JPH07292338A - Curing adhesive and sheet or tape - Google Patents

Abstract

PURPOSE:To obtain a curing adhesive exhibiting tacky adhesivity during the application, capable of tentatively binding on an objective body and producing strong adhesive force through curing by heating or only by sticking together and to obtain a sheet or a tape coated with the adhesive. CONSTITUTION:This curing adhesive is obtained by compounding (A) 100 pts.wt. of an adhesive rubber resin, (B) 30-150 pts.wt. of a compound having an oxygen absorbability and a peroxide-generating power at the same time, (C) a monomer or oligomer containing an ethylenic unsaturated group, (D) 0.1-15 pts.wt. of an organic peroxide and (E) 0.05-3 pts.wt. of an epoxy compound wherein the monomer or oligomer C containing an ethylenic unsaturated group is compounded in such a manner that the ethylenic unsaturated group of the compound C becomes 2-140-mol based on 1mol, of the active oxygen in the compound B. This invention also provides a curing adhesive sheet or tape obtained by laying or impregnating the curing adhesive on a non-gas permeable base material or a porous material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable pressure-sensitive adhesive which has tackiness at the time of bonding and can be temporarily adhered to an adherend, and which shows a strong adhesive force by being cured only by heating or laminating it. Coated sheet or tape (hereinafter referred to as sheet)
Regarding Among the fields in which adhesive tapes are currently used, high curability adhesive sheets are suitable for applications where high adhesive reliability is required and adhesive tapes are used with concern about reliability. On the other hand, in the field where a conventional adhesive is used, it is suitable as a substitute for an application in which convenience is obtained by being processed into a sheet and an application in which there is a concern that the working environment is deteriorated due to the use of the adhesive.

[0002]

2. Description of the Related Art A curable pressure-sensitive adhesive sheet that is tacky at the time of joining, can be easily temporarily adhered to an adherend, and hardens only by heating or pasting to provide a strong adhesive force is a typical one. As a moisture-curable type that is cured by moisture in the air or moisture of the adherend (Japanese Patent Publication No. 47440/1972, Japanese Patent Publication No.
5895, JP-A-54-64536, JP-A-58-171460, and JP-A-59-58071.
JP-A-61-145268, JP-A-61-145268
No. 148281) and an anaerobic curing type that cures by blocking air (Japanese Patent Publication No. 58-12918, Japanese Patent Publication No. 59-199784, and Japanese Patent Publication No. 59-1).
99785, JP-A-60-6773, JP-A-60-11568, and JP-A-60-13868) are known.

However, each curable pressure sensitive adhesive sheet has a serious problem. That is, the moisture curing type needs to be stored in a dry state until it is used, and requires special equipment for manufacturing. The anaerobic curable type requires a storage state in which it is always in contact with air, and it is difficult to balance the storage stability and the curability such that if the curability is improved, the storage stability becomes poor. It is very difficult to develop such a function with an ordinary curable adhesive sheet,
Even if it was possible, the pot life at the time of coating, the storage stability and curability of the coated sheet, and the balance between the adhesive property and the adhesive property could not be achieved.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a pressure-sensitive adhesive sheet which cures only when heated or laminated, and has a pot life during coating, storage stability when cured as a sheet and curing. The purpose is to make a curable pressure-sensitive adhesive sheet that is excellent in both properties. Furthermore, after sticking the adhesive surface of the curable adhesive sheet to one of the two adherends and performing processing such as punching with the release liner attached,
Assuming an adhesive method in which the release liner is peeled off and bonded to another adherend, it is intended to have the capability of heating after bonding or bonding and gradually advancing curing to bond. Among moisture-curing and anaerobic curing, the moisture-curing pressure-sensitive adhesive sheet not only needs to be manufactured by blocking moisture, but also needs to be sealed and stored, and curing starts immediately after opening. For this reason, it is difficult to open the pressure-sensitive adhesive sheet and leave the release liner attached, which is not suitable for solving this problem. On the other hand, heat and anaerobic curable pressure sensitive adhesive sheets do not have such a fatal problem, and it was widely accepted that it is the only curing method that can solve the above-mentioned problems, but the preservability and bonding before use There were many problems in achieving both curability afterwards. But,
The storage stability and curability when processed into a sheet have an antinomy relationship even with this heat and anaerobic curable pressure sensitive adhesive sheet, and if the curability is to be improved, the storage stability will be poor and the storage stability will be improved. If so, it is difficult to obtain a product having a level of performance that can be practically used, such as poor curability.

[0005]

Means for Solving the Problems The present invention has an adhesive rubber-based resin (A), which has both oxygen absorption ability and peroxide generation ability,
Compound (B) having an oxygen absorption amount of 0.1 to 3% (weight of absorbed oxygen / weight) and an amount of active oxygen of 0.01 to 1% (weight of active oxygen / weight), a monomer having an ethylenically unsaturated group Alternatively, it comprises an oligomer (C), an organic peroxide (D) and an epoxy compound (E), and is an adhesive rubber resin (A).
Based on 100 parts by weight, the compound (B) is 30 to 15
0 parts by weight, 0.1 to 15 parts by weight of the organic peroxide (D),
The epoxy compound (E) is 0.05 to 3 parts by weight, and the monomer or oligomer (C) having an ethylenically unsaturated group is relative to 1 mol of active oxygen of the compound (B).
It relates to a curable pressure-sensitive adhesive characterized in that the ethylenically unsaturated group of the monomer or oligomer (C) having an ethylenically unsaturated group is mixed in an amount of 2 to 140 mol.

