TW201821564A - Pressure sensitive adhesive - Google Patents

Abstract

Provided is a pressure-sensitive adhesive which comprises silicone release paper and a pressure-sensitive adhesive layer of a cured object obtained from a photocurable composition comprising (A) an organic polymer having a number-average molecular weight of 3,000 or higher and having a crosslinkable silicon-containing group, (B) a tackifier resin, (C) a silicon compound having an Si-F bond, and (D) a photobase generator, the pressure-sensitive adhesive layer having excellent separability from the silicone release paper. The pressure-sensitive adhesive comprises silicone release paper and, superposed thereon, a pressure-sensitive adhesive layer constituted of a cured object obtained from a photocurable composition comprising (A) an organic polymer having a number-average molecular weight of 3,000 or higher and having a crosslinkable silicon-containing group, (B) a tackifier resin, (C) a silicon compound having an Si-F bond, (D) a photobase generator, and (E) a compound having a number-average molecular weight less than 3,000 and having a hydrolyzable silicon-containing group.

Description

   Pressure sensitive adhesive   

The present invention relates to a pressure-sensitive adhesive. In particular, the present invention relates to a pressure-sensitive adhesive, which is a pressure-sensitive adhesive layer made of a hardened product of a composition containing an organic polymer having a crosslinkable silicon group and a tackifier resin having a number average molecular weight of 3,000 or more, Laminated with release paper.

A curable composition containing a polymer having a crosslinkable silicon group and a curing catalyst is crosslinked and cured by the action of moisture such as moisture in the air to produce a cured product. Therefore, a polymer composition having a crosslinkable silicon group is used for an adhesive and a sealing material.

Patent Documents 1 and 2 disclose a curable composition for producing a pressure-sensitive adhesive containing a polyether polymer (polyoxyalkylene polymer) having a crosslinkable silicon group. This hardenable composition is coated on a pressure-sensitive adhesive base material such as an adhesive tape, and the cross-linkable silicon group is cross-linked with moisture in the air to prepare a pressure-sensitive adhesive. The organic polymer having a crosslinkable silicon group used in the curable composition has a low viscosity and is easy to apply. Therefore, a pressure-sensitive adhesive can be produced without using a toxic and dangerous organic solvent.

As disclosed in Patent Documents 3 and 4, the pressure-sensitive adhesives of Patent Documents 1 and 2 described above have a problem of poor releasability from polysiloxane release paper. That is, the peel resistance of the adhesive and the release paper rises over time, and when it is defective, the release paper may break and fail to peel.

The present inventors have discovered a light containing (A) an organic polymer having a crosslinkable silicon group, (B) a tackifying resin, (C) a silicon compound having a Si-F bond, and (D) a photobase generator. The cured product of the curable composition is a pressure-sensitive adhesive having a pressure-sensitive adhesive layer, and is applied in the form of an international patent application PCT / JP2016 / 062820. The photocurable composition described in this international patent application has the advantages of not undergoing cross-linking and hardening due to moisture in the air, etc., even if heated to a high temperature, and it is rapidly cross-linking and hardening by light irradiation, Therefore, the pressure-sensitive adhesive can be easily manufactured. However, it has also been confirmed that the pressure-sensitive adhesive described in the international patent application also has a problem of poor peelability from the silicone release paper.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 55-056153

Patent Document 2 Japanese Patent Laid-Open No. 60-035069

Patent Document 3 Japanese Patent Laid-Open No. 61-060771

Patent Document 4 Japanese Patent Application Publication No. 2013-32450

The problem to be solved by the present invention is to provide a pressure-sensitive adhesive which contains (A) an organic polymer having a crosslinkable silicon group in a number average molecular weight of 3,000 or more, (B) a tackifying resin, and (C) having The silicon compound of the Si-F bond and the cured product of the photocurable composition of the (D) photobase generator are provided as a pressure-sensitive adhesive layer, and have excellent releasability from a silicone release paper.

The present inventors have found that (A) an organic polymer having a crosslinkable silicon group with a number average molecular weight of 3,000 or more, (B) a tackifying resin, (C) a silicon compound having a Si-F bond, and (D) In the photocurable composition of the photobase generator, when a compound having a hydrolyzable silicon group having a number average molecular weight of less than 3,000 (E) is further added, a pressure-sensitive adhesive having excellent peelability from a polysiloxane release paper can be obtained. .

That is, the present invention relates to a pressure-sensitive adhesive, which is formed by laminating a pressure-sensitive adhesive layer and a polysiloxane release paper, and the pressure-sensitive adhesive layer contains (A) a number having an average molecular weight of 3,000 or more and having crosslinking Organic silicon-based polymers, (B) tackifying resins, (C) silicon compounds with Si-F bonds, (D) photobase generators, and (E) hydrolyzable silicon with a number average molecular weight of less than 3,000 It is composed of a cured product of a photo-curable composition of a base compound.

Further, in the pressure-sensitive adhesive, the (A) organic polymer having a crosslinkable silicon group having a number average molecular weight of 3,000 or more may be a polyoxyalkylene-based polymer having a crosslinkable silicon group.

Among the pressure-sensitive adhesives, (B) the tackifying resin is preferably a terpene phenol resin and / or an aromatic petroleum resin.

In the pressure-sensitive adhesive, the silicon compound (C) having a Si-F bond is preferably an organic polymer having a Si-F bond.

Moreover, among the above pressure-sensitive adhesives, a pressure-sensitive adhesive of a silicone release paper having a lightly releasable layer on one side and a heavy releasable layer on the other side is preferably laminated.

A silicone release paper having a light release layer in one area of the pressure-sensitive adhesive layer and a silicone release paper having a heavy release layer in the other area can be used.

The pressure-sensitive adhesive of the present invention has the photocurable composition used, does not undergo cross-linking and hardening due to moisture in the air, and rapidly cross-links and hardens by light irradiation, so it can be easily produced. In addition, it has the effect of excellent peelability from silicone release paper.

Best Mode for Invention

(A) The organic polymer having a crosslinkable silicon group having a number average molecular weight of 3,000 or more is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group having a number average molecular weight of 3,000 or more. The organic polymer having a crosslinkable silicon group used in the present invention is an organic polymer whose main chain is not polysiloxane, except for polysiloxanes which have various main chain skeletons. In the field of electrical applications, From the viewpoint of not containing or not generating a low-molecular-weight cyclic siloxane that is a main cause of poor contact, it is preferable.

Examples of the main chain skeleton of the (A) organic polymer having a crosslinkable silicon group having a number average molecular weight of 3,000 or more include polyoxypropylene, polyoxybutylene, and polyoxyethylene-polyoxypropylene copolymerization. Materials such as polyoxyalkylene-based polymers; ethylene-propylene-based copolymers, polyisobutylene, polyisoprene, polybutadiene, and the like, hydrogenated polyolefin-based polymers obtained by hydrogenation Hydrocarbon polymers such as polymers; Polyester polymers obtained by condensation of a dibasic acid such as adipic acid with a diol, or by ring-opening polymerization of lactones; ethyl (meth) acrylate, ( (Meth) acrylate polymer obtained by radical polymerization of monomers such as butyl (meth) acrylate; monomers such as (meth) acrylate monomers, vinyl acetate, acrylonitrile, and styrene Ethylene polymer obtained by radical polymerization; Graft polymer obtained by polymerizing vinyl monomer in organic polymer; Polysulfide polymer; Polyamide polymer; Polycarbonate polymer ; Diallyl phthalate polymer and the like. These skeletons may be contained alone in the organic polymer having a crosslinkable silicon group (A), or may be contained in two or more kinds in a block or random form.

In addition, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, or polyoxyalkylene polymers, and (meth) acrylate polymers are due to the glass transition temperature. Lower, the resulting hardened product is excellent in cold resistance. In addition, polyoxyalkylene-based polymers and (meth) acrylate-based polymers are particularly preferred because they have high moisture permeability, and when they are formed into a one-liquid composition, they are excellent in deep hardenability.

The crosslinkable silicon group in the component (A) is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and can be crosslinked by forming a siloxane bond. The crosslinkable silicon group is preferably a group represented by the general formula (1).

In formula (1), R ¹ represents an organic group. R ¹ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among these, R ¹ is particularly preferably a methyl group. R ¹ may have a substituent. X represents a hydroxyl group or a hydrolyzable group. When two or more X are present, a plurality of X may be the same or different. a is any integer of 1, 2 or 3. From the standpoint of considering the hardenability and obtaining a photocurable composition having a sufficient hardening rate, in the formula (1), a is preferably 2 or more, and more preferably 3. From the viewpoint of obtaining a photocurable composition having sufficient flexibility, a is preferably 2.

