KR20130111277A - Adhesive composition and adhesive sheet - Google Patents

Abstract

PURPOSE: An adhesive composition has excellent balance of reworkability and durability by mixing a small amount of a specific silane coupling agent into adhesive components even when acid-free adhesive components are used. CONSTITUTION: An adhesive composition comprises an adhesive component; a silane coupling agent including an isocyanate group; and at least one component selected from a crosslinking agent and a hardener. The silane coupling agent with an isocyanate group is formed by the reaction of a polyisocyanate compound and an alkoxysilane compound which has a reactive organic functional group. The amount of the silane coupling agent mixed is 0.005-5 parts by weight per 100.0 parts by weight of the adhesive component. [Reference numerals] (A) 1 day later; (AA) Adhesive power [N/25mm]; (B) 21 days later; (BB) Mixing about of silane coupling agent including an isocyanate group [parts by weight]

Description

Adhesive composition and adhesive sheet {ADHESIVE COMPOSITION AND ADHESIVE SHEET}

The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet. In particular, even when an acid-free pressure-sensitive adhesive component is used, a relatively small amount of a specific silane coupling agent is added to the pressure-sensitive adhesive component, so that the pressure-sensitive adhesive composition excellent in the balance of reworkability and durability under a predetermined environment and the pressure-sensitive adhesive composition using such a pressure-sensitive adhesive composition It is about a sheet.

Conventionally, in the adhesive composition used for optical members, window films, etc., such as a polarizing plate, when the surfaces of different materials, such as a plastic material and glass, can be bonded together durable, and when a bonding miss arises, The thing which can peel (rework property) without leaving an adhesive composition on the glass surface is calculated | required.

Therefore, it is common that a silane coupling agent is added to the adhesive composition used for the above-mentioned use.

That is, since the silane coupling agent usually has an alkoxysilyl group portion and a bonding group portion in one molecule, the alkoxysilyl group portion acts on the glass surface, while the bonding group portion can react with a polymer or the like in the pressure-sensitive adhesive composition. By increasing the adhesive force over time, it is possible to impart predetermined durability to the adhesive sheet.

For this reason, even if the initial adhesive force of an adhesive sheet is designed comparatively low, by adding a silane coupling agent, adhesive force can be raised over time, and also the rework property of an adhesive sheet and durability can be aimed at. .

Therefore, the adhesive composition for optical members which mix | blends a predetermined amount with such a silane coupling agent with respect to the adhesive component containing a (meth) acrylic-type polymer, a predetermined crosslinking agent, and an optical crosslinking agent is disclosed (for example, a patent document) One).

More specifically, for optical members containing a predetermined amount of isocyanate-based crosslinking agent, a predetermined amount of photocrosslinking agent, and a predetermined amount of amino group-containing silane coupling agent in a (meth) acrylic polymer containing a predetermined amount of hydroxyl group-containing monomer. An adhesive composition is disclosed.

Moreover, for the purpose of providing the adhesive composition for optical members which is favorable in reworkability and can satisfy | fill workability and durability, it contains a predetermined amount of a (meth) acrylic-type polymer, a predetermined crosslinking agent, and a predetermined silane coupling agent. The adhesive composition for optical members formed is disclosed (for example, patent document 2).

More specifically, the pressure-sensitive adhesive composition for optical members containing a predetermined amount of isocyanate-based crosslinking agent and a predetermined amount of amino group-containing silane coupling agent in a (meth) acrylic polymer containing a predetermined amount of hydroxyl group-containing monomer is disclosed.

Moreover, after sticking to a glass plate, there is no external appearance change, such as yellowing with time, and an acrylic copolymer and an isoshi for the purpose of providing the adhesive composition which can also have the effect of preventing scattering of glass. The adhesive composition containing an anato group containing silane compound is disclosed (for example, patent document 3).

More specifically, the adhesive composition which mix | blends predetermined amount of (gamma) -isocyanate propyl trimethoxysilane with respect to an acryl-type copolymer is disclosed.

Moreover, even if the polarizing plate is fixed to a translucent adherend via an adhesive layer, the adhesive polarizing plate which an adhesive layer does not foam or peels is disclosed (for example, patent document 4).

More specifically, the pressure-sensitive adhesive polarizing plate in which a pressure-sensitive adhesive layer formed by blending a predetermined amount of a silane compound having a predetermined structure having an isocyanato group at least one end with an acrylic resin is laminated on one side of the polarizing film is Is disclosed.

Moreover, the primer composition which is excellent in weatherability etc. and is applicable widely also to the to-be-adhered body which differs extremely in surface form is disclosed (for example, patent document 5).

More specifically, (A ') a reaction product of a predetermined saturated hydrocarbon-based polymer having at least one reactive functional group, (B') an organic solvent, (C ') a polyisocyanate compound, a polyisocyanate compound, and a silane coupling agent, Moreover, the primer composition which contains at least 1 sort (s) chosen from the group which consists of these mixtures, and (D ') epoxy resin is disclosed.

Japanese Patent Laid-Open No. 2009-258499 (patent claims, etc.) Japanese Patent Laid-Open No. 2009-173772 (patent claims, etc.) Japanese Patent Laid-Open No. 2004-49710 (patent claims, etc.) Japanese Patent Laid-Open No. 9-288214 (patent claims, etc.) Japanese Patent Laid-Open No. 2001-152080 (patent claims, etc.)

However, since the adhesive composition for optical members disclosed by patent documents 1-2 adds an amino-group containing silane coupling agent and an isocyanate type crosslinking agent simultaneously to an acryl-type copolymer, and produces an adhesive composition, in order to obtain the outstanding adhesiveness and durability, It was necessary to consider the characteristic of a silane coupling agent and a crosslinking agent with respect to the acryl-type copolymer.

Therefore, it was not easy to aim at the optimization of the compounding amount and the compounding method of a silane coupling agent and a crosslinking agent, and the problem that manufacturing process control was not easy was seen.

Moreover, although the silane compound which has an isocyanato group acts as a silane coupling agent, the adhesive composition and adhesive polarizer which are disclosed by patent documents 3-4, the isocyanate group which reacts with an adhesive component, and the silicon atom which has an alkoxy group, The distance between and is relatively short, and the problem that the adhesiveness and durability which are required are not satisfied is seen.

In addition, in the primer composition disclosed in Patent Document 5, although it is mentioned to mix | blend the reactant of a polyisocyanate compound, a silane coupling agent, etc. as (C ') component, the said (C') component must be used a considerable amount. In other words, there was a problem of economic disadvantage.

And mix | blending (C ') component improves adhesiveness between the predetermined | prescribed saturated hydrocarbon type polymer which is (A') component, and the mortar etc. which have a porous surface form which is a to-be-adhered body, A liquid crystal cell In the pressure-sensitive adhesive composition used for bonding an optical film or the like, even when an acid-free pressure-sensitive adhesive component is used, it is possible to significantly improve the adhesiveness while maintaining good reworkability by a relatively small amount of compounding. Until a predetermined effect was not found.

Moreover, when mix | blending a mixture of a polyisocyanate compound and a silane coupling agent as (C ') component, the polyisocyanate compound and the reactive functional group which (A') component have reacted preferentially, and the storage stability of a primer composition is The problem that the fall, the applicability | paintability to a to-be-adhered body fell, and the adhesive improvement effect as (C ') component could not be acquired was seen.

Therefore, in view of the above circumstances, the present inventors have made a diligent effort to obtain an unusual silane coupling agent by reacting an organic alkoxysilane compound having a reactive organic functional group with a polyisocyanate compound, and blending it into an adhesive component or the like. By doing so, while discovering that the adhesiveness is remarkably improved while maintaining good reworkability, the present invention has been completed.

That is, the objective of this invention is an adhesive composition excellent in the balance of rework property and durability in a predetermined environment by mix | blending a small amount of an unusual silane coupling agent to an adhesive component etc. even when an acid-free adhesive component is used, and its It is providing the adhesive sheet which used the same adhesive composition.

According to this invention, it is an adhesive composition containing (A) adhesive component, (B) silane coupling agent which has isocyanato group, and (C) crosslinking agent and at least 1 component chosen from a hardening | curing agent, (B) iso The silane coupling agent having a cyanato group is a coupling agent compound obtained by reacting an organic alkoxysilane compound having a (b1) polyisocyanate compound and (b2) a reactive organic functional group, and (B) a silane having an isocyanato group. The compounding quantity of a coupling agent is made into the value within the range of 0.005-5 weight part with respect to 100 weight part of (A) pressure-sensitive adhesive components, and the above-mentioned problem can be solved.

That is, even when an acid-free adhesive component is used by mix | blending the silane coupling agent which has a predetermined isocyanato group in the ratio of a predetermined amount with respect to 100 weight part of adhesive components, it is reworkable and under predetermined environment, The adhesive composition excellent in the balance of durability can be obtained.

More specifically, in such a component (B), the distance between the silicon atom having an alkoxy group and the isocyanato group is relatively long, and the reactivity of the isocyanato group is high, so that the pressure sensitive adhesive component (functional group such as hydroxyl group) is used. ), The balance between the reworkability of the pressure-sensitive adhesive composition and the durability under a predetermined environment can be made good.

