JPH09143446A - Adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive giving strong adhesive strength by using two kinds of adhesives. SOLUTION: This two pack-type adhesive is composed of following adhesives (1) and (2): an adhesive (1) is composed of 50-200 pts.wt. of a tacky acrylic polymer having 10×10<4> -100×10<4> weight-average molecular weight, 1.5-15 pts.wt. of a polymerization initiator, 50-300 pts.wt. of a solvent and 100 pts.wt. of an unsaturated polyester oligomer having 1,000-5,000 weight-average molecular weight and having <=10<4> cPs viscosity at 25 deg.C, and an adhesive (2) is composed of 50-200 pts.wt. of a tacky acrylic polymer having 10×10<4> -100×10<4> weight- average molecular weight, 0.015-15 pts.wt. of decomposition accelerator of a polymerization initiator, 50-300 pts.wt. of a solvent and 100 pts.wt. of an unsaturated polyester oligomer having 1,000-5,000 weight-average molecular weight and having <=10<4> cPs viscosity at 25 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a property as a pressure-sensitive adhesive that exhibits tackiness at the time of bonding and easily adheres to various adherends without the need for temporary fixing. The present invention relates to an adhesive that hardens in a short time and exhibits a strong adhesive force.

[0002]

2. Description of the Related Art Most of the adhesives presently used in the world are liquid in the initial stage and harden due to some chemical change to develop an adhesive force, and it is necessary to perform temporary fixing or the like until the curing is completed. There is. As a bonding agent that has tackiness at the time of bonding to eliminate such complexity of operability, can be easily temporarily bonded to an adherend, and gradually hardens after being bonded to exhibit a strong adhesive force. Is a curable adhesive tape or the like. This curable pressure-sensitive adhesive tape (or sheet) is a moisture-curable tape (or Japanese Patent Publication No. 47) which is cured by moisture in the air or moisture in the adherend.
-44017, JP-B-49-5895, JP-A-54-64536, and JP-A-58-17146.
No. 0, JP-A-59-58071, JP-A-61.
No. 145268, JP-A No. 61-148281), a heat-curable thermosetting type (Japanese Patent Publication No. 50-12464).
JP-A-51-6235, JP-A-54-135
No. 02335, Japanese Patent Publication No. 55-8113, Japanese Patent Publication No. 59-14508, and Japanese Patent Publication No. 59-108072.
JP-A-60-217283, JP-A-61
-81467), photo-curing type curable by light (JP-A-56-120786, JP-A-57-159864).
JP-A No. 60-69178, JP-A No. 61-
162574), an anaerobic curing type that cures by shutting off air (Japanese Patent Publication No. 58-12918, Japanese Patent Publication No. 59-199984, Japanese Patent Publication No. 59-1997).
85, JP-A-60-6773, JP-A-60
-11568, JP-A-60-13868)
There is.

However, each of the curable adhesive tapes (or sheets) 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 thermosetting type cannot be applied to heat-sensitive materials, and the photocuring type can be used only with a tape using a transparent film that transmits light. The anaerobic curable type requires a storage state in which it is always in contact with air, and if the curability is to be improved, it is difficult to keep the balance between the curability and the preservability such that the preservability is inferior.

Originally, the most ideal curable pressure-sensitive adhesive tape (or sheet) is one which is cured and adhered only by being attached without applying any energy. The above-mentioned moisture-curing type and anaerobic-curing type correspond to this, but it is very difficult to express such a function with ordinary adhesive tape in terms of storability, and even if it is possible, it is a halfway balance with curability. I can only do something.

In order to solve such a problem, a curable pressure-sensitive adhesive tape of a type in which two tapes are attached at the time of use and the reactive components are contained in separate tapes (Japanese Patent Laid-Open No. 58-58).
No. 67777) is proposed. However, the design of the resin structure is very important in order to react easily at room temperature and to exert a strong adhesive strength, and conventional curable pressure-sensitive adhesive resins exhibit satisfactory performance. You cannot do it. The problem with the above-mentioned double-bonding type curable pressure-sensitive adhesive tape (or sheet) using a conventional resin is that the adhesive property at the time of bonding and the adhesive property after bonding and curing are unbalanced, and in most cases the adhesive property is If the characteristics were good, the adhesive strength was poor, and if the adhesive strength was high, the initial tackiness was poor. Therefore, even if the composition with the tape is a double-bonded type and the storage stability and curability are both achieved, a curable adhesive tape with an excellent balance of adhesive properties and adhesive properties can be obtained without proper resin design. I couldn't do it.
Further, in the form of tape, there is a limit to the wettability with respect to the adherend, and there is a problem that the cohesive force that the bonding agent originally has after curing cannot be fully utilized.