The hydrolyzable group represented by X is not particularly limited as long as it is other than the F atom. Examples thereof include an alkoxy group, a fluorenyloxy group, a ketoxime ester group, an aminooxy group, and an alkenyloxy group. Among these, an alkoxy group is preferable from a viewpoint that a hydrolyzable group can be handled smoothly. Among the alkoxy groups, a group having a small number of carbon atoms has high reactivity. In the order of methoxy> ethoxy> propoxy, the higher the carbon number, the lower the reactivity. It can be selected according to the purpose and application. Generally, methoxy and ethoxy can be used.

Specific structural aspects of the crosslinkable silicon group include trialkoxysilyl groups such as trimethoxysilyl groups and triethoxysilyl groups [-Si (OR) ₃ ], methyldimethoxysilyl groups, and the like. Dialkoxysilyl [-SiR ¹ (OR) ₂ ] such as methyl, methyldiethoxysilyl, etc., is highly reactive because of trialkoxysilyl [-Si (OR) ₃ ]. It is better to use trimethoxysilyl. Here, R is an alkyl group such as methyl or ethyl. The photocurable composition used in the present invention is a polymer having a trimethoxysilyl group having high reactivity, does not harden due to moisture in the air, and exhibits excellent stability. Despite being stable, it will harden quickly when exposed to light. Therefore, in the crosslinkable silicon group in the (A) component used for manufacture of a photocurable composition, a trimethoxysilyl group is the most preferable.

In addition, the crosslinkable silicon-based system may be used singly or in combination of two or more. The crosslinkable silicon group may be present in the main chain or the side chain, or either.

The organic polymer having a crosslinkable silicon group having a number average molecular weight of 3,000 or more may be linear or branched. When polystyrene is converted in GPC, the number average molecular weight is about 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number-average molecular weight is less than 3,000, there is a tendency that the tensile properties of the cured product are insufficient, and when it exceeds 100,000, the viscosity tends to increase and the workability tends to decrease. In addition, from the viewpoint of ensuring the flexibility of the cured product obtained by curing the photocurable composition, the higher the number average molecular weight is, the better.

In order to obtain a rubber-like hardened product with high strength, high elongation, and low elastic modulus, a crosslinkable silicon group contained in an organic polymer having a crosslinkable silicon group having a number average molecular weight of 3,000 or more is preferred There are more than 0.8 in one molecule of the polymer, preferably 1.0 or more, and more preferably 1.1 to 5 or more. When the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the hardenability is insufficient and it is difficult to exhibit good rubber elasticity. Further, from the viewpoint of reducing the crosslinking density, it is preferable to use an organic polymer in which the number of crosslinkable silicon groups contained in the molecule is 1.0 or less on average in combination. The crosslinkable silicon group may be at the end of the main chain or the side chain of the molecular chain of the organic polymer, or at both ends. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective mesh length of the organic polymer component contained in the final hardened product becomes longer, so high strength and high elongation can be easily obtained. And exhibits a rubber-like hardened product with a low elastic modulus.

The polyoxyalkylene-based polymer is essentially a polymer having a repeating unit represented by the general formula (2).

-R ² -O -... (2)

In the general formula (2), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and 2 to 4 carbon atoms A linear or branched alkylene group is more preferred.

Specific examples of the repeating unit represented by the general formula (2) include -CH ₂ CH ₂ O-, -CH ₂ CH (CH ₃ ) O-, -CH ₂ CH ₂ CH ₂ CH ₂ O- Wait. The main chain skeleton of the polyoxyalkylene-based polymer may be composed of only one repeating unit, or may be composed of two or more repeating units.

Examples of the synthesis method of the polyoxyalkylene-based polymer include a polymerization method using an alkali catalyst such as KOH, a polymerization method using a double metal cyanide complex catalyst, and the like, but there is no particular limitation. limited. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene-based polymer having a high molecular weight with a number average molecular weight of 6,000 or more, Mw / Mn of 1.6 or less, and a narrow molecular weight distribution can be obtained.

The polyoxyalkylene polymer may contain other bonds such as a urethane bond in the main chain skeleton. In terms of urethane bonds, examples include aromatic polyisocyanates such as toluene (methylenephenyl) diisocyanate, diphenylmethane diisocyanate, and the like; aliphatic polyisocyanates such as isophorone diisocyanate; and the like. A bond obtained by reaction with a polyoxyalkylene polymer having a hydroxyl group.

A polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group in the molecule, a functional group that is reactive to the functional group, and a functional group that has a crosslinkable silicon group. The reactant reacts to introduce a crosslinkable silicon group into the polyoxyalkylene-based polymer (hereinafter referred to as a polymer reaction method).

Examples of the polymer reaction method include hydrosilylation of a hydrosilane having a crosslinkable silyl group and a mercapto compound having a crosslinkable silyl group in a polyoxyalkylene-based polymer containing an unsaturated group. Or a method of thiolization to obtain a polyoxyalkylene polymer having a crosslinkable silicon group. An unsaturated group-containing polyoxyalkylene-based polymer is an organic polymer having a functional group such as a hydroxyl group, and an organic compound having an active group and an unsaturated group that are reactive to the functional group is reacted to obtain an organic compound containing an unsaturated group. Polyoxyalkylene polymer of saturated group.

In addition, as another example of the polymer reaction method, a method of reacting a polyoxyalkylene-based polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group may be mentioned, and an terminal having an isocyanate group. A method for reacting a polyoxyalkylene-based polymer with a compound having an active hydrogen group such as a hydroxyl group or an amine group, and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene-based polymer having a crosslinkable silicon group can be easily obtained.

The polyoxyalkylene-based polymer having a crosslinkable silicon group can be used alone or in combination of two or more kinds.

The saturated hydrocarbon polymer is a polymer that does not substantially contain other carbon-carbon unsaturated bonds except for the aromatic ring. The polymer having this skeleton can be obtained by (1) polymerizing an olefin-based compound having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, and isobutene, as a main monomer, or ( 2) A method of homopolymerizing a diene-based compound such as butadiene or isoprene, or copolymerizing a diene-based compound with an olefin-based compound, followed by a method such as hydrogenation. Isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferred because functional groups can be easily introduced at the ends, molecular weight can be easily controlled, and the number of terminal functional groups can be increased. Particularly preferred is an isobutylene-based polymer. The main chain skeleton is a saturated hydrocarbon-based polymer that is excellent in heat resistance, weather resistance, durability, and moisture resistance.

The isobutylene-based polymer may be formed of all the monomer units being isobutylene units, or may be a copolymer with other monomers. In terms of rubber characteristics, polymers containing 50% by mass or more of repeating units derived from isobutylene are preferred, polymers containing 80% by mass or more are more preferred, and polymers containing 90 to 99% by mass are particularly preferred. good.

As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods may be mentioned. In particular, various living polymerizations have been developed. Saturated hydrocarbon-based polymers, especially isobutylene-based polymers, can easily undergo transfer polymerization initiated by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, Vol. 15, p. 2843) and Manufacturing. According to this manufacturing method, a polymer having a molecular weight of about 500 to 100,000 and a molecular weight distribution of 1.5 or less can be obtained, and various functional groups can be introduced at the molecular end.

As an example of a method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group, a cationic polymerization using a combination of an organic halogen compound that generates a stable carbocation and a Friedel Crafts acid catalyst as a copolymerization initiator can be cited. law. Examples include the initiation of the transfer method disclosed in Japanese Patent No. 4-69659.

The saturated-based polymer having a crosslinkable silicon group can be used alone or in combination of two or more kinds.

As a (meth) acrylic acid ester monomer which comprises the main chain of a (meth) acrylic acid ester polymer, various monomers can be used. Examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearin (meth) acrylate (Meth) acrylic acid alkyl ester-based monomers; alicyclic (meth) acrylic acid ester-based monomers; aromatic (meth) acrylic acid ester-based monomers; 2-methoxyethyl (meth) acrylate (Meth) acrylate monomers such as esters; γ- (meth) acrylfluorenyloxypropyltrimethoxysilane, γ- (meth) acrylfluorenyloxypropyldimethoxymethyl Silane-containing (meth) acrylate-based monomers; derivatives of (meth) acrylic acid; fluorine-containing (meth) acrylate-based monomers and the like.

In the (meth) acrylate-based polymer, the (meth) acrylate-based monomer can be copolymerized with the following vinyl-based monomer. Examples of the vinyl-based monomer include styrene, maleic anhydride, and vinyl acetate.

These may be used singly or in a plurality of types. In addition, the number of crosslinkable silicon groups in the (meth) acrylate polymer can be controlled by the combined use of (meth) acrylate monomers containing a crosslinkable silicon group. Since the adhesion is good, a methacrylate polymer containing a methacrylate monomer is particularly preferable. When the viscosity is lowered, flexibility is provided, and adhesiveness is provided, an acrylate monomer is suitably used. In the present specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The manufacturing method of a (meth) acrylate type polymer is not specifically limited, For example, the radical polymerization method using a radical polymerization reaction can be used. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, and a crosslinkable silicon group can be introduced at a controlled position such as a terminal. Controlled radical polymerization. A polymer obtained by using a free radical polymerization method such as an azo compound as a polymerization initiator and a peroxide generally has a molecular weight distribution of 2 or more and a high viscosity. Therefore, in order to obtain a (meth) acrylic acid ester polymer having a narrow molecular weight distribution and a low viscosity, when a (meth) acrylic acid ester polymer having a crosslinkable functional group at a molecular chain end in a high proportion, It is desirable to use a controlled radical polymerization method.

