JP6868988B2 - Temporary fixing method of composition and member using it - Google Patents

Description

The present invention relates to compositions used to process various members. The present invention relates to a (meth) acrylic resin temporary fixing adhesive composition for temporary fixing, which is a method for temporary fixing / peeling when processing various members, and is suitable for the temporary fixing / peeling method. In particular, the present invention relates to a method and a peeling method for temporarily fixing the member when processing a member having a large area or a member having a thickness of 200 μm or less, which is difficult to be precision machined, and a temporary fixing adhesive composition suitable for the application.

Double-sided tape and hot-melt adhesives are used as temporary fixing adhesives for quartz, ceramics, glass, optical lenses, prisms, arrays, silicon wafers, semiconductor mounting parts, and the like. Members joined or laminated with these adhesives are cut into a predetermined shape, and then the adhesive is removed to manufacture the processed members. For example, in a semiconductor-mounted component, these components are fixed to a base material with double-sided tape, a desired component is cut, and the double-sided tape is further irradiated with ultraviolet rays to peel it off from the component. In the case of hot-melt adhesives, after joining the members, the adhesive is permeated into the gaps by heating, and then the desired parts are cut and heated to peel off the parts. Since the adhesive remains, the remaining adhesive needs to be cleaned with an organic solvent.

However, in the case of double-sided tape, it is difficult to obtain dimensional accuracy, the chipping property is inferior when processing parts due to its low adhesiveness, and it cannot be peeled off unless heat of 100 ° C or higher is applied. There was a challenge. Further, when peeling by ultraviolet irradiation, there is a problem that peeling cannot be performed if the adherend has poor transparency.

In the case of hot melt adhesives, it is necessary to use an organic solvent during cleaning after peeling, which is problematic from the viewpoint of protecting the global environment, and the cleaning process is complicated, so it is also workable. It was an issue.

In order to solve these drawbacks, Patent Document 1 is a photocurable adhesive composition characterized by controlling the glass transition temperature of a cured resin and adding an appropriate amount of a granular substance that does not dissolve in the resin composition. And a temporary fixing method using it has been proposed. However, there is no description about the composition of the present invention which can be peeled off even with a large-area adhesive and has no limitation on the members that can be used.

Patent Document 2 comprises a monofunctional monomer having a specific ethylenic double bond and a polymer substance having no polymerizable double bond in a specific molecule and having water solubility or swelling property due to water absorption. A temporary fixing method has been proposed in which a small article is temporarily fixed using an adhesive composition for temporary fixing, and then the small article is immersed in water and removed. However, the temporary fixing method using these adhesives has a problem that the working time becomes long for a member having a large area because the dissolution rate and the swelling rate of the adhesive at the time of removal are slow.

Further, Patent Document 3 describes a heat-removable adhesive that can be easily self-peeled due to a significant decrease in adhesiveness due to heat treatment after adhesion by adding organic heat-expandable particles to the adhesive at a specific ratio. It has been reported. However, since these adhesives have too strong adhesiveness, there is a problem that a large-area member cannot be peeled off even if it is heat-treated and cannot be put into practical use.

Patent Document 4 contains (a) a mono (meth) acrylate which does not contain a hydroxyl group, a carboxyl group and an epoxy group and has an aromatic ring, and (b) a fat ring which does not contain a hydroxyl group, a carboxyl group and an epoxy group. After bonding by adding organic heat-expandable particles in a specific ratio to an adhesive containing at least one of mono (meth) acrylates having a structure, the adhesiveness is significantly reduced by heat treatment and self-peeling is easily performed. Epoxide adhesives that can be produced have been reported. However, these adhesives have a low elastic modulus at the processing temperature, low dimensional accuracy, and because a granular substance for controlling the film thickness of the adhesive is not added at the time of bonding, the film thickness is organic heat. There is a problem that it depends on the particle size of the expandable particles, the dimensional accuracy at the time of processing is low, the chipping property is inferior, and it cannot be put into practical use.

Patent Documents 5 and 6 describe (a) an organic peroxide, (b) a curing accelerator that reacts with the organic peroxide to promote the polymerization of a monomer, and (c) a monofunctional (meth). A curable composition comprising an acrylate and (d) a polyfunctional (meth) acrylate, characterized in that (a) the organic peroxide is encapsulated in microcapsules, has been reported. Has been done. However, these adhesives have curability other than the components contained in the microcapsules by releasing the inclusion liquid containing the organic peroxide when the contained microcapsules are compressed and destroyed by an external force or the like. Since it reacts with the base of the composition and promotes curing, it cannot be peeled off even by heat treatment, and is not suitable as a temporary fixing adhesive used for processing.