Moreover, in forming the adhesive composition of this invention, it is preferable that (A) adhesive component is the (meth) acrylic acid ester polymer derived from the following (a1)-(a3) component as a monomer component.

(a1) Alkyl (meth) acrylic-acid alkylester of 1-20 carbon atoms of an alkyl group: 100 weight part

(a2) Polymeric double bond containing compound which has a hydroxyl group in a molecule: 0.5-10 weight part

(a3) Polymeric double bond-containing compound having a carboxyl group in the molecule: 0 parts by weight or 0 to 0.01 parts by weight (but not including 0 parts by weight)

With such a configuration, a balance between reworkability and durability under a predetermined environment is better, and an acrylic pressure-sensitive adhesive composition which is relatively inexpensive and easy to manufacture can be obtained.

Moreover, when using as an adhesive composition for affixing a polarizing plate, a retardation plate, etc. by restrict | limiting as little as possible with respect to the compounding quantity of (a3) component for superposing | polymerizing an adhesive component (A), the carboxy group in a molecule | numerator It is possible to effectively suppress the occurrence of metal corrosion problems such as conductive patterns due to

Moreover, in forming the adhesive composition of this invention, it is preferable that the (B) silane coupling agent which has an isocyanato group is a compound represented by following General formula (1) or General formula (2).

If it is such a silane coupling agent, compatibility with an adhesive component will be favorable, for example, even if it is a comparatively small amount of less than 0.5 weight part with respect to 100 weight part of adhesive components, under reworkability and a predetermined environment, Durability can be made more excellent.

(In general formula (1), some R <^1> and R <^2> is a C1-C6 alkyl group each independently, n is an integer of 1-8, and some a is an integer of 0-3. , X is a urea bond, a urethane bond, a thiourethane bond, an amide bond, an allophanate bond, a biuret bond, an isocyanurate bond, or a carbodiimide bond, Y is following General formula (3) It is a structure represented by (5))

(In general formula (2), R <^1> and R <^2> is a C1-C6 alkyl group each independently, n is an integer of 1-8, a is an integer of 0-3, X is A urea bond, a urethane bond, a thiourethane bond, an amide bond, an allophanate bond, a biuret bond, an isocyanurate bond, or a carbodiimide bond, Y is represented by following General formula (3)-(5) Is a structure)

(In general formula (3), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group, and R "is a C1-C8 trivalent alcohol group. Is a residue of

(In general formula (4), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group.)

(In general formula (5), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group.)

Moreover, in constructing the adhesive composition of this invention, it is preferable that the reactive organic functional group of the (b2) organic alkoxysilane compound is a primary or secondary amino group.

If it is the (b2) organic alkoxysilane compound which has such a reactive organic functional group, (B1) isocyanato group which reacts with isocyanate group of (b1) polyisocyanate compound relatively easily and quickly, and exhibits a predetermined effect. The silane coupling agent which has can be manufactured stably.

Therefore, when it mix | blends the silane coupling agent which has the (B) isocyanato group manufactured stably in the (A) adhesive component, when it coats an adhesive sheet etc., the balance of the favorable rework property and the outstanding durability in predetermined environment. Can be obtained.

Moreover, in constructing the adhesive composition of this invention, the compounding quantity of the at least 1 component chosen from (C) crosslinking agent and a hardening | curing agent is made into the value within the range of 0.001-30 weight part with respect to 100 weight part of (A) adhesive components. It is preferable.

If it is such a compounding quantity, (A) adhesive component can be bridge | crosslinked suitably, it can harden | cure (thermal curing or photocuring), and also the adhesiveness, rework property, durability, etc. of an adhesive composition can be improved significantly.

Moreover, another aspect of this invention is the adhesive sheet which provided the adhesive layer derived from any one of the adhesive compositions mentioned above on the base material.

Moreover, in forming the adhesive sheet of this invention, it is preferable that a base material is an optical film.

By setting it as the aspect of such an adhesive sheet, the balance of favorable rework property and durability in a predetermined environment can be exhibited.

Moreover, in forming the adhesive sheet of this invention, while a base material is a peeling film, it is also preferable to laminate another peeling film with respect to the opposite surface of the said peeling film in an adhesive layer.

By setting it as the aspect of the adhesive sheet (film adhesive) sandwiched with the peeling film in this way, For example, the versatility in carrying out adhesive processing of a film by peeling only a peeling film of one side, and later pasting it together with various types of films, And timeliness can be obtained, which is very beneficial from the point of view of practical use.

BRIEF DESCRIPTION OF THE DRAWINGS The figure provided in order to demonstrate the influence on the adhesive force of the compounding quantity of the silane coupling agent which has an isocyanato group.
FIG.2 (a)-(c) are figures where it demonstrates in order to demonstrate the influence on the adhesive force after 1 day, the adhesive force after 21 days, and a gel fraction based on the kind of silane coupling agent, respectively.
FIG.3 (a)-(b) are figures where it uses in order to demonstrate the reaction mechanism at the time of manufacturing the silane coupling agent which has isocyanato group, respectively.
4 is an FT-IR chart of a silane coupling agent (Example 1) having an isocyanato group.
5 is an FT-IR chart of xylene diisocyanate-trimethylolpropane adduct.
6 is an FT-IR chart of N-phenyl-γ-aminopropyltrimethoxysilane.
7 is an FT-IR chart of a reference example of a silane coupling agent having an isocyanato group.
8 is an FT-IR chart of another reference example of a silane coupling agent having an isocyanato group.
9 (a) to 9 (c) are diagrams for explaining the aspects of the adhesive sheet, respectively.
10 (a) to 10 (d) are diagrams for explaining the aspects of the adhesive sheet for optics, respectively.

[First Embodiment]

1st Embodiment of this invention is an adhesive composition containing (A) adhesive component, the (B) silane coupling agent which has isocyanato group, and (C) crosslinking agent and at least 1 component chosen from a hardening | curing agent, While the (B) silane coupling agent having an isocyanato group is a coupling agent compound obtained by reacting (b1) a polyisocyanate compound and (b2) an organic alkoxysilane compound having a reactive organic functional group, (B) isocyanato The compounding quantity of the silane coupling agent which has earthenware is made into the value within the range of 0.005-5 weight part with respect to 100 weight part of (A) adhesive components, It is an adhesive composition characterized by the above-mentioned.

EMBODIMENT OF THE INVENTION Hereinafter, the adhesive composition which is 1st Embodiment of this invention is demonstrated concretely with reference to an appropriate figure.

1. (A) component: adhesive component

(1) Type 1 (acrylic adhesive component)

Although it does not restrict | limit especially about the kind of adhesive component, Although it can select suitably according to a use, it is preferable that it is an acrylic acid ester polymer ((meth) acrylic acid ester derived from a (meth) acrylic acid ester monomer. Hereafter, it is the same). .

That is, adjustment of adhesiveness and cohesion force is comparatively easy by change of the kind of a (meth) acrylic acid ester monomer, compounding quantity, etc., and it can apply to various uses by making it an inexpensive acrylic acid ester polymer.

Moreover, it is more preferable that (A) adhesive component is the (meth) acrylic acid ester polymer derived from the following (a1)-(a3) component as a monomer component.

(a1) Alkyl (meth) acrylic-acid alkylester of 1-20 carbon atoms of an alkyl group: 100 weight part

(a2) Polymeric double bond containing compound which has a hydroxyl group in a molecule: 0.5-10 weight part

(a3) Polymeric double bond-containing compound having a carboxyl group in the molecule: 0 parts by weight or 0 to 0.01 parts by weight (but not including 0 parts by weight)

This reason is because crosslinking becomes possible using the hydroxyl group introduce | transduced in the molecule | numerator of an acrylate ester polymer. Therefore, the balance between the rework property and the durability under a predetermined environment becomes better, and an acrylic pressure-sensitive adhesive composition which is relatively inexpensive and easy to manufacture can be obtained.

Further, by limiting the amount of the component (a3) contained in the pressure-sensitive adhesive component as little as possible, even when used as an adhesive composition for affixing a polarizing plate, a retardation plate, or the like, metal corrosion such as a conductive pattern due to carboxyl groups in a molecule This is because the occurrence of a problem can be effectively suppressed.

(1) -1. Monomer component (a1)

(A) It is preferable that an adhesive component contains the (meth) acrylic-acid alkylester containing a C1-C20 alkyl group as a monomer component (a1) at the time of superposition | polymerization.

This reason is because when the carbon number of such an alkyl group becomes a value larger than 20, the adhesiveness of the adhesive composition obtained may fall by orientation and crystallization of side chains.

Therefore, it is more preferable to make carbon number of the alkyl group in a (meth) acrylic acid ester polymer into the value within the range of 1-10, and it is still more preferable to set it as the value within the range of 4-8.