Examples of the controlled radical polymerization method include a free radical polymerization method using a chain transfer agent having a specific functional group, or a living radical polymerization method. Additive-fragment transfer reaction (reversible addition-fracture chain transfer: RAFT) polymerization method, radical polymerization method using transition metal complex (transition metal-mediated living radical polymerization), and other living radical polymerization methods Better. Further, a reaction using a thiol compound having a reactive silicon group, or a reaction using a thiol compound having a reactive silicon group and a metallocene compound are also preferable.

The (meth) acrylate-based polymer having a crosslinkable silicon group may be used alone or in combination of two or more kinds.

These organic polymers having a crosslinkable silicon group having a number average molecular weight of 3,000 or more may be used alone or in combination of two or more kinds. Specifically, a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (methyl) group having a crosslinkable silicon group can also be used. An organic polymer in which two or more kinds of acrylate-based polymers are mixed. In particular, an organic polymer in which a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group are mixed has excellent characteristics. When such a polymer is used in a photocurable composition, the tensile shear adhesive force and the adhesive force of the pressure-sensitive adhesive can be improved.

Various methods can be mentioned as a manufacturing method of the organic polymer which mixed the polyoxyalkylene type polymer which has a crosslinkable silicon group, and the (meth) acrylate type polymer which has a crosslinkable silicon group. For example, in a crosslinkable silicon group, the molecular chain is substantially composed of a (meth) acrylate monomer unit represented by the general formula (3) and a (meth) acrylate monomer represented by the general formula (4) A method of producing a copolymer composed of units by mixing a polyoxyalkylene-based polymer having a crosslinkable silicon group.

-CH ₂ -C (R ³ ) (COOR ⁴ ) -... (3)

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms); -CH ₂ -C (R ³ ) (COOR ⁵ ) -... (4)

(In the formula, R ³ is the same as described above, and R ⁵ represents an alkyl group having 6 or more carbon atoms).

Examples of R ⁴ represented by the general formula (3) include an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, propyl, n-butyl, and tertiary butyl, and an alkane having 1 to 4 carbon atoms. A radical is preferred, and an alkyl group having 1 to 2 carbon atoms is more preferred. The alkyl group of R ⁴ may be used alone or in combination of two or more.

Examples of R ^{5 in the} general formula (4) include an alkyl group having 6 or more carbon atoms such as 2-ethylhexyl, dodecyl, and octadecyl, and generally an alkyl group having 7 to 30 carbon atoms. A long-chain alkyl group of 8 to 20 is preferred. Further, the same group of lines ⁴ and R R ^5, may be used alone or as a mixture of two or more.

The molecular chain of the (meth) acrylic acid ester polymer is substantially composed of monomer units of the formula (3) and the formula (4). Here, "substantially" means that the total of the monomer units of the formula (3) and the formula (4) existing in the copolymer exceeds 50% by mass. The total of the monomer units of the formula (3) and the formula (4) is preferably 70% by mass or more. In addition, the existence ratio of the monomer unit of the formula (3) and the monomer unit of the formula (4) is preferably 95: 5 to 40:60 in terms of mass ratio, and more preferably 90:10 to 60:40.

The number average molecular weight of the (meth) acrylate copolymer is preferably 3,000 to 10,000, more preferably 3,000 to 5,000, and even more preferably 4,000 to 4,500. By setting the number average molecular weight within this range, compatibility with a polyoxyalkylene-based polymer having a crosslinkable silicon group is improved. The (meth) acrylic polymer may be used alone or in combination of two or more kinds. The blending ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylate polymer having a crosslinkable silicon group is not particularly limited, but it is relative to the (meth) acrylate system. The total of the polymer and the polyoxyalkylene-based polymer is 100 parts by mass. The (meth) acrylate polymer is preferably within a range of 10 to 60 parts by mass, and more preferably within a range of 20 to 50 parts by mass. It is better to be in the range of 25 to 45 parts by mass. When the (meth) acrylic acid ester polymer is more than 60 parts by mass, the viscosity is increased and the handleability is deteriorated, which is not preferable.

Furthermore, an organic polymer in which a saturated hydrocarbon-based polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group are mixed may be used. As a method for producing an organic polymer obtained by mixing a (meth) acrylic acid ester copolymer having a crosslinkable silicon group, it is also possible to use (A) in the presence of an organic polymer having a crosslinkable silicon group. A method for polymerizing an acrylate-based polymer.

(B) The tackifying resin of the component is not particularly limited, and resins having a polar group such as rosin ester resin, phenol resin, xylene resin, xylenol resin, terpene phenol resin, and the like can be used; Various aromatic resins, aliphatic-aromatic copolymers, or alicyclic resins, or benzofuran resins, low molecular weight polyethylene resins, terpene resins, and these hydrogenated resins. Sticky resin. These systems can be used alone or in combination of two or more.

Examples of the aromatic petroleum resin include α-methylstyrene monopolymer resin [FTR Zero series, manufactured by Mitsui Chemicals Co., Ltd.], styrene monomer monopolymer resin [FTR 8000 series, Mitsui Chemicals Co., Ltd.], styrene monomer / aromatic monomer copolymer resin [FMR series, Mitsui Chemicals Co., Ltd.], α-methylstyrene / styrene copolymer resin [FTR 2000 series, Mitsui Chemical Co., Ltd.] and other aromatic styrene resins, or styrene monomer / aliphatic monomer copolymer resins [FTR 6000 series, manufactured by Mitsui Chemicals Co., Ltd.], styrene monomer / Alpha-methylstyrene / aliphatic monomer copolymer resins [FTR 7000 series, manufactured by Mitsui Chemicals Co., Ltd.] and other aliphatic-aromatic copolymer-based styrene resins.

From the viewpoint of compatibility with (A) organic polymers having a crosslinkable silicon group having a number average molecular weight of 3,000 or more, the tackifying resin is a solubility parameter calculated by the Small method using the Hoy constant (hereinafter, the principle The abbreviated "SP value" above is preferably 7.9 to 11.0, more preferably 8.2 to 9.8, and most preferably 8.5 to 9.5. From the viewpoint of the adhesive force of the pressure-sensitive adhesive, it is preferable to select a resin having a polarity consistent with the adherend. When the tackifying resin is used on an adherend having a low polarity, it is preferable to use a tackifying resin having a low polarity. When using a tackifying resin with a high polarity, a tackifying resin having a high polarity is preferred. When using a tackifying resin for a wide range of adherends from a highly polar adherend to a low-polar adherend, it is better to mix the user with the lower polar tackifier resin and the higher polar tackifier resin. . In addition, the polarity (SP value) of the terpene phenol resin is YS Polystar (manufactured by Yasuhara Chemical) U-series SP value 8.69, T-series SP value 8.81, S-series SP value 8.98, and G-series SP value It is 9.07 and the SP value of K series is 9.32. By selecting the polarity (SP value), it is possible to adapt to various types of adherends from low-polar adherends to high-polar adherends.

As the tackifier resin, a terpene phenol resin and an aromatic petroleum resin are preferred from the viewpoint of good compatibility with an organic polymer having a crosslinkable silicon group. As the aromatic petroleum resin, an aromatic styrene resin and an aliphatic-aromatic copolymer styrene resin are preferred, and an aliphatic-aromatic copolymer styrene resin is more preferred. From the standpoint of excellent adhesion, terpene phenol resin is the most preferable. From the viewpoint of VOC and fogging, it is preferable to use an aliphatic-aromatic copolymer-based styrene resin. Furthermore, from the viewpoint of operability, it is preferable to use an aliphatic-aromatic copolymer-based styrene resin that is hardly increased in viscosity.

With respect to 100 parts by mass of the component (A), the amount of the tackifying resin (B) used is preferably 10 to 200 parts by mass, and more preferably 20 to 150 parts by mass. When it is less than 10 parts by mass, the adhesive force is insufficient, and when it is more than 200 parts by mass, the adhesive force is insufficient due to the hardened material, or the operability may be lowered due to the excessive viscosity.

(C) As the silicon compound having a Si-F bond, various compounds including a silicon group (hereinafter, referred to as a fluorosilyl group) having a Si-F bond can be used. As the silicon compound as the component (C), either an inorganic compound or an organic compound can be used. The component (C) is preferably an organic compound having a fluorosilicon group, and an organic polymer having a fluorosilicon group is more preferable because of high safety. In addition, from the viewpoint that the photocurable composition has a low viscosity, a low-molecular organosilicon compound having a fluorosilicon group is preferred.