Patent Document 7 reports a photocurable fixing material for producing a translucent hard substrate laminate and peeling it off after processing. However, in the example fixing material 2 of the photocurable fixing material, isobutane gas, which is a flammable gas contained in the organic heat-expandable particles, leaks during storage, so that it is necessary to ensure safety during storage. There is. No organic heat-expandable particles are added to the fixing material 1, the fixing material 3, and the fixing material 4 exemplified above. There is no description that the large-area member can be easily peeled off by adding the organic heat-expandable particles.

Patent Document 8 reports a photocurable and room temperature curable two-part adhesive composition containing organic heat-expandable particles for producing a translucent hard substrate laminate and peeling it after processing. ing. However, Patent Document 8 does not describe the elastic modulus at the processing temperature. Patent Document 8 does not describe application to a member having a thickness of 200 μm or less, which is difficult to be precision machined. Patent Document 8 does not describe the suppression of leakage of flammable gas from organic heat-expandable particles contained in the adhesive during storage.

International Publication No. 2008/018252 Pamphlet Japanese Patent No. 2973991 Japanese Patent No. 3629021 Japanese Patent No. 4886369 Japanese Unexamined Patent Publication No. 2008-174707 International Publication No. 2009/150727 Pamphlet International Publication No. 2013/084953 Pamphlet International Publication No. 2013/039226 Pamphlet

In order to solve these problems of the prior art, for example, it can be applied to a member having a large area or a member having a thickness of 200 μm or less, which is difficult to be precision machined. A temporary fixing adhesive composition having excellent environmental friendliness and storage safety has been desired.

That is, the present invention relates to (1) (1-1) imide (meth) acrylate and / or cyclic trimethylolpropane formal (meth) acrylate, (1-2) urethane (meth) acrylate, (1-3) (1). 100 parts by mass of (meth) acrylate containing polyfunctional (meth) acrylate other than -2) and (1-4) alkyl (meth) acrylate,
(2) Radical polymerization initiator 0.1 to 20 parts by mass,
(3) 1 to 40 parts by mass of organic heat-expandable particles, which are heat-expandable microcapsules in which butane and / or isobutane are encapsulated in microcapsules by an organic material of an outer shell.
(4) Particulate matter (excluding the above-mentioned (3) organic swelling particles) A composition containing 0.1 to 5 parts by mass.
(1) (meth) acrylate in 100 parts by weight of a (1-4) alkyl (meth) acrylate composition containing 3 to 20 parts by weight, (1) (meth) acrylate in 100 parts by weight, (1- 1) The composition containing 30 to 75 parts by mass, (1-2) 10 to 50 parts by mass, (1-3) 3 to 20 parts by mass, and (1-4) 3 to 20 parts by mass, and further. , (1) The (meth) acrylate is the composition containing a monofunctional (meth) acrylate other than (1-5) (1-1) and (1-4), and (1) (meth) acrylate. Of 100 parts by mass, (1-1) 30 to 75 parts by mass, (1-2) 10 to 50 parts by mass, (1-3) 3 to 20 parts by mass, (1-4) 3 to 20 parts by mass, ( 1-5) The composition contains 1 to 15 parts by mass, and (3) the temperature at which the volume of the organic heat-expandable particles can be expanded three times or more is 80 ° C. to 120 ° C. The composition is (3) an organic heat-expandable particle having a temperature at which the volume can be expanded three times or more at 85 ° C. to 95 ° C., and (4) granular. The composition is such that the average particle size of the substance is 15 to 80 μm, (1-4) the alkyl (meth) acrylate is lauryl (meth) acrylate, and (2) the radical polymerization initiator is (2). 2-1) The composition containing a photoradical polymerization initiator, (2) the composition in which the radical polymerization initiator is (2-2) a thermal radical polymerization initiator, and (2) radical polymerization initiation. The agent is the composition containing (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator, and further (5) the composition containing a reducing agent. It is a two-part composition containing (2-2) a thermal radical polymerization initiator in the first agent and (5) a reducing agent in the second agent. / Or the composition containing the (2-1) photoradical polymerization initiator as the second agent, and in the cured product of the composition, the tensile storage elasticity at 23 ° C. is 40 to 4500 MPa, and the tensile strength at 90 ° C. The composition having a storage elastic coefficient of 0.5 to 10 MPa, and an adhesive composition containing the composition, which is used for quartz bonding, ceramics bonding, silicon bonding, and glass bonding. The adhesive composition for adhering one or more of the adherends of the above, and the adhesive composition for adhering the adherend having a thickness of 200 μm or less, and the use is for temporary fixing. The temporary fixing adhesive composition, and the temporary fixing adhesive. The temporary fixing adhesive composition is cured by temporarily fixing the member using the agent composition, the temporarily fixed member is processed, and the processed adhesive is immersed in water to temporarily fix the member. It is a method of temporarily fixing a member for removing a cured body of the fixing adhesive composition. The member is temporarily fixed using the temporary fixing adhesive composition, the temporary fixing adhesive composition is cured, and the temporary fixing adhesive composition is cured. This is a method for temporarily fixing a member for removing a cured body of the adhesive composition for temporary fixing by processing a temporarily fixed member and heating the processed adhesive to 80 to 300 ° C. This is a method for manufacturing a member for removing an adhesive by temporarily fixing 2 to 100 members to be processed using an adhesive composition and then immersing the adhesive in water after processing. The temporary fixing adhesive. A bonded body that joins members via a composition, the bonded body in which the member is one or more of the group consisting of quartz, ceramics, silicon, and glass, and the member has a thickness of 200 μm or less. It is a body, and the area of the member after processing is 60 cm ² or more.

