm x 170 mm, and the PET film was peeled off and attached to the glass substrate, and then held at 50 DEG C and 0.5 MPa for 20 minutes to adhere to each other to produce a test sample. Left at 25 ° C and 60% RH for 1 hour, aged at 70 ° C for 20 hours, and allowed to cool to 25 ° C.

Next, the polarizing plate was peeled off from the glass, and it was confirmed whether or not the polarizing plate or the glass plate was not broken and the peeling could be performed without leaving the adhesive on the glass surface, and evaluation was made based on the following criteria. The results are shown in Tables 7 and 8.

◎: Easily peelable (peel off)

○: Peelable (heavy)

?: Peeling was a little difficult, the adhesive remained on the glass surface (heavy)

X: Inability to peel off, breakage of glass or polarizing plate (heavy)

(2) Durability

The polarizing plate coated with the pressure-sensitive adhesive was cut to a size of 90 mm x 170 mm, the PET film was peeled off, and the resultant was adhered to a glass substrate, followed by autoclaving at 50 DEG C and 0.5 MPa for 20 minutes to adhere the polarizing plate to the glass. Subsequently, each of the substrates was allowed to stand in an atmosphere of 80 DEG C (DRY) and 60 DEG C / 90% RH for 1000 hours, respectively. Then, the presence or absence of formation of bubbles was checked and evaluated based on the following criteria. The results are shown in Tables 7 and 8. Further, before evaluating the state of the test piece, it was allowed to stand at room temperature (23 DEG C / 60% RH) for 24 hours.

?: No apparent change such as peeling was observed.

○: Although there is a slight but peeling, there is no practical problem.

X: There is significant peeling, there is a problem in practical use.

As shown in Tables 7 and 8, it was confirmed that the pressure-sensitive adhesive composition of each of the Examples was satisfactory in both reworkability and durability, and clearly superior to the pressure-sensitive adhesive composition of Comparative Example. INDUSTRIAL APPLICABILITY The pressure-sensitive adhesive composition of the present invention exhibits excellent durability and compatibility with rework performance even when an OH type acrylic resin containing a hydroxyl group as a functional group is used.

Claims (10)

(Meth) acrylic acid ester monomer and an organosiloxane having at least one hydrolyzable silyl group and an acid anhydride group in the molecule each represented by the following formula [1a] and a hydrolyzate thereof Of the pressure-sensitive adhesive composition.

(Wherein X represents a monovalent hydrocarbon group having an acid anhydride group, Y represents a monovalent hydrocarbon group having a polyether group, Z represents a monovalent hydrocarbon group having a hydrolyzable silyl group, R &lt; ¹ &gt; A hydrogen atom, or a monovalent hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom, M ¹ independently represents a group selected from X, Y, Z and R ¹ , c and d each represent an integer of 0? a? 100, 0? b? 100, 0? c? 100, 0? d? 100, provided that when a is 0, at least one of M ¹ is X 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. In parentheses a, b, c, The arrangement of each repeating unit may be random or block. (Meth) acrylate monomer having at least one hydrolyzable silyl group, an acid anhydride group and a polyether group in the molecule represented by the following formula [1b], and a copolymer of a polymerizable unsaturated monomer containing a Wherein the pressure-sensitive adhesive composition comprises at least one of cine and 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 hydrolyzable silyl group, R &lt; ¹ &gt; A hydrogen atom, or a monovalent hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom, M ¹ independently represents a group selected from X, Y, Z and R ¹ , c and d each represent an integer 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 B and c are integers of ^1? B? 100 and 1? C? 100, and when b is 0, at least one of M ¹ is Y, and a and c are 1? A? 100, 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? An array of each repeat unit in parentheses with b, c, and d May be a random block or a block. The polyimide resin 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 monovalent hydrocarbon having a polyether group represented by the following formula [3] Group, and Z is a monovalent hydrocarbon group having a hydrolyzable silyl group represented by the following formula [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 of 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 independently represent 0 Wherein at least one of e and f is an integer of 1 or more.

(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 an acyl group having 1 to 10 carbon atoms, n represents an integer of 2 or more, and g represents an integer of 1 to 3 Lt; / RTI &gt; Wherein the first to third according to any one of claims, wherein the pressure-sensitive adhesive composition of the first with at least one of said R ¹ having a perfluoroalkyl group wherein the hydrocarbon group. The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the organosiloxane and the hydrolyzate thereof have an acid anhydride group equivalent of 5,000 g / mol or less. The pressure-sensitive 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 monomer containing a carboxyl group and a structural unit derived from a monomer containing a hydroxyl group. The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the blending amount of at least one of the organosiloxane and the hydrolyzate thereof is 0.001 to 5 parts by mass based on 100 parts by mass of the copolymer. The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the crosslinking agent is contained in an amount of 0.01 to 40 parts by mass based on 100 parts by mass of the copolymer. The pressure-sensitive adhesive composition according to claim 8, wherein the crosslinking agent is at least one selected from an isocyanate crosslinking agent, an epoxy crosslinking agent, a metal crosslinking agent, an aziridine crosslinking agent and a peroxide crosslinking agent. A pressure-sensitive adhesive layer-adhering film characterized by having a film and a layer formed by using the pressure-sensitive adhesive composition according to any one of claims 1 to 9 on at least one side of the film.