(C) Preferred examples of the silicon compound having a Si-F bond include fluorosilane described in WO2015-088021 shown in formula (5), and WO2015-088021 shown in formula (6). Compounds having a fluorosilicon group (hereinafter also referred to as fluorinated compounds), organic polymers having a fluorosilicon group (hereinafter also referred to as fluorinated polymers) described in WO2015-088021, and the like.

R ⁶ _4-d SiF _d ... (5)

(In formula (5), R ⁶ each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ⁷ SiO- (R ^{7 is} each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, Or fluorine atom) any of the organosiloxy groups. D is any of 1 to 3, and d is preferably 3. When there are a plurality of R ⁶ and R ⁷ , these may be the same or different. .)

-SiF _d R ⁶ _e Z _f ... (6)

(In formula (6), R ⁶ and d are the same as those in formula (5), each Z is independently a hydrolyzable group other than a hydroxyl group or fluorine, e is any of 0 to 2, and f is any of 0 to 2 , D + e + f is 3. When there is a plurality of R ₆ , R ₇ and Z, these may be the same or different.)

Examples of the fluorosilane represented by the formula (5) include fluorodimethylphenylsilane, vinyltrifluorosilane, γ-methacryloxypropyltrifluorosilane, and octadecyltrisiloxane. Fluorosilane and so on.

Among the compounds having a fluorosilyl group represented by formula (6), the hydrolyzable group represented by Z is preferably an alkoxy group from the viewpoint of mild hydrolyzability and ease of handling, and R ⁶ is a methyl group Better.

As an example of the fluorosilyl group represented by the formula (6), a fluorosilyl group having no hydrolyzable group or a fluorosilyl group in which R ⁶ is a methyl group is more preferable, and a trifluorosilyl group is more preferable.

The compound having a fluorosilyl group represented by the formula (6) is not particularly limited, and any of a low-molecular compound and a high-molecular compound can be used. Examples include: inorganic silicon compounds; low-molecular-weight organic silicon compounds such as vinyldifluoromethoxysilane, vinyltrifluorosilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, etc .; ) And other polymer compounds such as fluorosilyl-based fluorinated polysiloxane. The fluorosilane represented by formula (5), a polymer having a fluorosilicon group represented by formula (6) at the end of the main chain or a side chain is preferable.

For the fluorinated polymer, various organic polymers having Si-F bonds can be used.

The fluorinated polymer may be a fluorosilyl group, and a single polymer having the same backbone skeleton, that is, the number of fluorosilyl groups per molecule, its bonding position, the F number of the fluorosilyl group, and the main chain. A single polymer with the same backbone. Moreover, any or all of these may be a mixture of different plural kinds of polymers. Any of these fluorinated polymers functions as a resin component of a photocurable composition that exhibits rapid hardening properties.

The fluorinated polymer may be linear or branched. The number average molecular weight of the fluorinated polymer is 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene in GPC.

(C) The compounding ratio of the silicon compound having a Si-F bond is not particularly limited, but it is preferably 0.01 to 30 parts by mass, and 0.05 to 100 parts by mass of the organic polymer containing (A) a crosslinkable silicon group. ~ 20 parts by mass is better. When using a polymer compound having a number average molecular weight of 3,000 or more as the fluorinated polymer (C), 0.01 to 80 parts by mass relative to 100 parts by mass of the organic polymer containing (A) a crosslinkable silicon group Good, 0.01 to 30 parts by mass is more preferred, and 0.05 to 20 parts by mass is even better. When a low-molecular-weight compound having a fluorosilicon group whose number average molecular weight is less than 3,000 as the component (C) is used, 0.01 to 10 parts by mass relative to 100 parts by mass of the organic polymer containing (A) a crosslinkable silicon group. Good, more preferably 0.05 to 5 parts by mass.

(D) Photobase generators act as hardening catalysts for (A) crosslinkable silicon-based organic polymers when irradiated with light. (D) Photobase generators generate alkali through the action of active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. (1) Salts of organic acids and bases that are decarbonated and decomposed by irradiation with active energy rays such as ultraviolet / visible light / infrared rays, etc., (2) Decomposed and released by intramolecular nucleophilic substitution reaction or rearrangement reaction, etc. Conventional (D) photobase generators that emit amine compounds or (3) compounds that emit a predetermined chemical reaction by irradiation with active energy rays such as ultraviolet, visible light, and infrared rays. The alkali produced by the (D) photobase generator has a function of hardening the (A) component.

As for the alkali generated from the (D) photobase generator, for example, an organic base such as an amine compound is preferred. For example, primary alkylamines, primary aromatic amines, and the like described in WO2015-088021 can be used. Primary alkylamines, amines having secondary amine groups and tertiary amine groups, tertiary alkylamines, tertiary heterocyclic amines, tertiary aromatic amines, pyrene, phosphazene derivatives. Among them, an amine compound having a tertiary amine group is preferable, and a fluorene or a phosphazene derivative with a strong base is more preferable. Any of the non-cyclic amidines and cyclic amidines may be used for the amidines, and the amidines are more preferable. These bases may be used alone or in combination of two or more.

As for the acyclic hydrazones, for example, guanidine-based compounds and biguanide-based compounds described in WO2015-088021 can be cited. Among the acyclic fluorene compounds, for example, the aryl-substituted guanidine-based compound described in WO2015-088021 or a photobase generator that generates an aryl-substituted biguanide-based compound is used as a catalyst for the polymer (A). It is preferred because it shows a tendency to improve the surface hardening property, and a tendency to improve the adhesion of the obtained hardened material.

The cyclic amidines include, for example, the cyclic guanidine-based compound, imidazoline-based compound, imidazole-based compound, tetrahydropyrimidine-based compound, triazabicyclic olefin-based compound, and diazabicyclic compound described in WO2015-088021. Olefin compounds.

Among the cyclic amidines, from the viewpoint that they can be easily obtained industrially, the pKa value of the conjugate acid is 12 or more. Based on the viewpoint of exhibiting high catalyst activity, 1,8-diazabicyclo [ 5.4.0] Undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are particularly preferred.

(D) Various types of photobase generators can be used. A photo-lattice amine compound that generates an amine compound through the action of active energy rays is preferred. The photo-latent amine compound is a light-latent primary amine that generates an amine compound having a primary amine group through the action of active energy rays, and a light that generates a secondary amine compound having a secondary amine group through the action of active energy rays Either a latent secondary amine or a photo-latent tertiary amine that generates an amine compound having a tertiary amine group through the action of active energy rays. From the viewpoint that the generated alkali exhibits a high hardening catalyst, a photo-latency tertiary amine is more preferable.

Examples of the photo-latent primary amine and photo-latent secondary amine include the o-nitrobenzyl urethane-based compounds described in WO2015-088021; and dimethoxybenzyl urethane. Compounds; benzoic acid benzoin; o-fluorenyl oxime; o-carbamidine oxime; N-hydroxyfluorenimine carbamate; formamidine aniline derivative; aromatic sulfonamide; Cobaltamine complexes, etc.

Examples of the photo-latent tertiary amine include α-aminoketone derivatives, α-ammonone ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, and α described in WO2015-088021. -Amine olefin derivatives, α-ammonium olefin derivatives, imines, benzyloxycarbonylamine derivatives that generate fluorene by light, and salts of carboxylic acids and tertiary amines.

Examples of α-amino ketone derivatives include 5-naphthyridylmethyl-1,5-diazabicyclo [4.3.0] nonane, 5- (4'-nitro) Benzamidinemethyl-1,5-diazabicyclo [4.3.0] nonane and other 脒 -aminoketone derivatives such as nonane; yield 4- (methylthiobenzyl) -1- Methyl-1-N- Porphyrinethane (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone (Irgacure 369), 2- (4-methylbenzyl) -2-dimethylamino-1- (4- An α-amino ketone compound having a tertiary amine group and a tertiary amine group composed of one nitrogen atom, such as phosphonophenyl) -butanone (Irgacure 379).

Examples of the α-ammonone derivatives include 1-naphthylmethylmethyl- (1-azenium ion-4-azabicyclo [2,2,2] -octane) tetraphenylboronic acid. Salt, 5- (4'-nitro) benzamidinemethyl- (5-azanium ion-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate and the like.

Examples of benzylamine derivatives include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane, 5- (anthracene-9-yl-methyl) -1,5 -Benzylamine derivatives such as diazabicyclo [4.3.0] nonane, 5- (naphtho-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane, etc. .

Examples of the benzylammonium salt derivative include (9-anthrylmethyl) -1-azabicyclo [2.2.2] octanium tetraphenylborate, and 5- (9-anthrylmethyl) ) -1,5-diazabicyclo [4.3.0] -5-nonium tetraphenylborate and the like.

Examples of the α-amino olefin derivative include 5- (2 '-(2 "-naphthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane and the like.

Examples of α-ammonium olefin derivatives include 1- (2'-phenylallyl)-(1-azenium ion-4-azabicyclo [2,2,2] -octane) Tetraphenylborate, etc.