The present invention is excellent in workability and environmental friendliness, for example. The present invention has the property that the cured product of the temporary fixing adhesive composition is peeled off from the adherend even if the member has a large area or a member having a thickness of 200 μm or less, which is difficult to be precision machined (hereinafter, simply “). It has excellent peelability), no adhesive residue after peeling, good dimensional accuracy and chipping property, and a processed member can be obtained. According to the present invention, for example, during storage, there is little leakage of flammable gas from the organic heat-expandable particles contained in the adhesive, and the safety is high.

The present invention will be described below. The monofunctional (meth) acrylate refers to a (meth) acrylate having one (meth) acryloyl group. The polyfunctional (meth) acrylate refers to a (meth) acrylate having two or more (meth) acryloyl groups.

The composition of the present invention can be used as a curable resin composition. The curable resin composition of the present invention can be used as a temporary fixing adhesive composition. (1) 100 parts by mass means a total of 100 parts by mass of (1-1), (1-2), (1-3), (1-4), and (1-5) contained as necessary. Say. In the case of a two-agent type temporary fixing adhesive composition, (1) 100 parts by mass means (1) 100 parts by mass, which is the sum of the first agent and the second agent.

(1) The polymerizable vinyl derivative is (1-1) imide (meth) acrylate and / or cyclic trimethylolpropane formal (meth) acrylate, (1-2) urethane (meth) acrylate, (1-3) (1). It contains polyfunctional (meth) acrylates other than -2) and (1-4) alkyl (meth) acrylates. Further, the (1) polymerizable vinyl derivative may contain a monofunctional (meth) acrylate other than (1-5) (1-1) and (1-4).

(1-1) The imide (meth) acrylate and / or the cyclic trimethylolpropane formal (meth) acrylate is a monofunctional (meth) acrylate.
Among the imide (meth) acrylates, the imide (meth) acrylate of the formula (1) is preferable.

Hydrogen is preferable for R ^1. R ² is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. n is preferably 1 to 6, more preferably 1 to 3. In the formula (1), 2- (1,2-cyclohexanedicarboxyimide) ethyl (meth) acrylate is preferable.

The amount of imide (meth) acrylate and / or cyclic trimethylolpropane formal (meth) acrylate used is 30 to 30 parts by mass in (1) 100 parts by mass in terms of dimensional accuracy, chipping property, peelability, and safety during processing. 75 parts by mass is preferable, 40 to 70 parts by mass is more preferable, and 45 to 65 parts by mass is most preferable. By setting this range, the tensile elastic modulus at 23 ° C. is 40 to 4500 MPa, the dimensional accuracy and chipping property at the time of processing are excellent, and the tensile storage elastic modulus at 90 ° C. is 0.5 to 10 MPa, which is organic at the time of peeling. The system thermally expandable particles expand and have excellent peelability. Furthermore, leakage of flammable gas from organic heat-expandable particles contained in the adhesive during storage can be suppressed.