Further, the present invention relates to a curable pressure-sensitive adhesive obtained by adding 0.001 to 1 part by weight of a polymerization inhibitor (F) to 100 parts by weight of the above-mentioned curable pressure-sensitive adhesive. Further, the present invention relates to a curable pressure-sensitive adhesive sheet or tape, which is obtained by laminating or impregnating the above-mentioned curable pressure-sensitive adhesive on a non-air-permeable substrate or a porous substrate.

The curable pressure-sensitive adhesive sheet of the present invention is one which, after adhering adherends to each other, heats or adheres them to each other and leaves them at room temperature to cure the resin to develop a strong adhesive force. In terms of adhesion due to curing, the curable pressure-sensitive adhesive sheet is almost the same as the conventional curable pressure-sensitive adhesive sheet. However, the curing mode at room temperature of the present invention is composed of two types of conventional anaerobic curing and a novel curing mechanism different from the conventional one. The anaerobic curable composition is composed of a polymerizable monomer (or an oligomer) and a polymerization initiator such as an organic peroxide as is known, and is cured by blocking oxygen. On the other hand, the novel curing mechanism of the present invention is
This is unique when a compound having a conjugated double bond, a tertiary carbon position or an allyl position is used as one of the compositions, and a chemical structure easily oxidizable such as a conjugated double bond, a tertiary carbon position or an allyl position is formed. It was used.

Although there are many reactions related to the conjugated double bond, the important reactions involved in the novel curing mechanism of the present invention are an oxidation reaction for absorbing oxygen in the air and a Diels-Alder reaction. In particular, a conjugated double bond, a third carbon position,
Autoxidation of the and allylic moieties gradually produces organic peroxides and accumulates active oxygen in the system. A radical is generated by the decomposition of the organic peroxide, and this radical initiates a crosslinking reaction of the resin and a reaction of an unsaturated bond to cause the curing of the resin. However, the rate of autoxidation is very high, even for a compound having a conjugated double bond, a tertiary carbon position, and an allylic position, because it is a solid-phase reaction in the processed pressure-sensitive adhesive sheet at room temperature. It is loose. This is the absorption and oxidation of oxygen,
It can be said that the reaction is a very slow and gentle reaction from the formation and decomposition of organic peroxide to the curing of resin by radicals. On the other hand, the radicals generated by the decomposition of the organic peroxide generated in the process of the autoxidation reaction that absorbs the ambient oxygen, contributes effectively to the curing reaction without being consumed by the ambient oxygen. However, during storage as a sheet without pasting the adherend, the radicals generated from the generated organic peroxide do not reach an amount enough to cause curing,
Radicals are consumed by a small amount of air contained in the adhesive layer or the release liner, and the curing reaction does not occur. Only after the adherends are adhered to each other, the supply of oxygen is interrupted and the peripheral oxygen is completely consumed by the oxidation, and radical contribution to the unsaturated resin becomes vigorous, causing a curing reaction. Therefore,
Until the adherends are bonded together, the production and decomposition of organic peroxides are constantly repeated at a very slow rate. However, since the compound (B) is present in a large amount, it is not completely oxidized during storage and the curability is maintained.

The peroxide (D) also decomposes only at a very slow rate at room temperature and does not cure if oxygen is sufficiently in the surroundings. However, in the present invention, the compound (B) acts to absorb the surrounding oxygen. And cause curing. Therefore, the curing of the present invention is due to the action of both the organic peroxide generated by the oxygen absorption of the compound (B) and the peroxide (D) added in advance. In order to make the storage stability and the curability of the sheet compatible with each other, the oxygen absorption ability and the organic peroxide generation ability of the compound (B) must be at appropriate levels. If the oxygen absorption capacity and the organic peroxide generation capacity are too large, the organic peroxide is excessively generated during storage as a sheet, and the sheet cannot be followed by the radical consumption by ambient oxygen and is cured. If it is too small, it hardly cures or the curing time is too long to be practically usable. It is presumed that most of the organic peroxides produced from the conjugated double bond or the tertiary carbon position or the allyl position are hydroperoxides, and the level of oxygen absorption ability and peroxide generation ability of the compound (B) is appropriate. Need to be In addition to the reaction by the peroxide, the Diels-Alder reaction becomes vigorous between the conjugated double bond portion and the ethylenically unsaturated group, and the effect of increasing the molecular weight also contributes to curing.