Examples of benzyloxycarbonylamine derivatives that generate fluorene through light include benzyloxycarbonylimidazoles, benzyloxycarbonylguanidines, diamine derivatives, and the like described in WO2015-088021.

Examples of the salt of a carboxylic acid and a tertiary amine include α-ketocarboxylic acid ammonium salts and carboxylic acid ammonium salts described in WO2015-088021.

(D) Among the photo-salt generators, from the viewpoint that the generated alkali exhibits a high catalytic activity, it is preferably a photo-latent tertiary amine, from the high efficiency of alkali generation and storage stability of the composition. For example, benzyl ammonium salt derivatives, benzyl substituted amine derivatives, α-amino ketone derivatives, and α-ammonone ketone derivatives are preferred. In particular, in terms of better base production efficiency, α-amino ketone derivatives and α-ammonone ketone derivatives are more preferred, and α-amino ketone is based on solubility in photocurable compositions. Derivatives are better. Among the α-amino ketone derivatives, from the viewpoint of the alkalinity of generating alkali, it is also preferable to generate α-amino ketone compounds of hydrazones. From the viewpoint of easy availability, examples include Α-amino ketone compounds of tertiary amines of tertiary amine groups composed of three nitrogen atoms.

These (D) light salt generating agents may be used alone or in combination of two or more kinds. (D) The blending ratio of the light salt generator is not particularly limited, but it is preferably 0.01 to 50 parts by mass and 0.1 to 40 parts by mass relative to 100 parts by mass of the organic polymer containing (A) a crosslinkable silicon group. More preferably, it is even better at 0.2 to 15 parts by mass. The blending ratio of (D) photo-salt generator and silicon compound (C) with Si-F bond used as hardening catalyst, (D): (C) is preferably 1: 0.008 ~ 1: 300 based on mass ratio. It is better to use 1: 0.016 ~ 1: 40.

The compound having a hydrolyzable silyl group having a number average molecular weight of less than 3,000 as the component (E) is not particularly limited. For example, a silanic compound having no functional group other than a hydrolyzable silyl group, an organic polysiloxane, and a silan Coupling agents, reactants and condensates of silane coupling agents have hydrolyzable silane compounds. Among them, a silane compound having no functional group other than a hydrolyzable silane group and a silane coupling agent are preferred. These can be used alone or in combination of two or more.

The hydrolyzable silicon group contained in the hydrolyzable silicon group-containing compound having a number average molecular weight of less than 3,000 as the component (E) is not particularly limited as long as it is other than an F atom. Examples include alkoxy, fluorenyloxy, ketoxime, amineoxy, and alkenyloxy. Among these, an alkoxy group is preferable from the viewpoint of stable hydrolyzability and easy handling. Among the alkoxy groups, those having a small carbon number are highly reactive. Such as the order of methoxy> ethoxy> propoxy, the reactivity decreases as the carbon number increases. Although it can be selected according to the purpose and application, methoxy and ethoxy are generally used.

Pressure-sensitive adhesives are mostly used with silicone release paper. However, in the present invention, the cured product of the photocurable composition containing the components (A), (B), (C), and (D) is used as the pressure-sensitive adhesive of the pressure-sensitive adhesive layer, and polysiloxane is used for peeling. In the case of paper, the properties of the pressure-sensitive adhesive, especially the adhesiveness, may be reduced after the paper is peeled off. However, when a photocurable composition containing the components (A), (B), (C), and (D) was further added, the compound having a hydrolyzable silicon group having a number average molecular weight of less than 3,000 (E) was found to peel off. After the paper is peeled off, the characteristics as a pressure-sensitive adhesive do not decrease.

Compounds with hydrolyzable silicon groups whose number-average molecular weight is less than 3,000. The number-average molecular weight in polystyrene conversion of GPC is preferably less than 3,000, more preferably less than 2,000, less than 1,000 and more preferably, and less than 700. Extraordinary.

Examples of the silane compound substituted with four hydrolyzable groups include tetrachlorosilane, tetraaminosilane, tetraethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane , Tetraphenoxysilane, tetrabenzyloxysilane, trimethoxysilane, triethoxysilane, etc.

Examples of the silane compound substituted with three hydrolyzable groups include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, and ethyl. Trimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silyl, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, and the like.

Examples of the silane compound substituted with two hydrolyzable groups include dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiethoxysilane, and dimethyldimethoxy Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, dibutyldimethoxysilane, etc. Further examples include silane compounds such as trimethylchlorosilane, hexamethyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane, and tributylethoxysilane.

Examples of the silane coupling agent include epoxy-containing compounds such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, and the like. Silanes; γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and other amine-containing silanes; N- (1,3 -Dimethylbutylene) -3- (triethoxysilyl) -1-propaneamine and other ketimine-type silanes; γ-mercaptopropyltrimethoxysilane and other mercapto-containing silanes; vinyl Vinyl unsaturated group-containing silanes such as trimethoxysilane, γ-methacryl methoxypropyltrimethoxysilane, and the like; chlorine-containing silanes such as γ-chloropropyltrimethoxysilane ; Isocyanate-containing silanes such as γ-isocyanatepropyltriethoxysilane, trimethoxysilylpropylisocyanate, etc .; tris (3-trimethoxysilylpropyl) trimeric isocyanate of these 3 polymers And other condensates; alkylsilanes such as decyltrimethoxysilane; phenyltrimethoxysilanes such as phenyltrimethoxysilane; but not limited to these.

Examples of the reactant and condensate of the silane coupling agent include silanes containing amine groups, epoxy-containing compounds containing the above-mentioned silanes, isocyanate-containing compounds, and (meth) acrylic acid-containing groups. The compound reacts with the modified amino group-containing silanes.

Examples of the organic polysiloxane include KR-517, KR-513, KR-511, KC-89S, and KR-213 manufactured by Shin-Etsu Chemical Industry Co., Ltd.

Amine-containing silanes act as silanol condensation catalysts, and ketimine-type silanes produce amine-containing silanes in the presence of moisture, which act as silanol condensation catalysts. Therefore, it is preferable to use a silane coupling agent other than an amine-containing silane or a ketimine-type silane. In addition, when using amine-containing silanes or ketimine-type silanes, it is necessary to pay attention to the type and the amount to be used within the scope of achieving the object / effect of the present invention.

As described above, amine-containing silanes or ketimine-type silanes are limited in use in the present invention. However, when it is necessary to use an amine-containing silane or a ketimine-type silane as an adhesiveness-imparting agent, a compound having an amine group is not generated before light irradiation, and an amine group-containing silane can be generated by light irradiation Compounds (hereinafter also referred to as compounds that produce photoaminosilanes). Examples of the compound that generates a photoamine silane include ortho-nitrobenzyl, p-nitrobenzyl, oxime residue, benzyl, benzamidine, or substituted as described in WO2015-088021. Compounds such as these. Examples of the photoamine silane-generating compound whose photofunctional group is o-nitrobenzyl include 2-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] amine Formate, 2-nitrobenzyl-N- [3- (triethoxysilyl) propyl] carbamate, 3,4-dimethoxy-2-nitrobenzyl-N -[3- (trimethoxysilyl) propyl] carbamate and the like. Examples of the photoamine silane-generating compound whose photofunctional group is o-nitrobenzyl include 4-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] amine Formate and so on. Examples of the photoamine-based silane-generating compound whose photofunctional group is benzyl include 1- (3,5-dimethoxyphenyl) -1-methylethyl-N- [3- ( Trimethoxysilyl) propyl] carbamate and the like. Examples of the photoamine silane-generating compound whose photofunctional group is an oxime residue include diphenyl ketone O-{[3- (trimethoxysilyl) propyl]} oxime and the like.

The compounding ratio of the hydrolyzable silicon-based compound having a number-average molecular weight of less than 3,000 is not particularly limited, but in the composition, it is preferably 0.01 to 20% by mass, and more preferably 0.025 to 10% by mass.

The photo-curable composition used in the pressure-sensitive adhesive of the present invention can be heated or even blended with a diluent to reduce the viscosity for coating if the workability during coating is considered. The viscosity of the photocurable composition at the time of coating is desirably 1 to 500 Pa. s, with 1 ~ 100Pa. s is better, especially 1 ~ 30Pa. The range of s is particularly preferable.

The photo-curable composition is applied while heating and adjusting to a desired viscosity range, and excellent coating workability can be obtained. The coating temperature is preferably 50 ° C or higher, more preferably 70 ° C or higher, and most preferably 75 to 120 ° C.

By blending the diluent, the physical properties such as the viscosity of the photocurable composition can be adjusted. As for the diluent, conventional diluents can be widely used without particular limitation. Examples of the diluent include saturated hydrocarbon solvents such as n-alkanes and iso-alkanes, and HS dimers (trade names of Fungoku Oil Co., Ltd.). Various solvents such as α-olefin derivatives, aromatic hydrocarbon solvents, alcohol solvents such as diacetone alcohol, ester solvents, citrate solvents such as triethylacetate, and ketone solvents.