(1-2) Urethane (meth) acrylate refers to (meth) acrylate having a urethane bond. As the urethane (meth) acrylate, urethane (meth) acrylate having two or more (meth) acryloyl groups at the terminal or side chain of the molecule is preferable. The urethane (meth) acrylate can be obtained by reacting a polyol compound (hereinafter, represented by X), an organic polyisocyanate compound (hereinafter, represented by Y), and a hydroxy (meth) acrylate (hereinafter, represented by Z). , Urethane (meth) acrylate is preferable. The method for producing urethane (meth) acrylate is described in, for example, JP-A-7-25957, JP-A-2002-173515, JP-A-7-292048, JP-A-2000-351819 and the like.

Examples of the polyol compound include polyhydric alcohols, polyether polyols, polyester polyols and the like.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol. 3-Methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, Examples thereof include polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polybutadiene polyol, and hydrogenated polybutadiene polyol. The polybutadiene polyol means a polybutadiene having two or more hydroxyl groups, for example, a polybutadiene having hydroxyl groups at both ends. The hydrogenated polybutadiene polyol means a hydrogenated polybutadiene having two or more hydroxyl groups, and for example, a hydrogenated polybutadiene having hydroxyl groups at both ends. Of the polyhydric alcohols, ethylene glycol and / or 1,4-butanediol are preferred.

Examples of the polyether polyol include polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol, polyethylene oxide, polypropylene oxide, and ethylene oxide / propylene. Examples thereof include a polyether polyol having at least one structure of block of oxide or random copolymerization. Among the polyether polyols, polyalkylene glycol is preferable.

Examples of the polyester polyol include a polyester polyol which is a condensate of a polyhydric alcohol or a polyether polyol and a polybasic acid. Examples of the polyhydric alcohol or polyether polyol used in the production of the polyester polyol include the above-mentioned compounds. Examples of the polybasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid and the like. Among the polybasic acids, adipic acid is preferable.

The organic polyisocyanate compound (Y) does not have to be particularly limited, but for example, aromatic, aliphatic, cyclic aliphatic, alicyclic polyisocyanates and the like can be used, and among them, triisocyanate. Ranged Isocyanate (TDI), Diphenylmethane Diisocyanate (MDI), Hydrogenated Diphenylmethane Diisocyanate (H-MDI), Polyphenylmethane Polyisocyanate (Crude MDI), Modified Diphenylmethane Diisocyanate (Modified MDI), Hydrogenated Xylylene Diisocyanate (H-) XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1, Polyisocyanates such as 3-bis (isocyanatomethyl) cyclohexane (H6XDI), trimeric compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, and the like are preferably used. Among these, one or more of the group consisting of tolylene diisocyanate (TDI), hydrogenated xylylene diisocyanate (H-XDI) and isophorone diisocyanate (IPDI) is preferable, and isophorone diisocyanate is more preferable.

Examples of the hydroxy (meth) acrylate (Z) include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate, and 2-. Hydroxyethyl (meth) acryloyl phosphate, 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, glycerindi (meth) acrylate, 2-hydroxy-3- (meth) acrylic Examples thereof include leuroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified 2-hydroxyethyl (meth) acrylate. Of these, hydroxyalkyl (meth) acrylates are preferred. Among the hydroxyalkyl (meth) acrylates, one or more of the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate is preferable, and 2-hydroxyethyl is preferable. (Meta) acrylate is more preferred.

Among urethane (meth) acrylates, polyester-based urethane (meth) acrylate and / or polyether-based urethane (meth) acrylate are preferable in terms of low viscosity and good workability, and polyether-based urethane (meth) acrylate is preferable. Acrylate is more preferred. In the polyester urethane (meth) acrylate, the polyol compound is a polyester polyol compound. In the polyether urethane (meth) acrylate, the polyol compound is a polyether polyol compound.

The polyester-based urethane (meth) acrylate has two or more (meth) acryloyl groups at the end or side chain of the molecule and has a polyester structure in the molecule. The polyester urethane (meth) acrylate is a reaction between a polyester polyol compound (hereinafter, represented by X), an organic polyisocyanate compound (hereinafter, represented by Y) and a hydroxy (meth) acrylate (hereinafter, represented by Z). Refers to urethane (meth) acrylate obtained by.

Examples of the polyester polyol compound (X) include a polyester polyol which is a condensate of a polyhydric alcohol or a polyether polyol and a polybasic acid. Among the polyhydric alcohols or polyether polyols used for producing polyester-based urethane (meth) acrylates, polyhydric alcohols are preferable. Among the polyhydric alcohols, one or more of the group consisting of ethylene glycol, 1,4-butanediol, and hydrogenated polybutadiene polyol is preferable.