Moreover, as a (meth) acrylic-acid alkylester whose carbon number of an alkyl group is a value in the range of 1-20, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) Pentyl acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoctyl (meth) acrylate, decyl (meth) acrylate and dodecyl (meth) acrylate, (meth) acrylic acid Single 1 type, or 2 or more types of combinations, such as myristyl, palmityl (meth) acrylate, and stearyl (meth) acrylate, are mentioned.

Moreover, since the (meth) acrylic acid ester which is a monomer component (a1) is a main component which comprises (A) adhesive component, it is preferable that it is normally the value of 50 weight% or more of all the monomer components which comprise (A) component, and 60 It is more preferable that it is a value in the range of -99.5 weight%, and it is still more preferable that it is a value in the range which is 85-99 weight%.

(1) -2. Monomer component (a2)

Moreover, it is preferable that (A) adhesive component contains the polymeric double bond containing compound which has a hydroxyl group in a molecule | numerator as a monomer component (a2) at the time of superposition | polymerization.

This reason is, by containing such a monomer component (a2), the said hydroxyl group turns into a crosslinkable functional group in a (meth) acrylic acid ester polymer. That is, when a crosslinking agent is added with respect to an adhesive composition, crosslinking of (A) adhesive component can be performed effectively, the cohesion force of the adhesive obtained can be improved, and adjustment of adhesive force and a storage elastic modulus can be performed easily.

Moreover, as a polymerizable double bond containing compound which has a hydroxyl group in a molecule | numerator, For example, hydroxy group containing vinyl ether, such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexyl dimethanol monovinyl ether, allyl alcohol, allyl glycol, Vinyl group-containing allyl ether, such as allyl diglycol, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl And single 1 type or 2 or more types of monomers, such as (meth) acrylic-acid hydroxyalkyl ester, such as 3-hydroxybutyl (meth) acrylic acid and 4-hydroxybutyl (meth) acrylic acid, are mentioned preferably.

Moreover, in consideration of compatibility with the (meth) acrylic acid ester monomer which is a main component which comprises a (meth) acrylic acid ester polymer, it is more preferable that it is (meth) acrylic-acid hydroxyalkyl ester, and it is (meth) acrylic-acid 2-hydroxyethyl And (meth) acrylic acid 4-hydroxybutyl.

Moreover, it is preferable to make the compounding quantity of a monomer component (a2) into the value within the range of 0.5-10 weight part with respect to 100 weight part of monomer components (a1).

This reason is because when the compounding quantity of a monomer component (a2) becomes a value less than 0.5 weight part, crosslinking between (A) components may become inadequate and durability in a predetermined environment may deteriorate.

On the other hand, when the compounding quantity of a monomer component (a2) becomes a value exceeding 10 weight part, it is because the adhesiveness of an adhesive composition may fall excessively.

Therefore, it is more preferable to make the compounding quantity of a monomer component (a2) into the value within the range of 1-5 weight part with respect to 100 weight part of monomer components (a1).

(1) -3. Monomer component (a3)

Moreover, it is preferable that (A) adhesive component does not contain the polymeric double bond containing compound which has a carboxy group in a molecule | numerator substantially as a monomer component (a3) at the time of superposition | polymerization.

More specifically, the compounding quantity of the monomer component (a3) at the time of superposing | polymerizing the (A) adhesive component is 0 weight part or 0-0.01 weight part with respect to 100 weight part of monomer components (a1) mentioned above, It is preferable to set it as the value within the range of 0 weight part).

This reason is that when the compounding quantity of such a monomer component (a3) exceeds a value of 0.01 parts by weight, when an adherend such as a liquid crystal cell has a transparent conductive film formed by metal deposition or the like, the occurrence of acid corrosion is stable. It is because it may become difficult to prevent this.

Moreover, after bonding the adhesive force in an adhesive composition with respect to a to-be-adhered body, it is easy to rise rapidly, and it may become difficult to exhibit stable rework property.

Therefore, also when mix | blending a monomer component (a3), it is more preferable to set it as the value within the range of 0.0001 to 0.01 weight part with respect to 100 weight part of monomer components (a1), and to set it as the value within the range which is 0.001 to 0.005 weight part. More preferred.

Moreover, as a kind of monomer component (a3), if it is a polymerizable double bond containing compound which has a carboxyl group in a molecule | numerator, it will not restrict | limit especially, For example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, a citraconic acid Etc. can be mentioned.

(2) Type 2 (other adhesive component)

Moreover, as a kind of adhesive component, in order to use it separately or together with the said acrylic acid ester polymer, a polyurethane polymer, a polyester polymer, a polyolefin polymer, a polycarbonate polymer, a natural rubber, a synthetic rubber, a styrene thermoplastic The polymer component (polymer resin) which consists of single 1 type or combination of 2 or more types, such as an elastomer, a silicone resin, and a phenol resin, is mentioned.

In particular, if it is a polyurethane polymer etc., it can be set as the adhesive component excellent in an elastic force or elasticity.

Moreover, if it is silicone resin, a phenol resin, etc., it can be set as the adhesive component which is more excellent in heat resistance, durability, etc ..

(3) compounding amount

Moreover, when making the compounding quantity of an adhesive component into 100 weight% of the total amount of an adhesive composition, it is preferable to set it as the value within the range of 30 to 99 weight%.

This reason is because when the compounding quantity of such an adhesive component becomes a value less than 30 weight%, an addition effect may not express.

On the other hand, when the compounding quantity of such an adhesive component exceeds the 99 weight%, it is because rework property, durability, etc. may fall remarkably.

Therefore, when the compounding quantity of an adhesive component makes the total amount of an adhesive composition 100 weight%, it is more preferable to set it as the value within the range of 50 to 95 weight%, and to make it the value within the range of 80 to 90 weight% further desirable.

2. Component (B): Silane coupling agent having isocyanato group

The component (B) is a silicon-containing compound as a silane coupling agent having an isocyanato group formed by reacting a (b1) polyisocyanate compound with an organic alkoxysilane compound having a (b2) reactive organic functional group.

(1) (b1) polyisocyanate compound

The polyisocyanate compound as the component (b1) is defined as a compound having a plurality of isocyanato groups. For example, specifically, tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tri Adducts using polyisocyanates such as phenylmethane triisocyanate or addition reaction products of these polyisocyanates, for example, trimethylolpropane, glycol, etc., these isocyanurate modified bodies, carbodiimide modified bodies and allophanates Single 1 type, or 2 or more types of combinations, such as a modified body and a burette modified body, are mentioned.

Among these, if it is an adduct of xylene diisocyanate etc. which used trimethylol propane, since polarity is very high and the reactivity with (b2) component is excellent, it is more preferable.

(2) (b2) an organic alkoxysilane compound having a reactive organic functional group

Moreover, as an organic alkoxysilane compound which has a reactive organic functional group as (b2) component, it is a compound which has a reactive organic functional group which has reactivity with isocyanato group other than hydrolysable reactive groups, such as an alkoxy group. As a reactive organic functional group which has reactivity with an isocyanato group, a primary amino group, a secondary amino group, a mercapto group, etc. are mentioned preferably, for example.

As such a (b2) component, specifically,

γ-mercaptopropyltrimethoxysilane,

γ-mercaptopropyltriethoxysilane,

γ-mercaptopropylmethyldimethoxysilane,

γ-mercaptopropylmethyldiethoxysilane,

N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane,

N- (β-aminoethyl) -γ-aminopropyltriethoxysilane,

N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane,

N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane,

N-phenyl-γ-aminopropyltrimethoxysilane,

N-phenyl-γ-aminopropyltriethoxysilane,

N-phenyl-γ-aminopropylmethyldimethoxysilane,

N-phenyl-γ-aminopropylmethyldiethoxysilane,

γ-aminopropyltrimethoxysilane,

γ-aminopropyltriethoxysilane,

γ-aminopropylmethyldimethoxysilane,

γ-aminopropylmethyldiethoxysilane,

Single 1 type, or 2 or more types of combinations, such as these, are mentioned.

Among them, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and the like are preferable because they have an amino group which is more reactive to isocyanato groups.

That is, it is preferable that it is a primary or secondary amino group as a reactive organic functional group of (b2) organic alkoxysilane compound.

Therefore, if it is the (b2) organic alkoxysilane compound which has such an amino group, (B1) isocyanato group which reacts isocyanate group of (b1) polyisocyanate compound relatively easily and quickly, and exhibits a predetermined effect. The silane coupling agent which has can be manufactured stably.

Therefore, when recoating to the adhesive sheet etc. by mix | blending the (B) component stably manufactured using the (b2) organic alkoxysilane compound which has such an amino group with respect to the (A) adhesive component, favorable rework property and Better balance of durability under certain circumstances can be obtained.

Moreover, since handleability and storage stability are improved when (b2) the organic alkoxysilane compound which has a reactive organic functional group and (b1) polyisocyanate compound is made to react, about (b2) the organic alkoxysilane compound which has a reactive organic functional group It is preferable to add the organic solvent mentioned later previously.

(3) organic solvent

Moreover, it is preferable to mix | blend an organic solvent in consideration of handleability, uniform mixing property, etc.