[0006]

DISCLOSURE OF THE INVENTION The present invention is a conventional two-sided bonding type curable adhesive tape produced without considering the structure and molecular weight of the resin, which has a poor balance between the adhesive property and the adhesive force after curing. The resin design that eliminates the above defects and takes into account the balance between the two, and by adopting a two-part adhesive as the form, has good preservability and excellent adhesive properties before curing, and wettability to the adherend. And an adhesive agent having sufficient adhesive strength after curing, and capable of curing in a short time at room temperature.

[0007]

The present invention is based on 100 parts by weight of an unsaturated polyester oligomer (A) having a weight average molecular weight of 1,000 to 5,000, and a tacky acrylic resin having a weight average molecular weight of 100,000 to 1,000,000. Polymer (B)
25 to 50 parts by weight, polymerization initiator (C) 1.5 to 15 parts by weight and solvent (D) 50 to 300 parts by weight 25
The present invention relates to an adhesive (1) having a viscosity at 10,000 ° C. or less.
Further, the present invention is based on 100 parts by weight of the unsaturated polyester oligomer (A) having a weight average molecular weight of 1000 to 5000, and 50 to 200 parts by weight of the tacky acrylic polymer (B) having a weight average molecular weight of 100,000 to 1 million, The composition has a viscosity of 1 to 0.015 to 15 parts by weight of a polymerization initiator (E) and 50 to 300 parts by weight of a solvent (D) at 25 ° C.
The present invention relates to an adhesive (2) of 10,000 cps or less.

Further, the present invention relates to a two-component curing type adhesive comprising the above adhesive (1) and the above adhesive (2). Further, the present invention provides the above unsaturated polyester oligomer (A)
Relates to the above adhesive, which is an oligomer obtained by ring-opening polymerization of a compound having a hydroxyl group, a cyclic acid anhydride and an epoxide having an ethylenically unsaturated group. Furthermore, in the present invention, the adhesive acrylic polymer (B) is -40 to 0.
The present invention relates to the above adhesive which is an acrylic polymer having a glass transition point in the range of ° C.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the unsaturated polyester oligomer (A) used in the adhesive (1) and the adhesive (2) is described in JP-A-61-126128. Preferred are 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. Generally unsaturated polyester has a double bond in the main chain, whereas the polyester oligomer of the present invention has an ethylenically unsaturated moiety such as a (meth) acryloyl group in the side chain of the polyester. The feature is that the reaction activity is extremely large, and it has curability that cures in a short time even at room temperature.

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 unsaturated polyester oligomer is synthesized by 1 mol of a cyclic acid anhydride, 1 mol of an epoxide having an ethylenically unsaturated group, and 0.05 to 0.05 of an organic compound having a hydroxyl group.
5.0 mol and 0.1 to 4 phr, preferably 0.1 to 1 phr of the radical polymerization inhibitor with respect to the epoxide are put in a reaction vessel, and the temperature is controlled at 60 to 95 ° C. with a heater capable of controlling with a uniform temperature distribution. And preferably stirred while heating to 80 to 90 ° C., and the oxygen concentration in the atmosphere in the reaction vessel is 1% to 10%
%, Preferably 1-5%. The unsaturated polyester oligomer has a weight average molecular weight of 1000 to 5 in order to secure sufficient cohesive force as a pressure-sensitive adhesive before curing and curability and adhesive force after bonding.
000 is preferred. That is, when the weight average molecular weight is 1000 or less, the cohesive force at the initial stage of adhesion is insufficient and deviation occurs, which requires temporary fixing.
If the above is the case, it takes a long time for the curing reaction after laminating, and the curability is significantly lowered.