The above curing reaction is different from the conventional simple anaerobic curing reaction, and both the storage stability and the curability, which have hitherto been difficult to achieve, can be secured by the curable pressure-sensitive adhesive sheet of the present invention. . Conventionally known anaerobic curable compositions are polyethylene glycol (meth) acrylates, epoxy acrylates, and the like (as described in JP-B-61-45674 and JP-B-2-5791). (Meth) acryloyl group-containing polymerizable monomer or oligomer, benzoyl peroxide, cumene hydroperoxide and other organic peroxides,
If necessary, ingredients such as accelerators and stabilizers are added. Even with this composition, a radical is generated by the decomposition of the organic peroxide to cause a curing reaction, but the trade-off between storage stability and curability cannot be resolved, and it is difficult to secure storage stability as a sheet. On the other hand, in the present invention, the compound (B) absorbs ambient oxygen and plays a role of creating an oxygen-deficient state by itself and a role of generating an organic peroxide,
With the ingenious mechanism of gradually repeating the generation and decomposition of organic peroxides, we were able to eliminate the trade-off between storage stability and curability. Further, in the present invention, by causing a reaction specific to a compound having a conjugated double bond such as a Diels-Alder reaction at room temperature, curing is promoted, and thus the conventional anaerobic curable composition and a sheet formed thereof are completely different from each other. It is a clear line. In addition, the adhesive rubber-based resin (A), the compound (B) and / or the compound (C) form a micro phase-separated structure having the adhesive rubber-based resin (A) as a matrix, and the compound (B) and ethylene Monomers or Oligomers (C) Having a Hydrophilic Unsaturation Group
Since it exists as a sea-island structure with spherical particles, the supply of oxygen is extremely gentle and the air oxidation is slow, so that a rapid increase in radicals can be suppressed. This greatly contributes to compatibility between storage stability and curability as a sheet.

In the curable pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive rubber-based resin (A) means a pressure-sensitive adhesive acrylic polymer, natural and synthetic cis-1,4-polyisoprene rubber, butyl rubber, halogenated butyl rubber, and partially added rubber. Sulfur butyl rubber, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), silicone rubber, chloroprene rubber, nitrile rubber, butadiene rubber, etc. It is used as a rubber-based resin for adhesives, and is a so-called elastomer. In particular, the tacky acrylic polymer can be produced freely in terms of structure and molecular weight, and forms a good microphase-separated structure with the compound (B) and the compound (C). ) Is suitable.
Adhesive acrylic polymers are hydroxyl groups, tertiary amino groups,
It has a functional group such as a carboxyl group, an amide group, and a nitrile group, and is generally used as an acrylic resin for pressure-sensitive adhesives. The acrylic polymer having these functional groups includes one or several kinds of monomers having a hydroxyl group, a tertiary amino group, a carboxyl group, an amide group, a nitrile group, an alkyl (meth) acrylate, vinyl acetate and vinyl propionate. , Copolymers with monomers such as vinyl ether and styrene.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and N-methylol acrylamide, and the monomer having a tertiary amino group includes dimethylaminoethyl ( (Meth) acrylate,
Examples thereof include diethylaminoethyl (meth) acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid and maleic acid. Examples of the amide group-containing monomer include acrylamide, methacrylamide, and N-methyl (meth) acrylamide. Examples of the monomer having a nitrile group include acrylonitrile, methacrylonitrile, crotononitrile, and fumaronitrile. Examples of alkyl (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. In addition, monomers generally used in the synthesis of acrylic polymers can also be used in the synthesis of tacky acrylic polymers.

The polymerization reaction of the tacky acrylic polymer is an ordinary radical polymerization, and there is no limitation on the reaction method, and it can be carried out by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, etc. Solution polymerization is preferred because it is easy and can be directly transferred to the next operation. Any solvent may be used as long as it can dissolve the resin of the present invention, such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate and butyl acetate, and may be a single solvent or a mixture of a plurality of solvents. Further, the polymerization initiator used in the polymerization reaction is also known such as benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, organic peroxides such as lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. Anything can be used, and there is no particular limitation.

The compound (B) of the present invention has both oxygen absorbing ability and organic peroxide forming ability, and has an oxygen absorbing amount of 0.1 to 3.
% (Weight of absorbed oxygen / weight), amount of active oxygen is 0.01 to 1
% (Active oxygen weight / weight). The oxygen absorption amount and the active oxygen amount are measured by the following methods. 1) Measurement of oxygen absorption amount Compound (B) was measured at 25 ° C., 300 ± 25 psi, 168
Under time conditions, the weight gain is measured. Samples should be crushed to 200-300 mesh or 20-300 mesh
The thin film has a thickness of 50 μm. 2) Measurement of active oxygen amount The compound (B) is dissolved in chloroform, an excess potassium iodide solution is added as a reducing agent, and liberated iodine is titrated with a sodium thiosulfate solution. Glacial acetic acid, if necessary
Add methanol. The sample is crushed to 200-300
Mesh or a thin film of 20-50 μm, 60
Measurement is performed immediately after leaving at 10 ° C. for 10 days.

The compound (B) of the present invention includes rosin,
Polymerized rosin and its polyhydric alcohol esters, butadiene, cyclodienes such as cyclopentadiene, furans, unsaturated higher fatty acids, and their triglycerides, terpenes, terpene phenols, rosin phenols, aromatic modified terpenes, hydrogenated terpenes, fats Group petroleum resins, aromatic petroleum resins, copolymer petroleum resins, and the like. Among them, rosin, polymerized rosin, and polyhydric alcohol ester thereof, terpene, terpene phenol, rosin phenol, aromatic modified terpene, hydrogenated terpene, aliphatic petroleum resin, aromatic petroleum resin, and copolymer petroleum resin are , A conjugated double bond, or a third carbon position or an allyl position, and their oxygen absorption ability and organic peroxide generation ability are optimal, and they are suitable for the compound (B) of the present invention. .