As such an organic solvent, aromatic hydrocarbons, such as benzene, xylene, and toluene, aliphatic hydrocarbons, such as n-hexane, ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters, such as methyl acetate, ethyl acetate, and butyl acetate And single 1 type or 2 or more types of combinations, such as ethers, such as diethyl ether, tetrahydrofuran, and dioxane, and halogenated hydrocarbons, such as dichloromethane, chloroform, and 1,2-dichloroethane.

(4) structural formula

Moreover, it is preferable that the (B) silane coupling agent which has an isocyanato group is a compound represented by the following general formula (1) or (2).

This reason is that if it is such a silane coupling agent, compatibility with the adhesive component which is (A) component is favorable, for example, even if it is a comparatively small amount compounding of less than 0.5 weight part with respect to 100 weight part of adhesive components, This is because the properties and durability under a predetermined environment can be made more excellent.

(In general formula (1), some R <^1> and R <^2> is a C1-C6 alkyl group each independently, n is an integer of 1-8, and some a is an integer of 0-3. , X is a urea bond, a urethane bond, a thiourethane bond, an amide bond, an allophanate bond, a biuret bond, an isocyanurate bond, or a carbodiimide bond, Y is following General formula (3) It is a structure represented by (5))

(In general formula (2), R <^1> and R <^2> is a C1-C6 alkyl group each independently, n is an integer of 1-8, a is an integer of 0-3, X is A urea bond, a urethane bond, a thiourethane bond, an amide bond, an allophanate bond, a biuret bond, an isocyanurate bond, or a carbodiimide bond, Y is represented by following General formula (3)-(5) Is a structure)

(In general formula (3), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group, and R "is a C1-C8 trivalent alcohol group. Is a residue of

(In general formula (4), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group.)

(In general formula (5), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group.)

In General Formula (1) or (2), X represents a urea bond, a urethane bond, a thiourethane bond, an amide bond, an allophanate bond, a burette bond, an isocyanurate bond, or a carbodi Although it is a mid bond, at least one of the hydrogen atoms which exist in such a bond may be substituted by other substituents, such as an alkyl group and an aryl group, for example.

In addition, the bond number which is not couple | bonded with the three R 'nitrogen atoms contained in the structure represented by General Formula (3)-(5) is X, as corresponding to General formula (1) or (2). Or isocyanate groups.

For example, the following formula (6) or formula (7) is mentioned as a specific example of the compound represented by General formula (1) or general formula (2) of the silane coupling agent which has (B) isocyanato group. have.

Here, in Formula (6) and Formula (7), X is a urea bond, and the hydrogen atom which exists in such a bond is substituted by the aryl group.

(5) compounding amount

Moreover, the compounding quantity of the silane coupling agent which has the isocyanato group which is (B) component is made into the value within the range of 0.005-5 weight part with respect to 100 weight part of adhesive components which are (A) component.

This reason is because when the compounding quantity of such (B) component becomes a value less than 0.005 weight part, an addition effect may not be expressed.

On the other hand, when the compounding quantity of such a (B) component exceeds the 5 weight part, the adhesive force of an adhesive composition may be saturated, or the adhesive force of an adhesive composition may fall.

Therefore, it is more preferable to make the compounding quantity of (B) component into the value within the range of 0.01-3 weight part with respect to 100 weight part of (A) component, and it is still more preferable to set it as the value within the range of 0.1-1 weight part.

Here, with reference to FIG. 1, the influence on the adhesive force of the adhesive composition of the compounding quantity of the (B) silane coupling agent which has isocyanato group is demonstrated.

That is, FIG. 1: shows the compounding quantity (weight part) of the silane coupling agent which has (B) isocyanato group per 100 weight part of (A) component on a horizontal axis, and shows the adhesive composition (based on Example 1) on a vertical axis. It shows adhesive force.

In addition, the characteristic curve A respond | corresponds to the adhesive force 1 day after a patch, and the characteristic curve B respond | corresponds to the adhesive force 21 days after a patch.

Therefore, as understood from the behavior of the characteristic curve A, the blending amount of the silane coupling agent having (B) isocyanato group was not blended with 0 parts by weight, that is, the silane coupling agent having (B) isocyanato group. The adhesive composition which mix | blended the silane coupling agent which has a predetermined amount (0.1, 0.2, 0.5, 1.0 weight part) of (B) isocyanato group compared with an adhesive composition has the tendency which the adhesive force after 1 day from a patch increases, respectively. Seemed.

And about 0.1, 0.2, 0.5 weight part of adhesive compositions with which the compounding quantity of the (B) silane coupling agent which has an isocyanato group has, such a compounding quantity increased, the adhesive force after 1 day from sticking tended to become high.

On the other hand, about the adhesive force after 1 day from the sticking of 1.0 weight part of adhesive compositions, the compounding quantity of (B) the silane coupling agent which has isocyanato group has such a compounding quantity being equal to or more than that of 0.5 weight part of adhesive compositions. A slightly lower tendency was seen.

That is, with respect to the compounding quantity of the silane coupling agent which has the (B) isocyanato group, in the range of 0.5-1.0 weight part, the value of the adhesive force after 1 day from a sticking tended to be saturated.

In addition, as understood from the behavior of the characteristic curve B, the blending amount of the silane coupling agent having (B) isocyanato group was not blended with 0 parts by weight, that is, the silane coupling agent having (B) isocyanato group. The adhesive composition which mix | blended the silane coupling agent which has a predetermined amount (0.1, 0.2, 0.5, 1.0 weight part) of (B) isocyanato group compared with an adhesive composition has the tendency for the adhesive force after 21 days from sticking to become higher, respectively. This looked.

And as for the compounding quantity of the silane coupling agent which has the (B) isocyanato group, about 0.1, 0.2 weight part of adhesive compositions, the more there is such a compounding quantity, the tendency which the adhesive force after 21 days from sticking increased.

On the other hand, about the adhesive force after 21 days from the sticking of 0.5 and 1.0 weight part of adhesive compositions, the compounding quantity of the silane coupling agent which has isocyanato group (B) showed that such compounding quantity tended to be lower than that of 0.2 weight part of adhesive compositions. .

That is, with respect to the compounding quantity of the silane coupling agent which has the (B) isocyanato group, in the range of 0.2-1.0 weight part, the tendency to saturate also about the value of the adhesive force 21 days after sticking.

Therefore, by making the compounding quantity of (B) component into the value within the range of predetermined amount, it is understood that the adhesive force 1 day after and 21 days after sticking can be adjusted, respectively.

Subsequently, FIGS.2 (a)-(c) show the kind of silane coupling agent, ie, the (B) silane coupling agent which has isocyanato group, and the commercially available silane coupling agent represented by Formula (6) mentioned later. It is a figure provided in order to demonstrate the influence on the adhesive force after 1 day, the adhesive force after 21 days, and gel fraction based on.

First, FIG.2 (a) shows the compounding quantity (weight part) of the silane coupling agent with respect to 100 weight part of (A) components on a horizontal axis, and it is 1 day from the sticking of an adhesive composition (based on Example 1) to a vertical axis | shaft. The later adhesive force is shown.

In addition, the characteristic curve A corresponds to the silane coupling agent which has (B) isocyanato group, and the characteristic curve C corresponds to the commercially available silane coupling agent.

Therefore, as easily understood from the behavior of the characteristic curve A, in the case of the (B) silane coupling agent having an isocyanato group, by containing a predetermined amount, the adhesive force became high but a tendency to saturate.

On the other hand, as it is easily understood from the behavior of the characteristic curve C, in the case of a commercially available silane coupling agent, it was not saturated, and the adhesive force obtained in proportion to the compounding quantity tended to increase.

Therefore, in the case of the (B) silane coupling agent which has an isocyanato group, it is understood that it is easy to control adhesive force to the value within a predetermined range.

In addition, FIG.2 (b) shows the compounding quantity (weight part) of a silane coupling agent with respect to 100 weight part of (A) components on a horizontal axis, and it is 21 days from the sticking of an adhesive composition (based on Example 1) to a vertical axis | shaft. The later adhesive force is shown.

In addition, the characteristic curve B corresponds to the silane coupling agent which has (B) isocyanato group, and the characteristic curve D respond | corresponds to the commercially available silane coupling agent.

Therefore, as easily understood from the behavior of the characteristic curve B, in the case of the (B) silane coupling agent having an isocyanato group, the adhesive force after 21 days was increased by containing a predetermined amount, but a tendency to saturation was observed. .

On the other hand, as is easily understood from the behavior of the characteristic curve D, in the case of a commercially available silane coupling agent, it was not saturated, but the adhesive force after 21 days showed the tendency to increase in proportion to compounding quantity.

Therefore, in the case of the (B) silane coupling agent which has isocyanato group, it is understood that it is easy to control the adhesive force after 21 days to the value within a predetermined range.

In addition, FIG.2 (c) shows the compounding quantity (weight part) of a silane coupling agent with respect to 100 weight part of (A) components on a horizontal axis, and shows the gel fraction of an adhesive composition (based on Example 1) on a vertical axis. .