The flash point of the diluent is not particularly limited, but when the safety of the composition is taken into consideration, the flash point of the composition should be high, and preferably the composition has less volatile matter. Therefore, the flash point of the diluent is preferably above 60 ° C, and more preferably above 70 ° C. When two or more diluents are mixed, the flash point of the mixed diluent is preferably 70 ° C or higher. In addition, in general, a diluent having a high flash point tends to reduce the dilution effect of the composition. Therefore, the flash point is preferably 250 ° C or lower.

When considering both the safety and dilution effect of the composition, the diluent is preferably a saturated hydrocarbon-based solvent, more preferably n-alkane and iso-alkane, and the carbon number of n-alkane and iso-alkane is preferably 10-16.

The blending ratio of the diluent is not particularly limited. From the viewpoint of improving the balance between coating workability and physical properties reduction by mixing, it is better to blend 0 to 25% in the composition, and it is better to blend 0.1 to 15%. It is better to mix 1 ~ 7%. These diluents can be used alone or in combination of two or more.

In the photocurable composition used in the pressure-sensitive adhesive, a photosensitizer, a filler, a plasticizer, a moisture absorbent, a condensation reaction other than the component (C) and the component (D) may be added as needed Compounds with functional groups that are radically polymerizable, physical property modifiers that improve tensile properties, strengthening agents, colorants, flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet absorbers, solvents, perfumes, Various additives such as pigments, dyes, conductive powders, thermally conductive powders, phosphors, and waxes.

As for the filler, a resin filler (resin fine powder) or an inorganic filler can be used. As for the resin filler, a granular filler made of an organic resin or the like can be used. For example, the resin filler can be polyethylene acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, urea resin, melamine resin, benzoguanamine resin, phenol resin, acrylic resin, styrene resin, etc. Organic particles.

The resin filler is preferably one that can easily obtain a spherical filler by suspension polymerization of a monomer (for example, methyl methacrylate) or the like. In addition, since a filler containing a resin filler is appropriately contained in the composition, a spherical crosslinked resin filler is preferred. In addition, when the pressure-sensitive adhesive is used in applications requiring light-shielding properties, such as a peripheral portion of a liquid crystal display device, the resin filler is preferably a resin filler containing black. By using a black resin filler having an average particle diameter of 1 to 150 µm, even if a single-wavelength LED lamp is used, good hardening properties can be obtained, and excellent light-shielding properties and hardening properties can be achieved.

Examples of the inorganic filler include talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrated silicon, calcium silicate, titanium dioxide, and carbon black. These can be used alone or in combination of two or more.

Examples of plasticizers include phosphate esters such as tributyl phosphate and tricresyl phosphate; phthalate esters such as dioctyl phthalate; fatty acid monoesters such as glycerol monooleate; Aliphatic dibasic acid esters such as dioctyl diacid, polypropylene glycols and the like. These can be used alone or in combination of two or more.

As the moisture absorbent, the above-mentioned silane coupling agent and silicate are suitable. The silicate is not particularly limited, and examples thereof include tetramethoxysilane, tetraalkoxysilane, and the like and partial hydrolyzed condensates thereof.

As for the condensation reaction promotion catalyst other than the (C) component and the (D) component, conventional condensation reaction promotion catalysts can be widely used without particular limitation, and examples thereof include organometallic compounds, acids, and amines. The base. Examples of organometallic compounds include organic tin compounds; dialkyltin oxides; reactants of dibutyltin oxide and phthalates; phthalates; organic aluminum compounds; titanium tetraacetamidine acetone And other chelating compounds; organic acid bismuth, boron trifluoride, boron trifluoride complexes, fluorinating agents, and alkali metal salts of polyvalent fluorine compounds. As for the silanol condensation catalyst, various other acidic catalysts and alkaline catalysts can be cited. Examples of the silanol condensation catalyst system include conventional acid catalysts and alkaline catalysts. However, depending on the amount of the organic tin compound added, the toxicity of the resulting composition may become strong. The (C) component and (D) component of the composition used in the present invention act as a condensation reaction promotion catalyst. Therefore, when using hardening catalysts other than these, the purpose of the invention and Users within the range of effects are better.

Examples of the compound having a radically polymerizable functional group include organic compounds having at least one group selected from the group consisting of radically polymerizable vinyl, vinylidene, and vinylidene. In particular, it is preferable to use an organic compound having a vinyl group. Furthermore, the radically polymerizable functional group may be at least one group selected from the group consisting of an acrylfluorenyl group and a methacrylfluorenyl group. As the organic compound, for example, a compound having a (meth) acrylfluorenyl group and an N-vinyl compound directly bonded to a vinyl group on a nitrogen atom can be used. When a compound having a radical polymerizable functional group is added, the peel strength can be increased immediately after light irradiation.

When a compound having a radical polymerizable functional group is used, a photo radical initiator may be used in combination. Examples of the photo radical initiator include arylalkyl groups such as benzoin ether derivatives, benzyl ketal derivatives, α-hydroxyacetophenone derivatives, and α-aminoacetophenone derivatives. Ketones, fluorenylphosphine oxides, titanocene, oxime ketones, thiobenzoic acid S-phenyl esters, and these polymerized derivatives.

The manufacturing method of the photocurable composition used in the present invention is not particularly limited, for example, by formulating a predetermined amount of the components (A), (B), (C), (D), and (E), and as required It can be manufactured by blending other blending substances and degassing. The preparation sequence of each component and other preparation materials is not particularly limited, and can be appropriately determined. The photocurable composition can be made into a one-liquid type as required, and can also be made into a two-liquid type, and especially a one-liquid type is suitable.

The pressure-sensitive adhesive of the present invention is formed by laminating a pressure-sensitive adhesive layer made of a cured product of a photocurable composition and a silicone release paper. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive without a base material formed of only a hardened material of the photocurable composition, or may be an attachment of a hardened material layer having a photocurable composition formed on at least one side of the base material. Substrate pressure sensitive adhesive. In addition, the pressure-sensitive adhesive may be a single-separated type in which one side of the release paper has a light release layer and the other side has a heavy release layer. It may also be a double-separated type in which two release papers each having a release treatment on at least one side of the release paper are laminated. When the pressure-sensitive adhesive of the present invention is used as a double-separator type, it is preferable that the release paper has a light release layer on one side of the pressure-sensitive adhesive layer and a heavy release layer on the other side. The pressure-sensitive adhesive can be formed in the form of a roll, or it can be formed in the form of a laminated sheet.

As the release paper, for example, a release paper in which a release treatment layer is formed on at least one side of a release paper substrate can be suitably used. Examples of such a base material for release paper include polyester films (such as polyethylene terephthalate films), olefin resin films, polyvinyl chloride films, polyimide films, polyimide films, and spiron Films, such as plastic-based substrate films, and paper (high-quality paper, Japanese paper, kraft paper, synthetic paper, top-coated paper, etc.). In addition, a plurality of layers (such as a complex of 2 to 3 layers) and the like such as a laminated layer are mentioned.

As the release treatment agent constituting the release treatment layer, a polysiloxane-based release treatment agent, a fluorine-based release treatment agent, a long-chain alkyl-based release treatment agent, and the like are known. In the present invention, from the viewpoint of releasability, a silicone release paper treated with a silicone release treatment agent is used.

The release paper used in the double-separated type is based on suppression of separation (when trying to release the release paper, the pressure sensitive adhesive part is peeled off along with the release paper on one side, and the other parts of the pressure sensitive adhesive layer are peeled off along with the release paper on the other side From the viewpoint of peeling), it is preferable to use two release papers having one side as a heavy release layer and the other side as a light release layer. The light release layer is capable of self-adhesive pressure-sensitive adhesive layer peeling with a peel force smaller than that of the heavy release layer. In addition, in this specification, "heavy peeling layer" and "light peeling layer" do not indicate the magnitude of peeling strength, but among two kinds of peeling layers, the one having a larger peeling force to the pressure-sensitive adhesive layer is called a heavy peeling layer or peeling. Those with less force are called light peeling layers. In addition, the difference between the peeling force of the heavy release layer to the pressure-sensitive adhesive layer and the peeling force of the light release layer to the pressure-sensitive adhesive layer is not particularly limited, but from the viewpoint of being more difficult to separate, the peeling is relative to the light-peeling layer The peeling force of the heavy peeling layer is preferably 1.5 times or more, and more preferably 2.0 times or more. In addition, in the single-separator type, a release paper having a peeling treatment on both sides is preferred. From the standpoint of suppressing separation, it is preferable to use one side as a light release layer and the other side as a heavy release layer.