Examples of the polyester-based urethane (meth) acrylate include "UV-3000B" manufactured by Nippon Synthetic Chem Industry Co., Ltd.

The polyether urethane (meth) acrylate has two or more (meth) acryloyl groups at the terminal or side chain of the molecule, and has a polyether structure in the molecule. The polyether urethane (meth) acrylate is a reaction between a polyether polyol compound (hereinafter, represented by X), an organic polyisocyanate compound (hereinafter, represented by Y) and a hydroxy (meth) acrylate (hereinafter, represented by Z). It refers to urethane (meth) acrylate obtained by allowing it to be mixed.

Examples of the polyether polyol compound (X) include the above-mentioned polyether polyol compound (X). Among the polyether polyols, polyalkylene glycol is preferable. Among the polyalkylene glycols, polypropylene glycol is preferable.

Examples of the polyether urethane (meth) acrylate include "UV-3700B" manufactured by Nippon Synthetic Co., Ltd., "UN-6200" manufactured by Negami Kogyo Co., Ltd., and "UN-6202" manufactured by Negami Kogyo Co., Ltd.

(1-2) The molecular weight of the urethane (meth) acrylate is preferably 1000 to 50000, more preferably 5000 to 45000, and most preferably 1500 to 40,000 in that the effect is large. The weight average molecular weight is determined by using tetrahydrofuran as a solvent, using a GPC system (SC-8010 manufactured by Tosoh Corporation) or the like, and preparing a calibration curve with commercially available standard polystyrene under the following conditions.

Flow velocity: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: Tosoh "TSK guardcolum MP (xL)" 6.0 mm ID x 4.0 cm 1 piece, Tosoh "TSK-GEL MULTIPOREHXL-M" 7.8 mm ID x 30.0 cm (theoretical plate number 16,000) ) 2 pieces, 3 pieces in total (32,000 theoretical plates as a whole)
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid transfer pressure: 39 kg / cm ²
Detector: RI detector

(1-2) The amount of urethane (meth) acrylate used is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and 20 parts by mass, out of (1) 100 parts by mass, in terms of workability and peelability. ~ 40 parts by mass is most preferable. If it is less than 10 parts by mass, the effect may be small, and if it exceeds 50 parts by mass, the viscosity becomes high, the workability when used as an adhesive composition is inferior, the tensile storage elastic modulus at 90 ° C. exceeds 10 MPa, and peeling occurs. Occasionally, the expansion of organic heat-expandable particles is hindered, resulting in poor peelability.

(1-3) Polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyl groups in the molecule, and refers to polyfunctional (meth) acrylate other than (1-2). Examples of the polyfunctional (meth) acrylate include a bifunctional (meth) acrylate monomer, a trifunctional (meth) acrylate monomer, and a tetrafunctional or higher functional (meth) acrylate monomer. Among the polyfunctional (meth) acrylates, a bifunctional (meth) acrylate monomer is preferable.

Examples of the bifunctional (meth) acrylate monomer include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, and 1,9-. Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, neopentyl glycol-modified trimethylolpropandi (meth) acrylate, stearic acid-modified pentaeristoldi (meth) Acrylate, Tripropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4- (meth) acrylic) Loxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxitetraethoxyphenyl) propane, dimethylol-tricyclodecanedi (meth) acrylate, 1,10-decanediol di (meth) acrylate, isocyanuric acid Examples thereof include ethylene oxide modified di (meth) acrylate. Among these, one or more of the group consisting of tripropylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and polypropylene glycol di (meth) acrylate is preferable in terms of large effect, and tripropylene glycol is preferable. Di (meth) acrylate is more preferred.

Examples of the trifunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, and the like.

Examples of the tetrafunctional or higher functional (meth) acrylate monomer include dimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Examples thereof include stall hexa (meth) acrylate.

The amount of (1-3) used is preferably 3 to 20 parts by mass, more preferably 4 to 18 parts by mass, and most preferably 5 to 15 parts by mass out of (1) 100 parts by mass in terms of peelability. If it is less than 3 parts by mass, the effect may be small, and if it exceeds 20 parts by mass, the tensile storage elastic modulus at 90 ° C. exceeds 10 MPa, and the expansion of the organic heat-expandable particles is hindered at the time of peeling, resulting in poor peelability. There is.