In the present invention, the adhesive acrylic polymer (B) used in the adhesive (1) and the adhesive (2) means a hydroxyl group, a tertiary amino group, a carboxyl group, an amide group,
It is a polymer having a functional group such as an N-substituted amide group and a nitrile group, and is generally used as an acrylic resin for pressure-sensitive adhesives. Moreover, even if the polymer alone has poor adhesiveness, the unsaturated polyester oligomer (A)
A polymer that exhibits good adhesive properties by adding or other resins can be used as the polymer (B) of the present invention. 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, an N-substituted amide group, a nitrile group, an alkyl (meth) acrylate, Examples thereof include copolymers with monomers such as vinyl acetate, vinyl propionate, vinyl ether and styrene.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and N-methylolacrylamide. Examples of the monomer having a tertiary amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. Examples of the monomer having an amide group or an N-substituted amide group include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide,
Examples include N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butylacrylamide, N-octylacrylamide, diacetone acrylamide. Examples of the monomer having a nitrile group include acrylonitrile, methacrylonitrile, crotononitrile, and fumaronitrile. Further, as the alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
There are alkyl (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and octyl (meth) acrylate. In addition, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. and alkyl (meth) acrylates in which the alkyl group is substituted with an aromatic ring group, a heterocyclic group, a halogen atom, etc. are generally used. The monomers used in the synthesis of acrylic polymers can also be used in the synthesis of the polymers of the invention.

The method for synthesizing the tacky acrylic polymer is ordinary radical polymerization, and there is no limitation on the reaction method, and known polymerization methods such as solution polymerization, bulk polymerization and emulsion polymerization can be used. Solution polymerization is preferred because it is easy and can be directly transferred to the next operation. The solvent may be any solvent, such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate, and butyl acetate, as long as it dissolves the resin of the present invention. A single solvent or a mixture of a plurality of solvents may be used. Also,
Known initiators such as benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, organic peroxides such as lauroyl peroxide, and azo initiators such as azobisisobutyronitrile are also used as polymerization initiators during the polymerization reaction. Anything is possible, and there is no particular limitation.

The tacky acrylic polymer has a weight average molecular weight of 100,000 to 1 in order to sufficiently secure the cohesive force as a pressure sensitive adhesive before curing and the curability and adhesive force after bonding.
The range of, 000,000 is preferable. That is, when the weight average molecular weight is 100,000 or less, the cohesive force at the initial stage of adhesion is insufficient, causing a shift or the like, which requires temporary fixing or the adhesive force after curing cannot be sufficiently obtained. On the other hand, when the weight average molecular weight is 1,000,000 or more, the viscosity is too high to apply uniformly to the adherend, or the compatibility with the unsaturated polyester oligomer is remarkably reduced to ensure sufficient adhesive strength after curing. Will be difficult to do.

The glass transition point of the tacky acrylic polymer is -40 in order to secure tackiness and curability at room temperature.
The range of ˜0 ° C. is preferred. That is, the glass transition point is −
A polymer of 40 ° C. or lower causes insufficient cohesive force at room temperature to cause a gap after adhesion. If it is 0 ° C. or higher, the initial adhesive force is extremely poor and bonding is not possible, and the adhesive layer contains a polymerization initiator. The decomposition accelerator cannot interdiffuse and the curing reaction does not proceed. The content of the tacky acrylic polymer (B) is the same as that of the adhesive (1) of the present invention.
And 50 to 200 parts by weight per 100 parts by weight of the unsaturated polyester oligomer (A) in the adhesive (2).

In the present invention, as the polymerization initiator (C) used in the adhesive (1), dialkyl peroxides such as di-tert-butyl peroxide, tert-butylcumyl peroxide and dicumyl peroxide are used. , Acetyl peroxide, lauroyl peroxide, benzoyl peroxide and other diacyl peroxides, methyl ethyl ketone peroxide,
Cyclohexanone peroxide, ketone peroxides such as 3,3,5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide, peroxyketals such as 1,1-bis (tert-butylperoxy) cyclohexane and tert-butylhydroper Oxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, etc. Peroxy compounds such as hydroperoxides, tert-butylperoxyacetate, tert-butylperoxy-2-ethylhexanoate and tert-butylperoxybenzoate Organic peroxides such as ester compounds,
There is no particular limitation as long as it is publicly known. The blending amount of the polymerization initiator (C) is usually 0.1 to 15 parts by weight based on 100 parts by weight of the unsaturated polyester oligomer (A) in the adhesive (1) of the present invention.