Regarding the substrate used in the pressure-sensitive adhesive with a substrate, as a substrate for an adhesive tape or a sheet, a conventional substrate can be appropriately selected and used. There is no particular limitation on the substrate. For example, plastic substrates such as polyethylene terephthalate, metal substrates such as aluminum foil, porous substrates such as non-woven fabrics, and paper substrates such as high-quality paper can be used. , Foamed substrates, etc. Among them, a plastic base material is preferred from the viewpoint of workability. The plastic base material is capable of suppressing deformability such as elongation by stretching.

The surface of the substrate used in the pressure-sensitive adhesive with a substrate can be subjected to common surface treatments such as corona treatment, chromic acid treatment, ozone exposure, etc. in order to improve the adhesion with the pressure-sensitive adhesive layer. Oxidation treatment by chemical or physical methods such as flame exposure, high voltage electric shock exposure, ionizing radiation treatment, etc. In addition, a coating treatment such as a primer may be performed.

The thickness of the substrate used in the pressure-sensitive adhesive with a substrate is not particularly limited, and may be appropriately selected according to the strength, flexibility, purpose of use, and the like, for example, 10 to 1000 μm, and preferably about 10 to 50 μm. In addition, the substrate may have a single layer or any of a plurality of layers.

The pressure-sensitive adhesive with a substrate is coated with a photocurable composition on at least one side of a substrate such as a PET film, and can be produced by laminating a release paper after irradiating light such as ultraviolet rays. Further, the photocurable composition may be coated on a transfer substrate and irradiated with light such as ultraviolet rays, and then transferred to the substrate to produce it.

The pressure-sensitive adhesive layer used in the present invention is produced by applying a photocurable composition on a release paper or a substrate and then irradiating light such as ultraviolet rays. In addition, the photocurable composition can be produced by applying the photocurable composition to a transfer substrate and irradiating light such as ultraviolet rays, and then transferring it to a release paper.

The coating thickness of the photocurable composition can be appropriately selected, and is generally 1 to 500 μm, preferably about 5 to 250 μm, and particularly preferably about 10 to 200 μm.

The photocurable composition is applied on at least one side of the release paper or the substrate with a roll coater, a die coater, a bar coater, a comma coater, a gravure coater, a Meyer bar coater, or the like.

After the photocurable composition is coated on the surface of a release paper or a substrate in this manner, the coated photocurable composition is irradiated with light such as ultraviolet rays, so that the photocurable composition coated on the release paper or the substrate is applied. The hardening component is crosslinked and hardened. At this time, the irradiation time of light such as ultraviolet rays is generally 1 second to 300 seconds, and preferably 1 second to 180 seconds.

The light in the present invention refers to active energy rays including electron beams, proton beams, neutron beams, and the like in addition to electromagnetic waves such as ultraviolet rays, visible light, infrared rays, and X-rays and γ-rays.

From the viewpoints of curing speed, availability of irradiation equipment, price, and ease of operation under sunlight and general lighting, those cured by ultraviolet or electron beam irradiation are preferred, and those cured by ultraviolet irradiation Better. In addition, ultraviolet rays include g rays (wavelength 436 nm), h rays (wavelength 405 nm), i rays (wavelength 365 nm), and the like. There is no particular limitation on the active energy ray source, but according to the nature of the photo-alkali generator used, for example: high-pressure mercury lamp, low-pressure mercury lamp, electron beam irradiation device, halogen lamp, light-emitting diode, semiconductor laser, metal halide Things.

The irradiation energy can be selected according to the amount of accumulated light and the irradiation time of the light. In order to shorten the irradiation time of light as much as possible, such as in the case of ultraviolet rays, the illumination is preferably 10 mW / cm ² or more, more preferably 50 mW / cm ² or more, 100 mW / cm ² or more, and 1,000 mW / cm Above ² is particularly good.

The upper limit of the irradiation energy is not particularly limited. Even if it is unnecessary to irradiate light, time and cost are wasted, and the substrate is damaged. Therefore, the irradiation intensity is preferably 20,000 mW / cm ² or less, and 10,000 mW / cm ² or less more preferably, ² or less and more preferably 8,000mW / cm, at 5,000mW / cm ² or less and still more preferably, at 3,000mW / cm ² or less is particularly preferred.

When the light is irradiated as described above, the crosslinking reaction is rapidly performed by the light. Furthermore, the pressure-sensitive adhesive produced in this way is wound through a release paper or the like. The width of the pressure-sensitive adhesive is not particularly limited. Although the tape-shaped pressure-sensitive adhesive has been mainly described above, a sheet-shaped pressure-sensitive adhesive sheet can also be produced in the same manner. Furthermore, the pressure-sensitive adhesive used in the present invention can also be used as a double-sided pressure-sensitive adhesive such as a double-sided tape or a double-sided sheet.

The pressure-sensitive adhesive is generally tape-shaped or sheet-shaped. However, it is also possible to directly exist on the adherend to be bonded without using an adhesive tape or a sheet. For example, after coating a photocurable composition on a first adherend such as a plastic molded product, the active energy ray may be irradiated, and another plastic molded product may be held at a position where the pressure-sensitive adhesive layer generated by curing is held. The second adherend is bonded to the first adherend. After irradiating active energy rays, the photocurable composition does not completely harden immediately, and is in an uncured state in a short time. During this time, when the second adherend is bonded to the first adherend, the pressure-sensitive adhesive easily penetrates into the adherend, and a more sufficient joint can be obtained. Further, the first adherend can be coated with a photocurable composition, and after irradiating active energy rays, the paper can be laminated. In this case, a disperser, a spray gun with a heating supply device such as a hot-melt gun for coating the adherend, a drum melter, and a dispenser equipped with a heating unit can be used.

The pressure-sensitive adhesive of the present invention can be used in electrical / electronic circuits, electronic parts, building materials and / or automobiles, transporters, civil engineering / construction, medical or leisure applications, office supplies for labels, image display devices, etc. Fitting and so on. In addition, civil engineering / building applications include pressure-sensitive adhesive sheets, waterproof sheets, and shock-proof sheets.

    [Example]    

In the following, the present invention is enumerated to illustrate the present invention more specifically, but these embodiments are only examples and should not be interpreted restrictively.

Unless otherwise stated, the number average molecular weight is determined by a gel permeation chromatography (GPC) under the following conditions. In the description of the examples, the maximum frequency molecular weight measured by GPC under the following measurement conditions and converted by standard polystyrene is referred to as "number average molecular weight".

‧Analyzers: Alliance (manufactured by Waters), 2410 differential refractometer (manufactured by Waters), 996 multi-wavelength detector (manufactured by Waters), Milleniam data processing device (manufactured by Waters)

‧Column: Plgel GUARD + 5μm mixed C × 3 (50 × 7.5mm, 300 × 7.5mm: manufactured by Polymer Lab)

‧Flow rate: 1mL / min

‧Converted polymer: polystyrene

‧Measuring temperature: 40 ℃

‧Solvent for GPC measurement: THF

    (Synthesis Example 1) Synthesis of polyoxyalkylene-based polymer A1 having a trimethoxysilyl group at the end    

Using ethylene glycol as a starting agent, propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-diglyme complex catalyst to obtain polyoxypropylene glycol. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the end of the obtained polyoxypropylene glycol was obtained. To this polymer, a solution of trimethoxysilane and platinum vinylsiloxane complex isopropanol as a hydrogenated silicon compound was added and reacted to obtain a polyoxyalkylene-based polymerization having a trimethoxysilyl group at the terminal.物 A1.

The molecular weight of the obtained polyoxyalkylene-based polymer A1 having a trimethoxysilyl group at the end was measured by GPC. The peak top molecular weight was 25,000, and the molecular weight distribution was 1.3. The number of trimethoxysilyl groups at the end measured by 1H-NMR was 1.7 per molecule.

    (Synthesis Example 2) Synthesis of polyoxyalkylene-based polymer A2 having a dimethoxysilyl group at the end    

Using ethylene glycol as a starting agent, propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-diglyme complex catalyst to obtain polyoxypropylene glycol. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the end of the obtained polyoxypropylene glycol was obtained. To this polymer, a solution of methyldimethoxysilane and platinum vinylsiloxane complex isopropanol as a hydrogenated silicon compound was added and reacted to obtain a polymer having a methyldimethoxysilyl terminal. Oxyalkylene polymer A2.

The molecular weight of the obtained polyoxyalkylene-based polymer A2 having a dimethoxysilyl group at the end was measured by GPC. The peak top molecular weight was 5,000, and the molecular weight distribution was 1.3. The number of dimethoxysilyl groups at the ends measured by 1H-NMR was 1.0 per molecule.

    (Synthesis example 3) Synthesis of fluorinated polymer C1    

Polyoxypropylene glycol having a molecular weight of about 2,000 was used as a starter, and propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-diglyme complex catalyst to obtain polyoxypropylene glycol. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the end of the obtained polyoxypropylene glycol was obtained. To this polymer, a solution of methyldimethoxysilane and platinum vinylsiloxane complex isopropanol as a hydrogenated silicon compound was added and reacted to obtain a polyoxysilane having a methyldimethoxysilyl terminal. Alkyl polymer A3.