Wood rosin (oxygen absorption:
9.25%, active oxygen amount: 2.61%, the same shall apply hereinafter), gum rosin, tall oil rosin, hydrogenated rosin and the like. Polyhydric alcohol esters of rosin include glycerin ester and pentaerythritol ester, and glycerin ester includes ester gum 8D (5.05%,
0.56%), ester gum 8L-JA (4.22%,
0.51%, all are Hercules rosin glycerin ester), and pentaerythritol ester includes pentaline A-JA (1.80%, 0.10%), pentaline A-J, ester R-95, ester R-. 105
(1.05%, 0.56%), pentaline 4850, pentaline 4851 (all are rosin pentaerythritol ester manufactured by Hercules). Examples of hydrogenated rosins include steberite and Foral AX (hydrogenated rosin manufactured by Hercules). The hydrogenated rosin ester includes methyl ester of hydrogenated rosin, triethylene glycol ester, glycerin ester, and pentaerythritol ester, and the hydrogenated rosin methyl ester includes Hercoline D (manufactured by Hercules) and hydrogenated rosin triethylene glycol ester. As the steberite ester 3 (manufactured by Hercules), and as the hydrogenated rosin glycerin ester, steberite ester 5J (<
0.10%, 0.04%), steberite ester 7,
Stevelite ester 10 (<0.10%, 0.04
%), Foral 85 (<0.10%, 0.12%, hydrogenated rosin ester manufactured by Hercules Co., Ltd.), and hydrogenated rosin pentaerythritol ester is pentaline H.
(<0.10%, 0.26%), Foral 105 (pentaerythritol ester manufactured by Hercules), and the like. Examples of the dibasic acid-modified rosin ester include pentaline 4820, pentaline 4821, and pentaline 474.
0, pentaline 830 (both are dibasic acid modified rosin ester manufactured by Hercules Co., Ltd.) and the like. Examples of the polymerized rosin include polypale (1.00%, 0.06%), Dymarex (0.30%, 0.14%, both are polymerized rosins manufactured by Hercules Co., Ltd.). Polymerized rosin esters include glycerin ester and pentaerythritol ester of polymerized rosin, and ester gum 10D
(0.52%, 0.35%, polymerized rosin glycerin ester manufactured by Hercules Co., Ltd.), pentaline CJ (0.1
5%, 0.18%), pentaline K, pentaline 259
0 (0.30%, 0.07%, both are polymerized rosin pentaerythritol ester manufactured by Hercules Co., Ltd.) and the like.

The terpene resin includes YS resin PX, P
XN, A, Z series (made by Yasuhara Chemical Co., Ltd.), Picolite A, C, S series (made by Hercules Co., Ltd.) and the like. Terpene phenolic resins include YS Polystar 2130 (1.10%, 0.36%), 2115, 2
100, T series, S series, Mighty ace G1
50 (1.05%, 0.35%), G125 (manufactured by Yasuhara Chemical Co.), Picofin T-125, A135 (manufactured by Hercules Co.) and the like. Examples of the rosin phenol resin include Sumilite resin PR12603 (manufactured by Sumitomo Juretsu Co., Ltd.) and Tamanor 803 (manufactured by Arakawa Chemical Co., Ltd.). Examples of the aromatic modified terpene resin include YS resin TO series (manufactured by Yasuhara Chemical Co.). Examples of hydrogenated terpene resins include Clearon P and M series (made by Yasuhara Chemical Co., Ltd.). For aliphatic petroleum resin, Pico Pale 1
00 (1.23%, 0.41%), Picotuck 95,
B, 115 (1.17%, 0.39%) (manufactured by Hercules), Clayton A, B, C, D, M, N, U, R
X (manufactured by Zeon Corporation). Examples of the aromatic petroleum resin include picolastic A, D series, crystalrex series (manufactured by Hercules Co., Ltd.), petrosin series (manufactured by Mitsui Petrochemical Co., Ltd.) and the like. Copolymer petroleum resins include Picotac HM2162, Hercotac 1148,
1149 (manufactured by Hercules).

Among the rosins, wood rosin, gum rosin, and tall oil rosin tend to have too large an oxygen absorption amount, and hydrogenated rosin tends to have an too small oxygen absorption amount, and either of them cannot be used alone as the compound (B). Many. These polyhydric alcohol esters also show similar tendency in oxygen absorption amount, but there are also those having an appropriate oxygen absorption amount, and rosin pentaerythritol ester such as ester R105 can be used as the compound (B). The polymerized rosin and the polymerized rosin polyhydric alcohol ester generally have an oxygen absorption amount of 0.1 to 3.0% (weight of absorbed oxygen / weight of compound),
The amount of active oxygen is also 0.001 to 0.5% (weight of active oxygen / weight of compound), and many are suitable as the compound (B) of the present invention. Particularly preferably, a polymerized rosin such as Daimalex resin and a polymerized rosin pentaerythritol ester such as pentaline CJ are suitable as the compound (B). The addition amount of the compound (B) is 30 to 150 parts by weight with respect to 100 parts by weight of the adhesive rubber resin (A), but 40 to 70 parts by weight is preferable for achieving both curability and storage stability. The rosin compound can be used as a tackifier, but the purpose of use of the present invention is its reactivity such as an organic peroxide formation reaction and Diels-Alder reaction, and it is essentially used as a conventional tackifier. Is different.

Examples of the monomer having an ethylenically unsaturated group include diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate. , Pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of polyhydric alcohols such as dipentaerythritol hexa (meth) acrylate, mono (meth) acrylate, etc., and the number average molecular weight of the oligomer is 400 to 10,000, Preferably up to 5000 polyester type, polyether type, polyurethane type, epoxy oligomer type, polysulfide type, polycarbonate Rorakuton system, such as poly (meth) acrylate or mono (meth) acrylates such as polycarbonate systems. In particular, unsaturated polyester oligomers obtained by ring-opening polymerization of a compound having a hydroxyl group, a cyclic acid anhydride, and an epoxide having an ethylenically unsaturated group, the production method of which is described in JP-A No. 61-126128. Are suitable as monomers or oligomers (C).