Moreover, the characteristic curve E corresponds to the silane coupling agent which has the (B) isocyanato group, and the characteristic curve F corresponds to the commercially available silane coupling agent.

Therefore, as easily understood from the behavior of the characteristic curve E, in the case of the (B) silane coupling agent having an isocyanato group, by containing a predetermined amount, a constant gel fraction is obtained, and (B) isocyana The gel fraction equivalent to the case of not containing the silane coupling agent having an earthenware was observed.

On the other hand, as easily understood from the behavior of the characteristic curve F, in the case of a commercially available silane coupling agent, the gel fraction tended to remarkably fall compared with the case where it did not contain by containing a predetermined amount.

Therefore, in the case of the (B) silane coupling agent having an isocyanato group, it is less likely to inhibit the crosslinking reaction of the pressure-sensitive adhesive component by the crosslinking agent (polyisocyanate compound), and in the case of a commercially available silane coupling agent, the crosslinking agent (poly It is estimated that the crosslinking reaction of the adhesive component by the isocyanate compound) may be inhibited.

(6) manufacturing method

Moreover, it does not specifically limit also about the manufacturing method of the silane coupling agent which has (B) isocyanato group, It is well-known reaction of (b1) polyisocyanate compound and (b2) organic alkoxysilane compound which has a reactive organic functional group. It mixes according to the method, What is necessary is just to make the at least one isocyanato group which (b1) component has, and to react the reactive organic functional group which the (b2) component has, and to make it the coupling agent compound which has at least one isocyanato group.

Reaction mechanism at the time of manufacturing the silane coupling agent which has (B) isocyanato group which made into the raw material the organic alkoxysilane compound which has (b1) polyisocyanate compound and (b2) reactive organic functional group as a raw material to FIG. An example is shown.

It is understood that the plural (two) silicon atom-containing groups and the single isocyanate group each have a terminal, and that the distance between the plural (two) silicon atom-containing groups and the isocyanato group is relatively long. do.

In contrast, as shown in Fig. 3B, a silane coupling agent having a commercially available isocyanato group represented by Formula (8) described later includes a single silicon atom-containing group and a single isocyanato group, respectively. It is understood that the distance between the single silicon atom-containing group and the isocyanato group is relatively short.

More specifically, (B) component can be manufactured according to the following processes.

1) The process of making it a uniform solution by stirring (b1) component and a predetermined organic solvent in the reaction container with a stirring device, respectively, at room temperature (25 degreeC) for 1 to 60 minutes.

2) Subsequently, with respect to the obtained solution, (b2) component is added and it is made to react for 10 minutes-24 hours, stirring, in the state maintained at the temperature condition of 20-60 degreeC, and it is set as a reaction liquid.

3) Subsequently, from the obtained reaction liquid, a predetermined organic solvent is removed by an evaporation operation or the like, if necessary, to form a silane coupling agent having an isocyanato group as the component (B).

And in reacting (b1) polyisocyanate compound and (b2) organic alkoxysilane compound which has a reactive organic functional group, (b1) Reactivity of the organic alkoxysilane compound with respect to the isocyanato group of a polyisocyanate compound It is preferable to make an organic functional group into the value within the range of 0.01-0.9 molar equivalent.

This reason is that (B) isocyanato group which (b1) polyisocyanate compound and (b2) organic alkoxysilane compound which has a reactive organic functional group react without gelation, and exhibits a predetermined effect in such a reaction ratio. It is because the silane coupling agent which has can be manufactured stably.

That is, when it coats the adhesive sheet etc. by mix | blending the silane coupling agent which has the (B) isocyanato group manufactured stably in this (A) adhesive component, the rework property and durability under predetermined environment are more favorable. Balance can be obtained.

Therefore, it is more preferable to make the addition amount of the (b2) organic alkoxysilane compound which has a reactive organic functional group into the value within the range of 0.1-0.8 molar equivalent with respect to the (b1) polyisocyanate compound, and is the range of 0.3-0.7 molar equivalent It is more preferable to set it as an internal value.

In addition, whether or not the component (b1) and the component (b2) react and the component (B) is reliably produced is determined by using a Fourier transform infrared spectrophotometer (FT-IR), the component (b1) and (b2) 4 to 6, the FT-IR chart was obtained for the component and the component (B), and whether absorption peaks due to, for example, urea bonding, which were not present in any of the raw material components, were observed. Judgment can be made by.

For example, as shown in the FT-IR chart of Fig. 4, the absorption peak derived from the carbonyl group of the urea bond with respect to the height is taken as the reference peak based on the absorption peak (1690 cm ^-1 ) derived from the carbonyl group in the urethane bond. If the ratio of the height of (1650 cm <^-1> ) is more than predetermined value, it can be judged that (b1) component and (b2) component react.

In addition, whether (B) component has an isocyanato group can be judged using the FT-IR whether the peak which belongs to an isocyanato group is observed.

More specifically, as shown in the FT-IR chart of Fig. 4, the absorption peak (1690 cm ^-1 ) derived from the carbonyl group in the urethane bond is taken as the reference peak, and is derived from the isocyanato group with respect to the height. If the ratio of the height of an absorption peak (2270 cm <^-1> ) is more than predetermined value, it can be judged that (B) component has an isocyanato group.

In addition, as shown in FIG. 5, an FT-IR chart of the component (b1) and an FT-IR chart of the component (b2) are obtained as shown in FIG. 6. It can be seen that there is no absorption peak attributable.

7-8, the FT-IR chart in the product (reference examples 1 and 2) at the time of changing the reaction ratio of (b2) component with respect to (b1) component is shown.

That is, FIG. 7 shows the FT-IR chart of the product (Reference Example 1) obtained when the reaction ratio of the component (b2) is relatively low, but the peak (2270 cm ^-1 ) attributed to the isocyanato group is Significantly observed.

8 shows the FT-IR chart of the product (Reference Example 2) obtained when the reaction ratio of the component (b2) is quite high, but the peak (2270 cm ^-1 ) attributed to the isocyanato group is almost Not observed

Therefore, whether the component (b1) and the component (b2) react and whether the component (B) is reliably produced varies the reaction ratio of the component (b2) with respect to the component (b1) to obtain a product, thereby obtaining their FT. It can be judged more reliably by confirming the size of the peak (2270 cm ^-1 ) attributable to the isocyanato group from the contrast of the -IR chart.

3. Component (C): at least one component selected from crosslinking agents and curing agents

(1) Type

Moreover, at least one component selected from a crosslinking agent and a hardening | curing agent is further mix | blended as (C) component which is one of the structural components of an adhesive composition. In addition, the above-mentioned (B) component is excluded from (C) component.

That is, by further containing such a crosslinking agent, it can react with the reactor etc. which an adhesive component has, and can make the said adhesive component high molecular weight and also three-dimensional crosslinking. Therefore, the adhesiveness, cohesion, etc. at the time of forming an adhesive layer can be controlled easily in a desired range.

More specifically, as a crosslinking agent of (C) component, 1 type individually or 2 or more types of combinations, such as a polyisocyanate compound like component (b1), are mentioned.

Among these, in the case of an adduct of xylene diisocyanate using trimethylolpropane and the like, the polarity is very high, and since it has strong crosslinkability, it is more preferable.

On the other hand, a hardening agent reacts with two or more other compounds of the same kind by itself by heat or active energy ray irradiation, and finally forms a rigid structure such as a three-dimensional network structure. Say the compound.

As such a hardening | curing agent, a polyfunctional (meth) acrylate type monomer etc. are used suitably, for example.

As a polyfunctional (meth) acrylate type monomer, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene, for example Glycol di (meth) acrylate, di (meth) acrylate of neopentyl glycol adipate, hydroxy pivalate neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone modified dicyclo Pentenyldi (meth) acrylate, ethylene oxide modified phosphate di (meth) acrylate, di (meth) acryloxyethyl isocyanurate, allylated cyclohexyldi (meth) acrylate, tricyclodecane dimethanol di (meth ) Acrylate, dimethyloldicyclopentanedi (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, neopentylglycol modified trimethylolpropanedi (meth) Bifunctional polyfunctional (meth) acrylate monomers such as acrylate, adamantanedi (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, and trimethyl All propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tree Trifunctional polyfunctional (meth) acrylate monomers such as (meth) acrylate and tris (meth) acryloxyethyl isocyanurate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate 4-functional types such as, for example, 5-functional polyfunctional (meth) acrylate monomers such as propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Single 1 type, or 2 or more types of combinations, such as 6 functional type polyfunctional (meth) acrylate type monomers, such as an acrylate and a caprolactone modified dipentaerythritol hexa (meth) acrylate, are mentioned.

Moreover, as such a polyfunctional (meth) acrylate type monomer, it is preferable to have a cyclic structure, for example, a carbocyclic structure, a heterocyclic structure, or either cyclic structure in a skeletal structure.

As such a polyfunctional (meth) acrylate type monomer, the polyfunctional which has isocyanurate structures, such as di (meth) acryloxyethyl isocyanurate and a tris (meth) acryloxyethyl isocyanurate, for example. (Meth) acrylate type monomer, dimethylol dicyclopentanedi (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol modified trimethyl Olpropanedi (meth) acrylate, adamantanedi (meth) acrylate, etc. are suitable.