In the present invention, the solvent (D) used for the adhesive (1) and the adhesive (2) is usually an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate and butyl acetate. What is called, etc. may be used, and anything that dissolves the unsaturated polyester oligomer (A), the tacky acrylic polymer (B), the polymerization initiator (C) and the decomposition accelerator (E) of the polymerization initiator of the present invention may be used. Of course, the solvents may be used alone or a plurality of solvents may be mixed. The blending amount of the solvent (D) may be determined when it is appropriately used depending on the method of applying the primer, but the unsaturated polyester oligomer (A) in the adhesive (1) and the adhesive (2) of the present invention is 100% by weight. It is usually used in a proportion of 50 to 300 parts by weight with respect to parts.

In the present invention, as the decomposition accelerator (E) of the polymerization initiator used for the adhesive (2), N, N-dimethylbenzylamine, triethylamine, tributylamine, N, N-diethylaniline, N , Tertiary amines such as N-dimethylaniline, N-phenyldiethanolamine, N-phenyldiisopropanolamine, dimethyl-p-toluidine, triethanolamine and 4-phenylmorpholine, lithium, calcium, strontium, barium, cerium and zirconium. , Vanadium, molybdenum, manganese, iron, cobalt, nickel,
Chelates such as fatty acid salts such as lauryl acid salts, naphthenic acid salts, octylic acid salts, oleic acid salts and octenoic acid salts of metals such as copper, zinc, tin and lead, resin acid salts such as rosin salts and acetylacetonate complex salts. One or more metal compounds selected from compounds and the like can be used as the promoter. Particularly, when an organic peroxide is used as the polymerization initiator (C), a decomposition accelerator (E) for the polymerization initiator
As either a tertiary amine or a metal compound,
Alternatively, it is preferable to use both of them in combination.

Of these accelerators, the tertiary amine is usually used in a proportion of 1 to 100 parts by weight with respect to 100 parts by weight of the organic peroxide, and the metal compound is added in an amount of 0.1% to 100 parts by weight of the organic peroxide. It is used in a proportion of 01 to 10 parts by weight. The purpose of the polymerization initiator and the decomposition catalyst of the polymerization initiator is to react with each other to generate active radicals. There is no limitation as to the use as the decomposition catalyst (E) of the initiator (C) and the polymerization initiator.

The adhesive (1) and the adhesive (2) are an unsaturated polyester oligomer, a tacky acrylic polymer,
It can be obtained by mixing the polymerization initiator or the decomposition accelerator of the polymerization initiator and the solvent at room temperature or with heating and stirring. It is sufficient to stir the mixture until it becomes uniform in appearance.

In the adhesion according to the present invention, when two adherends are joined, first, the adhesive (1) is brushed on one adherend,
Dry film thickness of 1 to 50 by roll or spray
It is applied so that it becomes about μ, and the solvent volatile matter is air-dried. In this case, since the coating thickness is very thin, the solvent component evaporates within a few minutes even at room temperature, but it can be dried by heating with hot air or an oven. Further, the adhesive (2) is similarly applied to the other adherend so that the dry film thickness is 1 to 50 μm.
Apply so that it becomes the extent. Adhesive (1) to this adherend
And when applying (2), the viscosity of each is 10,000 c
If it is larger than ps, the coating surface becomes uneven, the coating thickness becomes thick, or the coating itself becomes impossible by any of the methods such as brush coating, roll coating, spray coating, spin coating and silk screen printing. Therefore, it is necessary to adjust the viscosity using a solvent so that the viscosity is suitable for the coating method.

The adherend coated with the adhesive (1) and the adherend coated with the adhesive (2) are pressure-bonded and bonded to each other via the respective adhesive layers. Immediately after joining, it will be in a temporary fixing state without the need for a fixing device as with ordinary pressure-sensitive adhesives, and the curing reaction will proceed immediately after joining and reach the specified adhesive strength in about 1 hour even at room temperature to complete the adhesion. To do.

The curing mechanism of the adhesive in the present invention is that the polymerization contained in the adhesive (1) starts from the moment when the adhesive layer made of the adhesive (1) and the adhesive layer made of the adhesive (2) are brought into contact with each other. The agent and the decomposition accelerator of the polymerization initiator contained in the adhesive (2) start to generate active radicals even at room temperature through mutual diffusion and reaction with the unsaturated polyester oligomer and the adhesive acrylic polymer as a medium. . The generated active radicals then react with the unsaturated polyester oligomer, the ethylenically unsaturated group of the unsaturated polyester oligomer forms a crosslinked structure by a chain reaction by radical polymerization, and the adhesive layer is cured.