As the compound having a hydroxyl group used in the synthesis of the unsaturated polyester oligomer, general alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and isopropyl alcohol, and ethylene glycol, propylene glycol, 1,4-
Butylene glycol, 1,3-butylene glycol, butenediol, hexanediol, cyclohexanediol, bisphenol A, bisphenol F, diethylene glycol, dipropylene glycol and other low molecular weight diols, polyethylene glycol, polypropylene glycol, polypropylene-polyethylene glycol, polybutylene glycol , High molecular weight diols such as polyether diol and polyester diol. Trivalent or higher alcohol compounds such as glycerin, trimethylolpropane, 1,2,6-hexanetriol can be used, but diols are preferable. Examples of cyclic acid anhydrides include maleic anhydride, phthalic anhydride, and anhydrous 1,2-
Examples thereof include cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride, and succinic anhydride. Examples of the epoxide having an ethylenically unsaturated group include glycidyl acrylate and glycidyl methacrylate. The synthesis is carried out by using 1 mol of a cyclic acid anhydride, 1 mol of an epoxide having an ethylenically unsaturated group, 0.1 to 0.5 mol of an organic compound having a hydroxyl group, and 0.1 to 0.5 mol of a radical polymerization inhibitor with respect to the epoxide. 4 phr, preferably 0.1 to 1 phr is put in a reaction vessel, and the temperature can be controlled with a uniform temperature distribution in a heater at 60 to 95 ° C., preferably 80 to
Stirring is carried out while heating to 90 ° C., and further reaction is carried out under the condition that the atmospheric oxygen concentration in the reaction vessel is 1% to 10%, preferably 1 to 5%.

The amount of the monomer or oligomer (C) compounded is such that the amount of the ethylenically unsaturated group of the monomer or oligomer (C) is more than 0 mol and less than 140 mol with respect to 1 mol of the active oxygen of the compound (B). It is preferable. The amount of the ethylenically unsaturated group of the monomer or oligomer (C) is 140 per mol of the active oxygen of the compound (B).
If it is more than the molar amount, the curability becomes poor and the balance between the adhesive property and the adhesive property becomes poor. In order to achieve both storage stability and curability of the curable pressure-sensitive adhesive sheet and compatibility between the adhesive property before curing and the adhesive strength after curing, the adhesive rubber-based resin (A), compound (B), monomer or oligomer. It is necessary that (C) form a microphase-separated structure having the adhesive rubber resin (A) as a matrix. In particular, when the monomer or oligomer (C) is blended in an amount of 5 to 100 parts by weight with respect to 1 mol of active oxygen of the compound (B), the storage stability and curability are well balanced.

The peroxide (D) is preferably an organic peroxide, and examples thereof include dialkyl peroxides such as di-tert-butyl peroxide, tert-butylcumyl peroxide and dicumyl peroxide. Diacyl peroxides such as acetyl peroxide, lauroyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methyl cyclohexanone peroxide and other ketone peroxides, 1, Peroxyketals such as 1-bis (tert-butylperoxy) cyclohexane, tert-butylhydroperoxide, cumene hydroperoxide, 1, 1, 3, 3 Hydroperoxides such as tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, tert-butylperoxyacetate, tert- There are peroxyesters such as butylperoxy-2-ethylhexanoate and tert-butylperoxybenzoate. Among them, benzoyl peroxide is excellent in balance between curability and storage stability, and peroxide ( Suitable for D).
The peroxide (D) is 100 parts by weight of the adhesive rubber resin (A), 30 to 150 parts by weight of the compound (B), and the monomer or oligomer (C) is based on 1 mol of active oxygen of the compound (B). Ratio of usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on the curable resin composition in which the ethylenically unsaturated group of the monomer or oligomer (C) is 2 to 140 mol. Used in.

In order to secure a sufficient pot life at the time of coating and improve the adhesive property before curing, in the present invention, the epoxy compound (E) is added to the adhesive acrylic resin (A) and compound (B). ), The monomer or oligomer (C) is partially crosslinked to enhance the cohesive force. Examples of such epoxy compounds include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl. Ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene polyethylene glycol diglycidyl ether, propylene polypropylene glycol diglycidyl ether, polytetramethylene glycol di Glycidyl ether, diglyceride adipic acid Glycol ester, phthalic acid diglycidyl ester, hydroquinone diglycidyl ether, there is a polyglycidyl ester or a mixture of these polyglycidyl ethers and carboxylic acids such as glycols such as bisphenol S diglycidyl ether. The epoxy compound (G) is used in an amount of 0.05 to 2 parts by weight per 100 parts by weight of the anaerobic curable adhesive composed of the adhesive rubber resin (A), the compound (B), the compound (C) and the compound (D). Parts, preferably 0.1 to 1.5 parts by weight.