Among these, especially polyfunctional (meth) acrylate type monomer which has isocyanurate structure is preferable. Moreover, when using a hardening | curing agent, it is also preferable to use the polymerization initiator by light or heat.

(2) compounding amount

Moreover, it is preferable to make the compounding quantity of the at least 1 component chosen from the crosslinking agent and hardening | curing agent as (C) component into the value within the range of 0.001-30 weight part with respect to 100 weight part of adhesive components which are (A) component.

This reason is because when the compounding quantity of such (C) component becomes a value less than 0.001 weight part, an addition effect may not be expressed.

On the other hand, when the compounding quantity of such a component (C) exceeds 30 weight part, it is because characteristics, such as storage stability, adhesiveness, or rework property of an adhesive component, may fall remarkably.

Therefore, it is more preferable to make the compounding quantity of (C) component into the value within the range of 0.01-20 weight part with respect to 100 weight part of adhesive components, and it is still more preferable to set it as the value within the range which is 0.1-10 weight part.

4. Other components

(1) Type

Moreover, an adhesive composition may contain another structural component.

As such another structural component, 1 type (s) or 2 or more types of combinations, such as antioxidant, a ultraviolet absorber, an antistatic agent, an electroconductive material, an electrical insulation material, an antibacterial agent, a tackifier, a coloring agent, a filler, and a refractive index regulator, are mentioned.

(2) compounding amount

When it contains another structural component, although the compounding quantity is based also on a kind, it is preferable to set it as the value within the range of 0.001-30 weight part with respect to 100 weight part of adhesive components which are (A) component normally.

This reason is because when the compounding quantity of such an additive becomes a value below 0.001 weight part, an addition effect may not express.

On the other hand, when the compounding quantity of such an additive becomes a value exceeding 30 weight part, it is because control of adhesiveness, rework property, etc. of an adhesive composition may become difficult.

Therefore, it is more preferable to make the compounding quantity of such an additive into the value within the range of 0.05-20 weight part with respect to 100 weight part of adhesive components, and, as for the value within the range which is 2-10 weight part.

[Second Embodiment]

2nd Embodiment is an adhesive composition containing (A) adhesive component, the (B) silane coupling agent which has isocyanato group, and (C) crosslinking agent and at least 1 component chosen from a hardening | curing agent, (B) The silane coupling agent having an isocyanato group is a coupling agent compound obtained by reacting an organic alkoxysilane compound having a (b1) polyisocyanate compound and (b2) a reactive organic functional group, and also has (B) an isocyanato group. The adhesive sheet which provided the adhesive layer derived from the adhesive composition characterized by setting the compounding quantity of a silane coupling agent to the value within the range of 0.005-5 weight part with respect to 100 weight part of (A) adhesive components on the base material to be.

Hereinafter, the adhesive sheet of 2nd Embodiment of this invention is demonstrated concretely with reference to FIGS. 9-10.

1. Pressure-sensitive adhesive composition and pressure-sensitive adhesive layer

(1) blending composition

Since it can be set as the compounding composition of the adhesive composition as demonstrated in 1st Embodiment, description here is abbreviate | omitted.

(2) form

In addition, the form of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is not particularly limited, but is preferably set to the pressure-sensitive adhesive layer 10 having a predetermined thickness as shown in Fig. 9A.

That is, by making it into the adhesive layer whose thickness is 10-200 micrometers normally, the favorable adhesiveness and durability with respect to a to-be-adhered body can be exhibited.

In addition, as shown in FIG. 9 (b), the pointed pressure-sensitive adhesive layer 10 may be arranged regularly or irregularly. That is, by setting it as a viscous adhesive layer whose original equivalent diameter is 1-200 micrometers, adhesiveness with respect to a to-be-adhered body can be finely controlled and favorable re-peelability can be exhibited.

2. Description

(1) Type

Moreover, as a kind of base material 101 shown to FIG. 9 (a)-(b), polyester resin, a polycarbonate resin, a polyolefin resin, a polyacrylic resin, a polyurethane resin, an epoxy resin, paper, a fiber, glass, etc. Can be mentioned.

And it is also preferable that surface treatments, such as a corona treatment, a primer treatment, a saponification treatment, and a flame oxidation treatment, are given to the surface of the base material which consists of various resins.

This reason is because the adhesiveness of the adhesive layer with respect to a base material can be improved remarkably by such a surface treatment.

On the other hand, as shown in FIG.9 (c), while the base material is provided in both surfaces of the adhesive layer 10, it is also preferable that one is comprised by the peeling member 2 among them.

That is, by containing such a peeling member, it can apply easily to adherends, such as a liquid crystal cell.

(2) form

Moreover, although it does not restrict | limit especially as a form of a base material, A sheet form (including film form), a nonwoven fabric form, a perforated film, a surface asperity film, etc. are mentioned.

For example, by using various sheet-like optical films as a base material, the polarizing plate shown in FIG. 10 (a), the retardation plate shown in FIG. 10 (b), the light-diffusion polarizing plate shown in FIG. 10 (c), and FIG. 10 (d) The antireflection film etc. which are shown by) can be comprised.

Moreover, by using the base material which has a predetermined | prescribed coloring layer, a decorative layer, a printing layer, an antistatic layer, a hard coating layer, etc., an adhesive tape, an adhesive decorative sheet, a marking film, an antistatic film with an adhesive layer, a surface protection film, etc. It is also preferable to set it as.

3. Manufacturing Method

(1) Preparation process of adhesive composition

The preparation process of an adhesive composition is a process of preparing the adhesive composition which has a predetermined compounding composition.

Therefore, for example, after accommodating the adhesive component as (A) component in the container provided with a stirring apparatus, the silane coupling agent which has the isocyanato group as (B) component, and the crosslinking agent as (C) component are added one by one. In addition, it can be set as the adhesive composition which has stirred for 10 minutes-24 hours in the state hold | maintained at the temperature conditions of 20-60 degreeC, and has a uniform compounding composition.

(2) Coating process of adhesive composition

Subsequently, the coating step of the pressure-sensitive adhesive composition is obtained by using a known coating method, for example, a roll coating method, a knife coating method, a gravure coating method, a screen coating method, an inkjet method, a die coating method, or the like. It is a process of apply | coating on a base material, drying it, and making it an adhesive layer.

Therefore, after apply | coating an adhesive composition on a base material by the conventional application | coating method, it can be set as the adhesive layer of predetermined thickness by heat-drying, for example for 10 second-10 minutes on 40-120 degreeC temperature conditions.

In addition, when using a photocuring agent as (C) component, after heating and drying, active energy rays, such as an ultraviolet-ray and an electron beam, are irradiated.

(3) Seasoning process

Subsequently, although a seasoning process is an arbitrary process, the crosslinking reaction of the adhesive composition which used the adhesive layer on the base material is advanced, and it is a process made into the adhesive layer which the cohesion force improved.

Therefore, it is preferable to perform this seasoning process, and to leave it for 1 to 10 days on the conditions of room temperature (23 degreeC) and 50% RH, for example, and to fully crosslink an adhesive composition.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

1. Preparation of pressure-sensitive adhesive composition

The adhesive composition which consists of 100 parts of adhesive components as a following (A) component, 0.1 weight part of silane coupling agents which have isocyanato group as (B) component, and 0.15 weight part of crosslinking agents as (C) component was prepared.

In addition, the numerical value of Table 1 shows the value converted into solid content. In addition, in Table 1, the compounding quantity of a monomer component means the weight part at the time of making the whole monomer component into 100 weight part. In addition, the compounding quantity of the silane coupling agent and (C) crosslinking agent which has (B) isocyanato group means the weight part at the time of making 100 weight part of (A) adhesive components, respectively.

(1) Preparation of (A) adhesive component

Under a nitrogen atmosphere, n-butyl acrylate (BA) (95 parts by weight) as a component (a1) and 4-hydroxybutyl acrylate (4HBA) as a component (a2) (5 parts by weight) in a container with a stirring device. And 0.3 weight part of azobisisobutyronitrile as a polymerization initiator, and 150 weight part of ethyl acetate were accommodated.

Subsequently, radical solution polymerization was performed on 60 degreeC and the conditions of 8 hours, and the weight average molecular weight obtained the (meth) acrylic acid ester polymer solution of 1.5 million as (A) component.

In addition, the weight average molecular weight of the (meth) acrylic acid ester polymer was measured by the gel permeation chromatography method (hereinafter abbreviated as GPC method).

That is, first, a calibration curve was created using polystyrene. Then, a weight average molecular weight is shown by polystyrene conversion value. Subsequently, the tetrahydrofuran (THF) solution of 1 weight% of density | concentrations of the measurement targets, such as a (meth) acrylic acid ester polymer, is prepared, manufactured by Tosoh Corporation, GEL PERMEATION CHROMATOGRAPH HLC-8020 (TSK _GEL , GMH _XL , The weight average molecular weight was measured on 40 degreeC, THF, and 1 ml / min conditions by three columns of TSK _GEL GMH _XL , TSK _GEL , and G2000 _HXL . And TSK GUARD COLUMN by Toso Corporation was used as a guard column.