For the purpose of improving the adhesive properties before curing, and especially for enhancing the cohesive strength, in the present invention, polyisocyanate is added to the adhesives (1) and (2) to partially crosslink the adhesive acrylic polymer. It is also possible to let. Such polyisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,5-
Diisocyanates such as naphthalene diisocyanate, isophorone diisocyanate, lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, or both end isocyanate adducts of these with glycols or diamines, or mixtures thereof If necessary, trifunctional or higher polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate can also be used as a mixture with diisocyanates.

The adhesives (1) and (2) of the present invention include
If necessary, pigments, dyes, inorganic fillers, organic solvents, silver powder, copper powder, metal powders such as nickel powder, carbon black, graphite, xylene resin, terpene resin and rosin resin, as long as the performance is not impaired. A tackifier, a silane coupling agent, a leveling agent, etc. can be added.

[0027]

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 Polyester Oligomer Oligomer 1 Ethylene glycol 3.4 parts Hexahydrophthalic anhydride 50.3 parts Glycidyl methacrylate 46.3 parts N, N-Dimethylbenzylamine 0.9 parts Hydroquinone 0.2 parts Ethyl acetate 25.0 Parts The above compositions were mixed and reacted in an air atmosphere at 80 ° C. for 10 hours, and after cooling, 125 parts of ethyl acetate was added to obtain a solution of a polyester oligomer having a weight average molecular weight of 2100 (solid content: 40%). .

Synthesis of acrylic polymer Polymer 1 Butyl acrylate 92.0 parts Acrylamide 2.8 parts 2-Hydroxyethyl methacrylate 5.2 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts Heated to 80 ° C. Mixture 125 of each of the above compositions
To the parts, 125 parts of the above-mentioned mixture having the same composition was added dropwise, and after completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of an acrylic polymer having a weight average molecular weight of 570,000 (solid content: 40%).

[0030]

Example 1 100 parts solution of oligomer 1 polymer 1
Solution of 100 parts, benzoyl peroxide 2.5 parts,
Adhesive (1) was obtained by thoroughly mixing 100 parts of ethyl acetate. 100 parts of a solution of oligomer 1, 100 parts of a solution of polymer 1, 2.5 parts of N-phenyldiethanolamine,
Adhesive (2) was obtained by thoroughly mixing 100 parts of ethyl acetate. The adhesive (1) was applied to a 0.5 mm thick aluminum plate with a hand applicator so as to have a dry film thickness of 25 μ, and dried in an oven at 60 ° C. for 3 minutes to obtain an aluminum plate having an adhesive layer (1). It was Similarly, the adhesive (2) is applied to an aluminum plate having a thickness of 0.5 mm by a hand applicator so as to have a dry film thickness of 25 μ, and dried in an oven at 60 ° C. for 3 minutes to have an adhesive layer (2). Got

About the obtained aluminum plate having the adhesive layer, the adhesive properties (peeling adhesion, tack, holding power) before curing
Table 1 shows the measurement results of the shear adhesive strength after curing.

(1) Peeling adhesive strength before curing A thickness of 50 is obtained on the surfaces of the obtained adhesive layers (1) and (2).
2 μm polyethylene terephthalate sheet
After pressure bonding with a kg roller, cutting to a width of 25 mm and leaving for 30 minutes, the 180 degree peeling adhesive force was measured at a peeling speed of 300 mm / min under the conditions of 25 ° C. and relative humidity of 65%.

(2) Tack before curing The obtained adhesive layer was set on the slope having an inclination angle of 30 degrees,
Running distance of 10 cm under conditions of 25 ° C and 65% relative humidity
Then, roll the stainless steel ball to the adhesive surface 10
The number of the highest ball that stopped within cm 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 The obtained aluminum plate having an adhesive layer is cut into a width of 25 mm and a length of 100 mm, and one end thereof has a thickness of 50 μm and a width of 25 mm.
mm, 100 mm long polyethylene terephthalate sheet (PET) is pasted in an area of 25 mm x 25 mm, a weight of 250 g is attached to the other end of PET, and aluminum is erected vertically at 25 ° C and relative humidity of 65%. Condition P
The time (seconds) until the ET dropped from the aluminum plate was measured.

(4) Shearing adhesive strength after curing An aluminum plate having an adhesive layer (1) and an aluminum plate having an adhesive layer (2) are cut into a length of 50 mm and a width of 10 mm, respectively. 10m to make sufficient contact
Adhesion was performed by press-bonding in an area of m × 10 mm, and at 25 ° C. and 65% relative humidity, shear strength was measured 30 minutes after press-bonding at a pulling speed of 5 mm / min.