As the polymerization inhibitor (F), hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, p-benzoquinone, 2-mercaptobenzimidazole, 2,2,4-trimethyl-1,2-
Dihydroquinoline, N, N-di-β-naphthyl-p-phenylenediamine, 4,4-butylidene-bis (3-methyl-6-t-butylphenol, phenyl-β-naphthylamine, 2,2-methylenebis (4- Methyl-6-
Radical polymerization inhibitors such as t-butyl) phenol, 2-mercaptobenzimidazole, diphenylpicrylhydrazyl, galbinoxyl, N-nitrosophenylhydroxylamine aluminum salt, sulfur and nitro compounds are used. Among these polymerization inhibitors, N-nitrosophenylhydroxylamine aluminum salt is particularly preferable for satisfying both storage stability and curability of the curable pressure-sensitive adhesive sheet. By adding the polymerization inhibitor (F),
Storage stability is significantly improved, but the time required for curing tends to be long. The amount of the polymerization inhibitor (F) added is 100 parts by weight of the curable adhesive composed of the adhesive rubber resin (A), the compound (B), the monomer or oligomer (C), and the peroxide (D). , 0.001 to 1 part by weight, preferably 0.005 to 0.5 part by weight.

The curable pressure-sensitive adhesive of the present invention may contain a pigment, a dye, an inorganic filler, a metal powder, a silane coupling agent, a tackifier, etc., if necessary. The curable pressure-sensitive adhesive of the present invention is coated on a release liner made of paper or cloth treated with silicone, and the solvent is removed by drying if necessary, and processing such as cutting is performed if necessary.
Form into a double-sided or single-sided curable adhesive sheet. A non-air-permeable base material such as cellophane or a polyethylene terephthalate film may be used as a core material to apply a curable pressure-sensitive adhesive for reinforcement and impact relaxation. Further, a breathable base material such as a nonwoven fabric may be impregnated with a curable pressure-sensitive adhesive in a non-breathable manner. The double-sided pressure-sensitive adhesive sheet thus obtained is sandwiched between two adherends of the same kind or different kinds, temporarily adhered due to its good adhesiveness, and then allowed to stand at room temperature to be cured to be adhered to each other. Can be firmly adhered. The curable pressure-sensitive adhesive sheet of the present invention cures in a few hours to a week and reaches practical strength.

EXAMPLES The present invention will be described below with reference to examples. In the examples, "part" means "part by weight" and "%" means "% by weight".

Synthesis of adhesive rubber resin (A) Polymer 1 Butyl acrylate 93.1 parts Acrylic acid 6.9 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts Heating to 80 ° C. in a nitrogen atmosphere 125 parts of the above mixture having the same composition was added dropwise to 125 parts of the above composition, and after completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of polymer 1 (solid content 40%). . Polymer 2 Butyl acrylate 92.0 parts Acrylamide 2.8 parts 2-Hydroxyethyl methacrylate 5.2 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts Each of the above heated to 80 ° C. in a nitrogen atmosphere. To 125 parts of the mixture having the composition, 125 parts of the mixture having the same composition was dropped, and after the completion of the dropping, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of polymer 2 (solid content 40%). Polymer 3 Califlex TR-1101 40.0 parts (SBS, an adhesive rubber-based polymer manufactured by Shell Chemical Co., Ltd.) Toluene 60.0 parts The above composition is dissolved by stirring at 50 ° C. in a nitrogen atmosphere, and a solution of polymer 3 ( Solid content 40%) was obtained.

Preparation of Solution of Compound (B) Rosin Compound 1 Pentaline 2590 40.0 parts (Polymerized rosin pentaerythritol ester manufactured by Hercules Co., Ltd.) Ethyl acetate 60.0 parts The mixture having the above composition is stirred at room temperature for 1 hour to prepare rosin compound 1 To obtain a solution (solid content 40%). Rosin compound 2 ester R105 40.0 parts (Hercules rosin pentaerythritol ester) Ethyl acetate 60.0 parts The mixture of the said composition was stirred at room temperature for 1 hour, and the solution of rosin compound 2 (solid content 40%) was obtained. . Rosin compound 3 Chinese rosin 40.0 parts Ethyl acetate 60.0 parts The mixture having the above composition was stirred at room temperature for 1 hour to obtain a solution of rosin compound 3 (solid content: 40%). Rosin compound 4 Foral 85 40.0 parts (Hercules hydrogenated rosin glycerin ester) Ethyl acetate 60.0 parts The mixture having the above composition is stirred for 1 hour at room temperature to obtain a solution of rosin compound 4 (solid content 40%). It was Terpene compound 1 YS Polystar 2130 40.0 parts (Yasuhara Chemical Co. terpene phenol copolymer) Ethyl acetate 60.0 parts The mixture of the above composition is stirred at room temperature for 1 hour to give a solution of terpene compound 1 (solid content 40%). Obtained. Terpene compound 2 Mighty ace G 40.0 parts (Yasuhara Chemical Co. terpene phenol copolymer) Ethyl acetate 60.0 parts The mixture of the above composition is stirred for 1 hour at room temperature to give a solution of terpene compound 2 (solid content 40%). Obtained.

Petroleum resin compound 1 Picopeil 100 40.0 parts (Hercules aliphatic petroleum resin) Ethyl acetate 60.0 parts The mixture having the above composition is stirred at room temperature for 1 hour to prepare a solution of petroleum resin compound 1 (solid content). 40%).