(2) Preparation of (B) component

Subsequently, the xylene diisocyanate-trimethylol propane adduct (TD-75, made by Soken Chemical Co., Ltd., 75 weight% of solid content, ethyl acetate solution) as (b1) component was accommodated in the container with a stirring apparatus. Then, ethyl acetate was further added, and it diluted to predetermined density | concentration.

Then, N-phenyl- (gamma)-aminopropyl trimethoxysilane (KBM-573, the Shin-Etsu Chemical Co., Ltd. make, 100 weight% of solid content) as (b2) component was previously diluted with toluene, and it converted into solid content, To 100 parts by weight of the component (b1), the component (b2) is slowly added to the container so as to have a ratio of 73.0 parts by weight (2 molar equivalents of the amino group of (b2) to the isocyanato group of (b1)), and at room temperature And it stirred for 1 hour, and obtained the silane coupling agent (I) which has an isocyanato group as (B) component.

In addition, FT-IR chart of the silane coupling agent which has isocyanato group as (B) component in FIG. 4, FT-IR chart of (b1) xylene diisocyanate trimethylol propane adduct, FIG. (B2) FT-IR chart of N-phenyl- (gamma)-aminopropyl trimethoxysilane is shown.

That is, as shown in FIG. 5, the absorption peak (1690 cm <^-1> ) derived from the carbonyl group in a urethane bond, and the absorption peak (2270) derived from an isocyanato group as a main absorption peak with respect to (b1) component as shown in FIG. Cm- ¹ ) and the like, but it was confirmed that there was no absorption peak (1650 cm ^-1 ) derived from the carbonyl group in the urea bond.

As shown in FIG. 6, although the absorption peak (3000 cm <^-1> ) derived from a silicon atom etc. are mentioned as a main absorption peak with respect to (b2) component, the absorption peak (1650) originating in the carbonyl group in a urea bond. Cm- ¹ ) was confirmed to be absent.

And as shown in FIG. 4, using the absorption peak (1690 cm <^-1> ) derived from the carbonyl group in a urethane bond as a reference peak, the absorption peak (1650 cm <^-1> ) derived from the carbonyl group in a urea bond, Since it has the height of a predetermined ratio, it was judged that (b1) component and (b2) component reacted and the component (B) which is an addition compound was obtained.

In addition, as shown in FIG. 4, the absorption peak (1690 cm <^-1> ) derived from the carbonyl group in a urethane bond is made into the reference peak, and the absorption peak (2270 cm < ^-1 ) derived from the isocyanato group with respect to the height is shown. Since ratio of the height of is more than predetermined value, it judged that (B) component has an isocyanato group.

(3) Formulation of crosslinking agent

Xylene diisocyanate-trimethylolpropane adduct (TD-75, Soken Chemical Co., Ltd. product), solid content 75 weight%, ethyl acetate as a crosslinking agent which is (C) component with respect to 100 weight part of obtained adhesive components as (A) component. Solution) was added so as to be 0.15 parts by weight in terms of solid content.

(4) Adjustment of the pressure-sensitive adhesive composition

Finally, the silane coupling agent having (B) isocyanato group is added to 100 parts by weight of the pressure-sensitive adhesive component (in terms of solid content) so as to have a proportion of 0.10 parts by weight following the crosslinking agent (C) described above. After stirring until it became uniform, it diluted with ethyl acetate so that solid content concentration might be 20 weight%, and the adhesive composition (adhesive composition solution) was obtained.

2. Application of pressure-sensitive adhesive composition

Subsequently, with respect to the peeling process surface of the polyethylene terephthalate release film (lintec Co., Ltd. product, SP-PET3811) of 38 micrometers in thickness as a peeling film, the knife after drying the obtained adhesive composition solution is set to 25 micrometers. It applied using the formula coater, and formed the application layer.

Subsequently, after performing the drying process at 90 degreeC for 1 minute about the obtained application layer, it bonded together with the polarizing plate of 180 micrometers in thickness, and obtained the laminated body which consists of an application layer of an adhesive composition, and a polarizing plate.

3. Seasoning of pressure-sensitive adhesive composition

Subsequently, the obtained laminated body was left to stand (sealing) for 7 days on 23 degreeC and 50% RH conditions, and the adhesive composition was fully bridge | crosslinked, and the polarizing plate with an adhesive layer of Example 1 was obtained.

4. Evaluation of pressure-sensitive adhesive composition

(1) Evaluation of adhesive force

After bonding the obtained polarizing plate with an adhesive layer to the alkali free glass which is a to-be-adhered body, the adhesive force in the polarizing plate with an adhesive layer in 1 day after and 21 days after was measured, respectively.

That is, the obtained polarizing plate with an adhesive layer was cut out to the magnitude | size of width 25mm x length 100mm using the cutting device (The Ogino Seisakusho Co., Ltd. super cutter), and it was set as the measurement sample.

Subsequently, after peeling a peeling film from the obtained measurement sample, it bonded together to the alkali free glass (The Corning Co., Ltd. product, Eagle XG).

Subsequently, after putting the alkali free glass which the measurement sample bonded together to the autoclave (made by Kurihara Seisakusho Co., Ltd.), and pressurizing for 20 minutes on 0.5 MPa and 50 degreeC conditions, 23 degreeC and 50% RH Under the condition of, it was left to stand for 1 day.

Then, about the measurement sample, adhesive force was measured on condition of the following using the tensile tester (made by Orient Tech Co., Ltd.), and it evaluated according to the following reference | standard. The obtained results are shown in Table 1.

Peeling Speed: 300 mm / min

Peeling Angle: 180 °

(Double-circle): The value of adhesive force is a value over 3.5 N / 25 mm and 5.5 N / 25 mm or less.

(Circle): The value of adhesive force is a value exceeding 2.5N / 25mm and 3.5N / 25mm or less, or a value exceeding 5.5N / 25mm and 8.0N / 25mm or less.

(Triangle | delta): The value of adhesive force is a value over 1.0N / 25mm, 2.5N / 25mm or less, or a value over 8.0N / 25mm and 10.0N / 25mm or less.

X: The value of adhesive force is a value of 1.0 N / 25 mm or less, or the value exceeded 10.0 N / 25 mm.

In addition, after bonding the measurement sample to the alkali free glass similarly, the adhesive force at the time of leaving it for 21 days (504 hours) on 23 degreeC and 50% RH conditions was measured, and it evaluated according to the following reference | standard. The obtained results are shown in Table 1.

(Double-circle): The value of adhesive force is a value of 5.0 N / 25 mm or more and 20 N / 25 mm or less.

(Circle): The value of adhesive force is a value of 3.0 N / 25 mm or more and less than 5.0 N / 25 mm.

(Triangle | delta): The value of adhesive force is a value below 2.0 N / 25 mm and less than 3.0 N / 25 mm.

X: The value of adhesive force is a value less than 2.0 N / 25 mm, or the value exceeded 20 N / 25 mm.

(2) evaluation of durability

The durability of the polarizing plate with an adhesive layer under predetermined conditions was evaluated.

That is, the polarizing plate with an adhesive layer obtained was cut out to the magnitude | size of 233 mm x 309 mm using the cutting device (the Ogino Seisakusho Co., Ltd. make, super cutter), and it was set as the measurement sample.

Subsequently, after peeling a peeling film from the obtained measurement sample, it bonded together to the alkali free glass (The Corning Co., Ltd. product, Eagle XG).

Subsequently, the alkali free glass to which the measurement sample was bonded was put into the autoclave (made by Kurihara Seisakusho Co., Ltd.), and it pressed for 20 minutes on 0.5 Mpa and 50 degreeC conditions. After this sample was put under drying at 80 ° C., 60 ° C./90% RH, and heat shock (HS) conditions (one cycle at −35 ° C. (30 minutes) / 70 ° C. (30 minutes)), It was left for 100 hours and 500 hours, respectively.

Then, about the state of a measurement sample, observation was performed using 10 times loupe, and durability was evaluated according to the following reference | standard. The obtained results are shown in Table 1.

◎: No lifting or peeling off of the polarizing plate

(Circle): There exists lifting and peeling of 0.5 mm or less from the edge part (There is no lifting and peeling at the position exceeding 0.5 mm from the edge part)

(Triangle | delta): There exists a lifting and peeling of 1.0 mm or less from an edge part (there is no lifting and peeling at the position exceeding 1.0 mm from an edge part).

X: There exists lifting and peeling more than 1.0 mm from an edge part

(3) Evaluation of gel fraction

The gel fraction of the adhesive composition was evaluated. That is, after apply | coating an adhesive composition on the peeling layer of a peeling film, and heat-processing at 90 degreeC for 1 minute, it replaces a polarizing plate, The polyethylene terephthalate release film of 38 micrometers in thickness as another peeling film (made by Lintec Corporation) , SP-PET3801) was bonded to the coating layer so that the release layer was in contact with the coating layer.