The molecular weight of the obtained polyoxyalkylene-based polymer A3 having a methyldimethoxysilyl group at the terminal was measured by GPC. The peak top molecular weight was 15,000, and the molecular weight distribution was 1.3. The number of methyldimethoxysilyl groups at the end measured by 1H-NMR was 1.7 per molecule.

Next, using 2.4 g of BF ₃ ether complex, 1.6 g of dehydrated methanol, 100 g of polymer A3, and 5 g of toluene, according to the method of Synthesis Example 4 of WO2015-088021, polyoxyalkylene-based polymerization having a fluorosilyl group at the end was obtained (Hereinafter referred to as fluorinated polymer C1). When the 1H-NMR spectrum of the obtained fluorinated polymer C1 was measured, the peak (m, 0.63 ppm) corresponding to the silane methylene (-CH ₂ -Si) of the polymer as a raw material disappeared, and the low magnetic field side (0.7 ppm ~) Broad peaks appear.

    (Examples 1 to 8, Comparative Examples 1 to 9)    

As shown in Table 1, in a flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a water-cooled condenser, put (A) an organic polymer with a crosslinkable silicon group and an average molecular weight of 3,000 or more ( B) Tackifying resin, stirred at 120 ° C under reduced pressure to dissolve the tackifying resin. Then, (C) a silicon compound having a Si-F bond, (D) a photobase generator, and (E) a compound having a hydrolyzable silicon group having a number-average molecular weight of less than 3,000, and stirred under reduced pressure to obtain Example 1 Photocurable composition. The characteristics of the obtained composition were evaluated by the following methods. The evaluation results are shown in Table 1. Moreover, among the samples for evaluating the hardenability after light irradiation, those who hardened by light irradiation have adhesiveness that can be used as a pressure-sensitive adhesive layer. Furthermore, the same operation as in Example 1 was performed to prepare the photocurable compositions of Examples 2 to 8, and the characteristics of the composition were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. In addition, for Comparative Examples 1 to 9, the photocurable composition was prepared in the same manner as in Example 1 except that the formulation shown in Table 2 was changed, and the characteristics were evaluated. The results are shown in Table 2.

In Tables 1 and 2, the blending amount of each blending substance is expressed in g, and details of other blending substances are as follows. It should be noted that the softening point is a value according to JIS K 2207 (ring and ball method).

* 1 SP value 8.81, softening point 130 ° C, trade name "YS Polystar T130", manufactured by Anhara Chemical Co., Ltd.

* 2 SP value 9.32, softening point 125 ° C, trade name "YS Polystar K125", manufactured by Anhara Chemical Co., Ltd.

* 3Styrenic monomer / aliphatic monomer copolymer resin, softening point: 95 ° C, trade name "FTR-6100", manufactured by Mitsui Chemicals

* 4 50% PC (propylene carbonate) solution with the trade name "IRGACURE 379EG", manufactured by BASF

* 5 Trade name "KBM-403", manufactured by Shin-Etsu Chemical Industry Co., Ltd.

* 6 Trade name "KBM-3103C", manufactured by Shin-Etsu Chemical Industry Co., Ltd.

* 7 Trade name "KBM-503", manufactured by Shin-Etsu Chemical Industry Co., Ltd.

* 8 Trade name "KBM-3066", manufactured by Shin-Etsu Chemical Industry Co., Ltd.

* 9 Trade name "Ethyl Silicate 28", manufactured by Colcoat Co., Ltd.

* 10 10% PC (propylene carbonate) solution of boron trifluoride monoethylamine

* 11 Trade name "DBU", manufactured by San Apro Co., Ltd.

* 12 Trade name "AlumiChelate D", manufactured by Kawaken Fine Chemical Co., Ltd.

* 13 Trade name "Neostan U-100", manufactured by Nitto Chemical Industry Co., Ltd.

    1) Moisture stability (wet stability test without UV irradiation)    

Into a cylindrical container with a diameter of 100mm and a height of 1mm, inject the photohardenable composition so that the thickness is 1mm. In a dark room, at 23 ° C and 50% RH, touch the light every 5 minutes to confirm the light. The state of the hardening composition. After 8 hours or more, after the finger touches, there is an attachment remaining on the finger (that is, a case where the photocurable composition is liquid), and after 4 hours or more and less than 8 hours, there is no attachment remaining on the finger It is △ and less than 4 hours, and when there is no attached matter on the finger, it is × (that is, when the photocurable composition is gel-like or solid).

    2) Surface hardening test    

A polysilicone release paper was coated with a photocurable composition so that the thickness became 200 μm, and then UV-irradiated [irradiation conditions: UV-LED 365 nm, illumination: 1000 mW / cm ² , cumulative light amount: 3000 mJ / cm ² ] , Immediately in a dark room, 23 ° C, 50% RH, touch the surface with a finger every minute and measure the time until the surface hardens. In addition to the components (C) and (D), the samples of Comparative Examples 3 to 7 in which other silanol condensation reaction-promoting catalysts were prepared. After coating, the samples were applied in a dark room at 23 ° C and 50% RH per minute. Touch the finger and measure the time until the surface hardens. If the surface hardening time is less than 1 hour, it is rated as "○", and if it is more than 1 hour, it is rated as "X". In addition, the samples of Comparative Examples 8 and 9 were not hardened.

    3) Suitability test on silicone release paper    

On the PET film, a photocurable composition was applied so that the thickness became 200 μm, and immediately after irradiation with UV [irradiation conditions: UV-LED365nm, illuminance: 1000mW / cm ² , cumulative light amount: 3000mJ / cm ² ], Silicone release paper (manufactured by OjiF-Tex Corporation; N-64-GPS) is bonded. Then, it aged at 50 degreeC for 24 hours. In addition, a sample was prepared for 24 hours at 50 ° C without sticking to the release paper. After the curing, the release paper was peeled off by hand, and the tackiness of the pressure-sensitive adhesive layer was evaluated by finger touch. Compared with the pressure-sensitive adhesive layer not bonded to the release paper, the non-reduced tackiness was ◎, the reduced tackiness was ○, and it was difficult to peel off the release paper by hand or the tackiness almost disappeared was ×.

    4) Separation test on silicone release paper    

The pressure-sensitive adhesive of Example 1 was coated with a photocurable composition on a polysiloxane heavy-duty paper (manufactured by Oji F-Tex Co., Ltd .; N-80-GS) so that the thickness became 200 μm. After irradiating UV [irradiation conditions: UV-LED365nm, illumination: 1000mW / cm ² , cumulative light amount: 3000mJ / cm ² ], immediately with a silicone light release paper (manufactured by Oji F-Tex Corporation; N-64- GPS) fit. Then, it aged at 50 degreeC for 24 hours. After curing, the silicone light release paper is peeled off by hand. Those who are easy to separate are ○ and those who are not easy to separate are ×.

As shown in Table 1, any of the pressure-sensitive adhesives in the examples had good releasability from the silicone release paper, and the hardening composition used was hardened due to moisture in the air, that is, In addition to being excellent in stability at the time of coating, it is easy to manufacture because it undergoes a rapid crosslinking reaction through the irradiation of light. In addition, among the samples for evaluating the hardenability after light irradiation, the sample hardened by light irradiation has adhesiveness that can be used as a pressure-sensitive adhesive layer.

The embodiments and examples of the present invention have been described above, but the above-mentioned embodiments and examples do not limit the scope of the invention for which the patent is applied. Furthermore, it should be noted that all of the feature combinations described in the implementation modes and the embodiments are not limited to the means for solving the problems of the present invention.

Claims (6)

    A pressure-sensitive adhesive, which is formed by laminating a pressure-sensitive adhesive layer and a silicone release paper, and has light containing the following (A), (B), (C), (D), and (E) Hardened product of hardening composition: (A) organic polymer having crosslinkable silicon group in number average molecular weight of 3,000 or more, (B) tackifying resin, (C) silicon compound having Si-F bond, (D) Photobase generator, (E) A compound having a hydrolyzable silicon group having a number average molecular weight of less than 3,000.         The pressure-sensitive adhesive according to claim 1, wherein the (A) organic polymer having a cross-linkable silicon group having a number average molecular weight of 3,000 or more is a polyoxyalkylene-based polymer having a cross-linkable silicon group.         The pressure-sensitive adhesive according to claim 1 or 2, wherein the (B) tackifying resin-based terpene phenol resin and / or aromatic petroleum resin.         The pressure-sensitive adhesive according to any one of claims 1 to 3, wherein (C) the silicon compound having a Si-F bond is an organic polymer having a Si-F bond.         The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the silicone release paper is a silicone release paper having a light release layer on one side and a heavy release layer on the other side.         The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein a silicone release paper having a light release layer is provided on one area of the pressure-sensitive adhesive layer, and a silicone release having a heavy release layer is provided on the other area. Made of paper.