Preparation of Monomer or Oligomer Having Ethylenically Unsaturated Group (C) Solution Unsaturated Polyester Oligomer 1 Ethylene glycol 2.0 parts Hexahydrophthalic anhydride 51.0 parts Glycidyl methacrylate 47.0 parts N, N-dimethylbenzyl Amine 0.9 parts Hydroquinone 0.2 parts Ethyl acetate 25.0 parts The above compositions are mixed and reacted in an air atmosphere at 80 ° C. for 10 hours. After cooling, 125 parts of ethyl acetate is added to the unsaturated polyester. Oligomer 1 (number average molecular weight 1
670) solution (solid content 40%) was obtained. Unsaturated polyester oligomer 2 ethylene glycol 2.5 parts succinic anhydride 40.3 parts glycidyl methacrylate 57.2 parts N, N-dimethylbenzylamine 1.1 parts hydroquinone 0.2 parts ethyl acetate 25.0 parts After mixing and reacting at 80 ° C. for 10 hours in an air atmosphere and cooling, 125 parts of ethyl acetate was added to the unsaturated polyester oligomer 2 (number average molecular weight 2
050) solution (solid content 40%). Epoxy acrylate 1 Lipoxy SP1509 40.0 parts (Epoxy acrylate manufactured by Showa Polymer Co., Ltd.) Ethyl acetate 60.0 parts The above composition was dissolved by stirring at room temperature to obtain a solution of epoxy acrylate 1 (solid content 40%). .

Preparation of Epoxy Compound (E) Solution Epoxy Compound 1 Denacol EX-313 40.0 parts (Nagase Kasei Co., Ltd., glycerol polyglycidyl ether) Ethyl acetate 60.0 parts The above composition was dissolved by stirring at room temperature. A solution of the epoxy compound 1 (solid content 40%) was obtained. Epoxy compound 2 Denacol EX-421 40.0 parts (Nagase Kasei Co., Ltd., diglycerol polyglycidyl ether) ethyl acetate 60.0 parts The above composition was dissolved by stirring at room temperature to obtain a solution of epoxy compound 2 (solid content 40 %) Was obtained.

Preparation of Polyisocyanate Solution Polyisocyanate 1 Coronate L 53.3 parts (Nippon Polyurethane Industry Co., Ltd. adduct polyisocyanate) ethyl acetate 46.7 parts The above composition was dissolved by stirring at room temperature to give polyisocyanate 1
To obtain a solution (solid content 40%).

Preparation of Polymerization Inhibitor Solution Polymerization inhibitor 1 N-nitrosophenylhydroxylamine aluminum salt 40.0 parts Ethyl acetate 60.0 parts The above composition was dissolved by stirring at room temperature to prepare a solution of polymerization inhibitor 1 (solid content). 40%).

Example 1 45.0 parts of solution of polymer 1, solution 3 of rosin compound 1
0.0 parts, solution 2 of unsaturated polyester oligomer 1
5.0 parts, Niper BMT-K40 (benzoyl peroxide 40% xylene solution manufactured by NOF CORPORATION) 3.0
Parts and 0.5 parts of a solution of the epoxy compound 1 are sufficiently mixed and the thickness after drying is 30 μm on a polyethylene-coated high-quality paper (hereinafter referred to as a release liner) treated with silicone.
It was applied so as to have a thickness of m, dried at 60 ° C. for 3 minutes, and overlapped with a release liner to obtain an adhesive sheet. The pressure-sensitive adhesive sheet thus obtained was evaluated for pressure-sensitive adhesive properties (peeling adhesive strength, tack, holding power) before curing, shear adhesive strength after curing, and storage stability of the pressure-sensitive adhesive sheet and pot life during coating. The above measurement results are shown in Table 2.

(1) Peel adhesion before curing One release liner was peeled off, a polyethylene terephthalate sheet having a thickness of 50 μm was attached to the adhesive surface of the obtained adhesive sheet, cut into a width of 25 mm, and then the other side. The release liner was peeled off, and the resulting adhesive surface was adhered to a # 280 sandpaper-polished stainless steel plate (SUS304), left for 30 minutes, and then peeled off at 25 ° C. and 65% relative humidity. The 180 degree peel adhesion was measured at 300 mm / min. (2) Tack before curing The release liner on one side of the obtained pressure-sensitive adhesive sheet was peeled off on the slope having an inclination angle of 30 degrees, the release surface was set, and the running distance was 10 cm under conditions of 25 ° C and relative humidity of 65%. The balls made of stainless steel were rolled, and the number of the largest ball stopped within 10 cm of the adhesive surface was measured. The number of the ball is represented by 32 times as many as 31 kinds of "name of ball" from 1/16 to 1. (3) Holding power before curing One release liner was peeled off, a polyethylene terephthalate sheet having a thickness of 50 μm was attached to the adhesive surface of the obtained adhesive sheet, and cut into a width of 25 mm and a length of 100 mm. The other release liner was peeled off, and the 25 mm wide and 25 mm wide portion of the resulting adhesive surface was polished with sandpaper # 280 to make a stainless steel plate (SUS3
04), and the time (second) until the adhesive sheet dropped from the stainless steel plate was measured at 40 ° C. and a load of 1 kg.