As the (1-4) alkyl (meth) acrylate, for example, a monofunctional (meth) acrylate represented by the following formula (2) can be preferably used. By using the alkyl (meth) acrylate, leakage of flammable gas from the organic heat-expandable particles contained in the adhesive during storage can be suppressed.
CH ₂ = C (R ⁴ ) COOR ⁵ ... Equation (2)

^{Here, R 4} in the formula (2) is a hydrogen atom or a methyl group. R ⁵ is an alkyl group. R ⁵ is preferably a chain alkyl group having 1 to 22 carbon atoms (hereinafter, such a range of carbon atoms may be referred to as “C1-22”). Dimensional accuracy during machining, chipping resistance, peel properties, in terms of suppressing leakage of the combustible gas from organic-based heat expandable particles included in the adhesive during storage, R ⁴ is preferably a hydrogen atom, R ⁵ is C8 A chain alkyl group of -12 is preferred. If R ⁵ is a C8-12 chain alkyl group, leakage of flammable gas from the organic heat-expandable particles can be suppressed.

As the alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl ( Meta) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) Meta) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) Acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate, ecocil (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Examples thereof include isostearyl (meth) acrylate and behenyl (meth) acrylate. Examples of the alkyl (meth) acrylate in which R ⁵ is a chain alkyl group of C8-12 include octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, and decyl (meth) acrylate. , Isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate and the like. These alkyl (meth) acrylates can be used in combination of one or more. Among these, lauryl (meth) acrylate and / or octyl (meth) acrylate is preferable, and lauryl (meth) acrylate is more preferable.

(1-4) The amount of alkyl (meth) acrylate used is dimensional accuracy during processing, chipping property, peelability, and suppression of leakage of flammable gas from organic heat-expandable particles contained in the adhesive during storage. In terms of (1) 100 parts by mass, 3 to 20 parts by mass is preferable, 4 to 18 parts by mass is more preferable, and 5 to 15 parts by mass is most preferable. If it is less than 3 parts by mass, the effect of suppressing leakage of flammable gas may be small, and if it exceeds 20 parts by mass, the effect of dimensional accuracy and chipping property at the time of processing may be small.

(1) The polymerizable vinyl derivative may further contain a monofunctional (meth) acrylate other than (1-5) (1-1) and (1-4).
Among the monofunctional (meth) acrylates other than (1-5) (1-1) and (1-4), phenol (ethylene oxide 2 mol-modified) (meth) acrylate and methoxytriethylene glycol (meth) acrylate And one or more of the group consisting of methoxypolyethylene glycol (meth) acrylate are preferable.
The amount of (1-5) used is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, and 5 to 8 parts out of 100 parts by mass of (1) in terms of dimensional accuracy, chipping property, and peelability. The mass part is the most preferable. When the amount of (1-5) used is in this range, the tensile storage elastic modulus at 23 ° C. is 40 to 4500 MPa, which is excellent in dimensional accuracy and chipping property during processing, and the tensile storage elastic modulus at 90 ° C. is 0.5. It is 10 MPa and has excellent peelability.
(1) When the polymerizable vinyl derivative contains (1-1), (1-2), (1-3), and (1-4), (1) in 100 parts by mass of the polymerizable vinyl derivative, (1) It preferably contains (1-1) 30 to 75 parts by mass, (1-2) 10 to 50 parts by mass, (1-3) 3 to 20 parts by mass, and (1-4) 3 to 20 parts by mass. It is more preferable to contain 1-1) 40 to 70 parts by mass, (1-2) 15 to 45 parts by mass, (1-3) 4 to 18 parts by mass, and (1-4) 4 to 18 parts by mass. Most preferably, it contains (1-1) 45 to 65 parts by mass, (1-2) 20 to 40 parts by mass, (1-3) 5 to 15 parts by mass, and (1-4) 5 to 15 parts by mass. ..
(1) When the polymerizable vinyl derivative contains (1-1), (1-2), (1-3), (1-4), (1-5), (1) the polymerizable vinyl derivative Of 100 parts by mass, (1-1) 30 to 75 parts by mass, (1-2) 10 to 50 parts by mass, (1-3) 3 to 20 parts by mass, (1-4) 3 to 20 parts by mass, ( 1-5) It is preferable to contain 1 to 15 parts by mass, (1-1) 40 to 70 parts by mass, (1-2) 15 to 45 parts by mass, (1-3) 4 to 18 parts by mass, (1-5) 1-4) 4 to 18 parts by mass, (1-5) 3 to 10 parts by mass, more preferably (1-1) 45 to 65 parts by mass, (1-2) 20 to 40 parts by mass, Most preferably, it contains (1-3) 5 to 15 parts by mass, (1-4) 5 to 15 parts by mass, and (1-5) 5 to 8 parts by mass.