[0036]

Example 2 100 parts of solution of oligomer 1 polymer 1
Solution of 160 parts, benzoyl peroxide 2.5 parts,
40.0 parts of a 50% ethyl acetate solution of a tackifier YS2130 manufactured by Yasuhara Chemical Co., Ltd., 0.5 parts of leveling agent SH29PA manufactured by Toray Dow Corning Silicone Co., Ltd., and 200 parts of ethyl acetate were sufficiently mixed to obtain an adhesive (1 ) Got. 100 parts of solution of oligomer 1, solution 1 of polymer 1
60 parts, N-phenyldiethanolamine 2.5 parts, 40.0 parts of 50% ethyl acetate solution of tackifier YS2130 manufactured by Yasuhara Chemical Co., Ltd. Leveling agent SH29PA 0.5 parts manufactured by Toray Dow Corning Silicone Co., Ltd., ethyl acetate 200 The parts were thoroughly mixed to obtain an adhesive (2).

The adhesive (1) was applied with a diameter of 120 mm having a thickness of 1.0 mm.
A polycarbonate disc having an adhesive layer (1) was obtained by spin-coating on a polycarbonate disc having a diameter of 10 mm so as to have a dry film thickness of 10 μm, and further rotating the disc for 30 seconds to air-dry. Similarly, an adhesive agent (2) was spin-coated on a polycarbonate plate having a thickness of 1.0 mm to a dry film thickness of 10 μm, and the disc was further rotated for 30 seconds to air-dry to obtain a polycarbonate disc having an adhesive layer (2). Obtained. With respect to the obtained polycarbonate disc, the adhesive property before curing and the shear adhesive force after curing were measured in the same manner as in Example 1. The results are shown in Table 1.

[0038]

[Table 1]

[0039]

As shown in Table 1, the adhesive of the present invention has a peel adhesion before curing of 1200 gf / 25 mm or more,
The tack is 7 or more and the holding power is 3600 seconds or more. Furthermore, it cures within 30 minutes at room temperature and its shear adhesive strength is 25k.
It is gf / cm ² or more, and the adhesive property before curing and the adhesive force after curing are excellent. Further, in the adhesive of the present invention,
Since it is stored in the form of the adhesive (1) and the adhesive (2) until use, the components that cause the curing reaction do not react in a non-contact manner until joining, which is a problem with the conventional curable pressure-sensitive adhesive tape. Shelf life was significantly improved.

As described above, according to the present invention, it is highly adhesive at the time of joining and can be temporarily adhered to an adherend, mechanical temporary fixing is unnecessary, and it is cured at room temperature in a short time to show a strong adhesive force,
It has become possible to obtain an adhesive having an excellent balance between the adhesive property before curing and the adhesive strength after curing and having excellent storage stability.

Claims (5)

[Claims] 1. An adhesive acrylic polymer (B) having a weight average molecular weight of 100,000 to 1,000,000 and 50 to 200 parts by weight, based on 100 parts by weight of an unsaturated polyester oligomer (A) having a weight average molecular weight of 1,000 to 5,000. Polymerization initiator (C) 1.5 to 15 parts by weight and solvent (D) 50 to 30
An adhesive (1) consisting of 0 parts by weight and having a viscosity at 25 ° C. of 10,000 cps or less. 2. Based on 100 parts by weight of an unsaturated polyester oligomer (A) having a weight average molecular weight of 1000 to 5000, 50 to 200 parts by weight of an adhesive acrylic polymer (B) having a weight average molecular weight of 100,000 to 1 million, The composition has a viscosity of 1 to 0.015 to 15 parts by weight of a polymerization initiator (E) and 50 to 300 parts by weight of a solvent (D) at 25 ° C.
Adhesive (2) below 10,000 cps. 3. A two-component curable adhesive comprising the adhesive (1) and the adhesive (2). 4. The unsaturated polyester oligomer (A) is an oligomer obtained by ring-opening polymerization of a compound having a hydroxyl group, a cyclic acid anhydride and an epoxide having an ethylenically unsaturated group. Glue. 5. The adhesive acrylic polymer (B) comprises:
The adhesive according to any one of claims 1 to 4, which is an acrylic polymer having a glass transition point in the range of -40 to 0 ° C.