(4) Shear adhesive strength after curing Two aluminum plates having a length of 50 mm, a width of 10 mm, and a thickness of 0.5 mm, and one release liner of an adhesive sheet cut to a length of 10 mm and a width of 10 mm at one end on one side. The adhesive surface of the pressure-sensitive adhesive sheet obtained by peeling was peeled off, the other release liner was peeled off, and the resulting adhesive surface was pasted so that air bubbles did not enter, and heat-cured and laminated and cured. The heat curing was performed by using a hot press and pressing at 100 ° C. for 20 seconds at a pressure of 1 kg per 1 cm 2. The laminating and curing was performed by leaving it at 20 ° C. for 1 week to cure it. After curing, the shear strength was measured at a pulling rate of 5 mm / min under the conditions of room temperature of 25 ° C. and relative humidity of 65%. (5) Pot life during coating 200 parts of the finished adhesive solution was placed in a glass container, and the container was further immersed in a hot water bath at 40 ° C. for 4 hours, and then treated with silicone to give a good quality polyethylene coating. The thickness after drying on paper (hereinafter referred to as release liner) is 30μ
It was applied so as to have a thickness of m and dried at 60 ° C. for 3 minutes. Good that the surface condition is smooth and the film is uniform,
Those in which spots, streaks, etc. were observed and those in which coating was not possible were considered defective. (6) Storage stability of pressure-sensitive adhesive sheet One release liner was peeled off, a silicone-treated polyethylene terephthalate sheet having a thickness of 50 μm was attached to the pressure-sensitive adhesive surface of the obtained pressure-sensitive adhesive sheet, and the other release liner was peeled off. Another silicon-treated 50 μm thick
Attach the polyethylene terephthalate film of
After storage at 50 ° C. for 2 weeks in a state of poor oxygen permeation, storage stability was evaluated by whether or not there was stickiness. Those that were cured and had no tackiness were rated as bad, and those that were sufficiently tacky were rated as good.

Examples 2 to 11 In the same manner as in Example 1, adhesive rubber resin, compound (B),
Compound (C), Niper BMT-K which is an organic peroxide
40, the compound (E) and the polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum salt) were mixed at the compounding ratio shown in Table 1 to prepare an adhesive sheet. Further, it was aged at 50 ° C. for 3 days. The pressure-sensitive adhesive sheet thus obtained was evaluated for tackiness before curing, shear adhesive strength after curing, storage stability of the pressure-sensitive adhesive sheet, and pot life during coating. The above measurement results are shown in Table 2.

Comparative Examples 1 to 5 As in Example 1, an adhesive rubber resin, compound (B),
Compound (C), Niper BMT-K which is an organic peroxide
40, the compound (E) (polyisocyanate in the case of Comparative Example 5) and the polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum salt) were mixed at the compounding ratio shown in Table 1 to prepare a pressure-sensitive adhesive sheet. Further, it was aged at 50 ° C. for 3 days. The pressure-sensitive adhesive sheet thus obtained was evaluated for tackiness before curing, shear adhesive strength after curing, storage stability of the pressure-sensitive adhesive sheet, and pot life during coating. The above measurement results are shown in Table 2.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

The curable pressure-sensitive adhesive of the present invention has a peel adhesive strength before curing of 1500 g / 25 mm or more, a tack of 3 or more,
Holding power is 1 hour or more. Shear adhesive strength of 20 kg / cm after heating or pasting for 1 week
^{It is 2} or more, and it has excellent adhesive properties before curing and adhesive strength after curing. In addition, the pot life of the coating liquid after blending has been secured, which is sufficiently compatible with the coating environment in the summer. As described above, according to the present invention, the adhesive property before curing and the adhesive property before curing are excellent in adhesive properties at the time of bonding, and they are hardened immediately after heating or gradually hardened after bonding to show a strong adhesive force. A curable pressure-sensitive adhesive having an excellent balance can be obtained. The curable pressure-sensitive adhesive sheet coated with this curable pressure-sensitive adhesive was excellent in both storage stability after being processed into a sheet and curability during use. From this, it became possible to use it for various uses.

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Claims (4)

[Claims] 1. An adhesive rubber-based resin (A), which has both oxygen absorption ability and peroxide generation ability, and has an oxygen absorption amount of 0.1 to 3%.
(Absorbed oxygen weight / weight), active oxygen amount is 0.01-1%
(Active oxygen weight / weight), compound (B), monomer or oligomer (C) having ethylenically unsaturated group, organic peroxide (D) and epoxy compound (E)
The compound (B) is 30 to 150 parts by weight, the organic peroxide (D) is 0.1 to 15 parts by weight, and the epoxy compound (E) is based on 100 parts by weight of the adhesive rubber resin (A). Is 0.05 to 3 parts by weight, and the monomer or oligomer (C) having an ethylenically unsaturated group has a monomer or oligomer (C) having an ethylenically unsaturated group with respect to 1 mol of active oxygen of the compound (B). (2) The ethylenically unsaturated group is mixed in an amount of 2 to 140 mol. 2. The compound (B) is rosin, polymerized rosin,
And at least one selected from polyhydric alcohol ester thereof, terpene, terpene phenol, rosin phenol, aromatic modified terpene, hydrogenated terpene, aliphatic petroleum resin, aromatic petroleum resin, and copolymer petroleum resin.
The curable pressure-sensitive adhesive according to claim 1, which is a seed. 3. The curable adhesive 1 according to claim 1 or 2.
A curable pressure-sensitive adhesive obtained by adding 0.001 to 1 part by weight of a polymerization inhibitor (F) to 100 parts by weight. 4. A curable pressure-sensitive adhesive sheet or tape obtained by laminating or impregnating the curable pressure-sensitive adhesive according to any one of claims 1 to 3 on a non-breathable substrate or a porous substrate.