As the (2) radical polymerization initiator, (2-1) photoradical polymerization initiator and / or (2-2) thermal radical polymerization initiator is preferable, and (2-1) photoradical polymerization initiator and (2-2-). 2) It is preferable to use a thermal radical polymerization initiator in combination.
(2) The amount of the radical polymerization initiator used is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to (1) 100 parts by mass.

(2-1) The photoradical polymerization initiator is used to promote photocuring of the composition by sensitizing it with active light of visible light or ultraviolet light.

Examples of the photoradical polymerization initiator include benzophenone and its derivatives, benzyl and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin derivatives such as benzyl dimethyl ketal, and di. Acetphenone derivatives such as ethoxyacetophenone and 4-t-butyltrichloroacetonone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and its derivatives, camphorquinone, 7,7-methyl-2,3- Dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-bromoethyl ester, 7 , 7-Dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] Benzoyl quinone derivatives such as heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( Α-Amino such as 4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one Alkylphenone derivative, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyposphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldi Acylphosphine oxide derivatives such as ethoxyphenylphosphine oxide, oxy-phenyl-acetylid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetylid 2- [2-hydroxy -Ethoxy] -ethyl ester and the like can be mentioned. One or more photoradical polymerization initiators can be used in combination. Among these, benzoin derivatives are preferable because they have a large effect. Among the benzoin derivatives, benzyldimethyl ketal is preferable because it has a large effect.

The amount of the (2-1) photoradical polymerization initiator used is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to (1) 100 parts by mass. Within this range, the effect of promoting curing can be surely obtained.

In the present invention, (2-2) thermal radical polymerization initiator may be used.

(2-2) As the thermal radical polymerization initiator, an organic or inorganic peroxide is preferable, and an organic peroxide is more preferable. Examples of organic peroxides include diacyl peroxides such as t-lauroyl peroxide and benzoyl peroxide, t-butylperoxy-3,5,5-trimethylhexanoate, cumylperoxyneodecanoate, and hexylper. Alkylpers such as oxyvivalate, t-butylperoxyisobutyrate, t-butylperoxybivalate, t-butylperoxyacetate, t-butylperoxybenzoate, tertiary butylperoxy-2-ethylhexanate, etc. Oxyesters, diisopropyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, dinormal propyl peroxy dicarbonate, bis (4-terriary butylcyclohexyl) peroxy dicarbonate, di-2-ethoxyethyl peroxy Peroxydicarbonates such as dicarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and diallyl peroxydicarbonate, peroxy such as t-butylperoxyisopropylcarbonate Carbonates, peroxyketals such as di-t-butylperoxycyclohexane, di- (t-butylperoxy) butane, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide Dialkyl peroxides such as, cumene hydroperoxide, hydroperoxides such as tetramethylbutyl hydroperoxide, and ketone peroxides such as ketone peroxide and cyclohexanone peroxide. Among these, alkyl peroxy esters and / or hydroperoxides are preferable, and hydroperoxides are more preferable. Among the hydroperoxides, cumene hydroperoxide is the most preferable.

(2-2) The amount of the thermal radical polymerization initiator used is preferably 0.1 to 5 parts by mass, more preferably 1 to 3 parts by mass with respect to (1) 100 parts by mass. If it is 0.1 part by mass or more, curability is surely obtained, and if it is 5 parts by mass or less, sufficient storage stability is obtained and skin irritation is lowered.

(3) As the organic heat-expandable particles, organic heat-expandable particles containing butane and / or isobutane are preferable.

(3) Examples of the organic heat-expandable particles include heat-expandable microcapsules in which butane and / or isobutane is encapsulated in microcapsules by an organic material (polymer) of an outer shell. (3) As the organic heat-expandable particles, heat-expandable microcapsules in which butane and / or isobutane in the inner shell are wrapped in an outer shell are preferable. (3) The organic heat-expandable particles are particles in which the organic material in the outer shell is softened by heating and the butane and / or isobutane in the inner shell expands. As the organic material of the outer shell, a thermoplastic resin is preferable. Among the thermoplastic resins, a polymer or copolymer of one or more monomers in the group consisting of vinylidene chloride, (meth) acrylonitrile, and methyl (meth) acrylate is preferable, and a polymer or copolymer containing vinylidene chloride is preferable. Is more preferable. When vinylidene chloride is used, it is difficult to be compatible with the matrix composition, so that butane and / or isobutane in the inner shell is less likely to leak from the outer shell during storage, and is excellent in safety.