Then, the adhesive sheet was obtained by leaving it to stand (sealing) for 12 days on 23 degreeC and 50% RH conditions.

Subsequently, the peeling film of both surfaces of the obtained adhesive sheet was peeled off, about 0.1 g of adhesive composition was taken out, wrapped in Tetron mesh (# 200), and the Soxlay extracting apparatus (Tokyo Glass Machine Co., Ltd.) which used ethyl acetate as a solvent. The non-gel powder of the adhesive composition was extracted using the reflux by the lubricating agent and the fat extractor, and the gel fraction was calculated from the ratio with the initial mass. The obtained results are shown in Table 1.

(4) Evaluation of haze value

The haze value of the adhesive layer was evaluated. That is, the adhesive sheet was obtained like (3) the evaluation of a gel fraction.

Subsequently, peeling film of both surfaces of the obtained adhesive sheet was peeled off, and it was set as the measurement sample, and JIS was obtained using the integrated sphere light transmittance measuring apparatus (made by Nihon Denshoku Kogyo Co., Ltd., NDH-2000). Based on K7105, the diffuse transmittance (Td%) and total light transmittance (Tt%) were measured, and the haze value was computed by following formula (3). The obtained results are shown in Table 1.

Haze value = (Td / Tt) × 100 (3)

[Examples 2 to 4]

In Examples 2-4, the compounding quantity of (B) the silane coupling agent (I) which has an isocyanato group was made into 0.2 weight part, 0.5 weight part, and 1.0 weight part, respectively with respect to 100 weight part of (A) adhesive components. In the same manner as in Example 1, a polarizing plate with a pressure-sensitive adhesive layer was prepared, and the adhesive strength and the like were evaluated. The obtained results are shown in Table 1.

[Example 5]

In Example 5, N-octyl-2-methylpyridinium hexafluoride (ILP-18-2-60T, manufactured by Koei Chemical Co., Ltd.) was used as an antistatic agent. On the other hand, the polarizing plate with an adhesive layer was created like Example 2 except having added 3.0 weight part further, and the adhesive force etc. were evaluated. The obtained results are shown in Table 1.

Comparative Example 1

In Comparative Example 1, except that the (B) silane coupling agent having an isocyanato group was not added, the polarizing plates with an adhesive layer were prepared in the same manner as in Example 2, respectively, and the adhesive strength and the like were evaluated. The obtained results are shown in Table 1.

Comparative Example 2

In Comparative Example 2, a polarizing plate with a pressure-sensitive adhesive layer was prepared in the same manner as in Example 2 except that the (C) crosslinking agent was not added, and the adhesive strength and the like were evaluated. The obtained results are shown in Table 1.

[Comparative Example 3]

In the comparative example 3, (B) (gamma) -isocyanate propyl triethoxysilane (type II, brand name KBE-9007, Shin-Etsu Chemical Co., Ltd.) represented by Formula (8) instead of the silane coupling agent which has an isocyanato group. Except for using the agent), the polarizing plate with an adhesive layer was created like Example 2, respectively, and the adhesive force etc. were evaluated. The obtained results are shown in Table 1.

[Comparative Example 4]

In Comparative Example 4, instead of the silane coupling agent having an isocyanato group (B), N-phenyl-γ-aminopropyltrimethoxysilane (Type III, trade name KBM-573, Shin-Etsu) represented by formula (9) Except having changed to Kaku Kogyo Co., Ltd., the polarizing plate with an adhesive layer was created like Example 2, respectively, and the adhesive force etc. were evaluated. The obtained results are shown in Table 1.

[Comparative Example 5]

In Comparative Example 5, (C) the crosslinking agent is 0.30 part by weight based on 100 parts by weight of the pressure sensitive adhesive component, and (B) represented by the above formula (9) instead of the silane coupling agent having an isocyanato group Except having changed into 0.30 weight part of N-phenyl- (gamma)-aminopropyl trimethoxysilane (Type III, KBM-573, Shin-Etsu Chemical Co., Ltd. product), the polarizing plate with an adhesive layer was produced like Example 2, respectively. And adhesive strength were evaluated. The obtained results are shown in Table 1.

[Comparative Example 6]

In Comparative Example 6, N-octyl-2-methylpyridinium hexafluoride (ILP-18-2-60T, manufactured by Koei Chemical Co., Ltd.) was used as an antistatic agent based on 100 parts by weight of the (A) pressure-sensitive adhesive component. Except having added 3.0 weight part further, the polarizing plate with an adhesive layer was created like the comparative example 3, and the adhesive force etc. were evaluated. The obtained results are shown in Table 1.

[Table 1]

As described above, according to the present invention, even when an acid-free pressure sensitive adhesive component is used, even when a relatively small amount of addition is used, (B) specific silane coupling agent or (C) crosslinking agent with respect to the pressure sensitive adhesive component (A) By mix | blending etc., the adhesive composition excellent in the balance of rework property and durability in a predetermined environment, and excellent in the corrosion resistance with respect to metal, and the adhesive sheet using the same can be obtained.

Therefore, the adhesive composition of this invention etc. are various, including optical films (polarizing plate, retardation plate, light-diffusion plate, etc.) applied to a liquid crystal display device, a plasma display device, an organic electroluminescent device, an inorganic electroluminescent device, etc. It is anticipated that it will remarkably contribute to the quality improvement of a film.

1: Coating layer of adhesive composition 2: Release film
10: pressure-sensitive adhesive layer 20: polarizer
22: low refractive index layer 24: hard coating layer
26: TAC film 28: adhesive layer
30: protective layer 32: protective film
34: polarizing film 36: transparent base film
38: light diffusing layer 40: retardation film
42: transparent resin film 44: surface treatment layer
46: light diffusion film 48: surface treatment film
50, 300: polarizer 60: reflective film
100: adhesive sheet 101: base material
200: adherend 310: phase difference plate
320: light diffusing polarizing plate 330: antireflection film

Claims (8)

(A) an adhesive component,
(B) a silane coupling agent having an isocyanato group,
(C) an adhesive composition containing at least one component selected from a crosslinking agent and a curing agent,
While the silane coupling agent having the (B) isocyanato group is a coupling agent compound obtained by reacting an organic alkoxysilane compound having a (b1) polyisocyanate compound and (b2) a reactive organic functional group,
The compounding quantity of the silane coupling agent which has the said (B) isocyanato group is made into the value within the range of 0.005-5 weight part with respect to 100 weight part of said (A) adhesive components, The adhesive composition characterized by the above-mentioned. The method of claim 1,
Said (A) adhesive component is the (meth) acrylic acid ester polymer derived from the following (a1)-(a3) component as a monomer component, The adhesive composition characterized by the above-mentioned.
(a1) Alkyl (meth) acrylic-acid alkylester of 1-20 carbon atoms of an alkyl group: 100 weight part
(a2) Polymeric double bond containing compound which has a hydroxyl group in a molecule: 0.5-10 weight part
(a3) Polymeric double bond-containing compound having a carboxyl group in the molecule: 0 parts by weight or 0 to 0.01 parts by weight (but not including 0 parts by weight) The method of claim 1,
The silane coupling agent which has the said (B) isocyanato group is a compound represented by following General formula (1) or General formula (2), The adhesive composition characterized by the above-mentioned.

(In general formula (1), some R <^1> and R <^2> is a C1-C6 alkyl group each independently, n is an integer of 1-8, and some a is an integer of 0-3. , X is a urea bond, a urethane bond, a thiourethane bond, an amide bond, an allophanate bond, a biuret bond, an isocyanurate bond, or a carbodiimide bond, Y is following General formula (3) It is a structure represented by (5))

(In general formula (2), R <^1> and R <^2> is a C1-C6 alkyl group each independently, n is an integer of 1-8, a is an integer of 0-3, X is A urea bond, a urethane bond, a thiourethane bond, an amide bond, an allophanate bond, a biuret bond, an isocyanurate bond, or a carbodiimide bond, Y is represented by following General formula (3)-(5) Is a structure)

(In general formula (3), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group, and R "is a C1-C8 trivalent alcohol group. Is a residue of

(In general formula (4), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group.)

(In general formula (5), some R 'is respectively independently a C1-C8 alkylene group or a C6-C18 arylene group.) The method of claim 1,
The reactive organic functional group of the said (b2) organic alkoxysilane compound is a primary or secondary amino group, The adhesive composition characterized by the above-mentioned. The method of claim 1,
The compounding quantity of the at least 1 component chosen from the said (C) crosslinking agent and a hardening | curing agent is made into the value within the range of 0.001-30 weight part with respect to 100 weight part of said (A) adhesive components. The adhesive layer derived from the adhesive composition of Claim 1 was provided on the base material, The adhesive sheet characterized by the above-mentioned. The method according to claim 6,
The said base material is an optical film, The adhesive sheet characterized by the above-mentioned. The method according to claim 6,
While the said base material is a peeling film, the other adhesive film is laminated | stacked with respect to the opposite surface of the said peeling film in the said adhesive layer, The adhesive sheet characterized by the above-mentioned.

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