(3) There is no particular limitation on the heat expansion property of the organic heat-expandable particles, but in terms of peelability and suppression of leakage of flammable gas from the organic heat-expandable particles contained in the adhesive during storage, 3 The temperature at which the volume can be expanded more than twice is preferably 80 ° C. to 120 ° C., more preferably in the range of 85 ° C. to 100 ° C., and even more preferably in the range of 85 ° C. to 95 ° C. If the temperature at which volume expansion is possible three times or more is less than 80 ° C, it may be inferior in terms of suppressing leakage of flammable gas, and the temperature at which volume expansion is possible three times or more is 120 ° C or more. Expandable particles may be inferior in releasability.

For heat expansion, ethylene vinegar-based emulsion and organic heat-expandable particles are mixed at a solid content ratio of 2: 1 and coated on a test paper so as to have a thickness of 100 μm when dried, and 80 ° C., 85 ° C., 90 ° C., 95 ° C. A heat foaming test was conducted in an oven adjusted to ° C., 100 ° C., 105 ° C., 110 ° C., 115 ° C., and 120 ° C., and the temperature expanded more than 3 times after 1 minute was increased to 3 times or more. Set to a possible temperature.

(3) The average particle size of the organic heat-expandable particles is preferably 2 to 50 μm, preferably 5 to 30 μm, and most preferably 8 to 20 μm. If it is 2 μm or more, the peelability of the composition is excellent, and if it is 100 μm or less, the adhesiveness of the composition before peeling does not decrease.

(3) The amount of the organic heat-expandable particles used is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass with respect to (1) 100 parts by mass, in terms of promotion of peeling and adhesiveness. 8 to 20 parts by mass is most preferable. If it is 1 part by mass or more, the effect of promoting peeling can be surely obtained, and if it is 40 parts by mass or less, sufficient adhesiveness can be obtained.

(4) As the particulate matter, a particulate matter having an average particle size of 15 to 80 μm is preferable. As the particulate matter having an average particle diameter of 15 to 80 μm, a particulate matter having an average particle diameter of 15 to 80 μm measured by a laser method is preferable. By using a particulate matter with an average particle size of 15 to 80 μm (hereinafter sometimes referred to as a particulate matter), it becomes easy for the cured product to maintain a constant thickness, and even a member having a thickness of 200 μm or less has dimensions. It can be processed with improved accuracy and chipping property, and stable peelability can be obtained by controlling the thickness of the cured product. The average particle size is more preferably 15 to 40 μm in terms of dimensional accuracy and chipping property.

(4) The particulate matter may be either organic particles or inorganic particles. Particulate matter refers to those excluding the above-mentioned (3) organic heat-expandable particles. Examples of the organic particles include polyethylene particles, polypropylene particles, crosslinked poly (meth) methyl acrylate particles, crosslinked polystyrene particles, and crosslinked poly (meth) methyl acrylate copolymer particles. Examples of the inorganic particles include ceramic particles such as glass, silica, alumina, and titanium.

(4) The particulate matter is preferably spherical in terms of improving processing accuracy, that is, controlling the film thickness of the composition. Among the organic particles, cross-linked poly (meth) methyl acrylate particles, cross-linked polystyrene particles, and cross-linked poly (meth) acrylic acid are characterized in that the deformation of the particles is small and the thickness of the cured product does not vary due to the variation in particle size. One or more of the group consisting of methyl polystyrene copolymer particles is preferable. The crosslinked poly (meth) methyl acrylate particles, the crosslinked polystyrene particles, and the crosslinked poly (meth) methyl acrylate copolymer particles are known as, for example, a (meth) methyl acrylate monomer or a styrene monomer, and a crosslinkable monomer. It is obtained as monodisperse particles by polymerizing by the emulsification polymerization method of. As the inorganic particles, spherical silica is preferable because there is little deformation of the particles and there is little variation in the film thickness of the cured product due to variations in particle size. Among these, organic particles are preferable in terms of storage stability due to sedimentation of the particles and the reactivity of the composition.

The particle size in the present invention can be measured by, for example, the "laser diffraction type particle size distribution measuring device SALD-2200" manufactured by Shimadzu Corporation.

(4) The amount of the granular substance used is preferably 0.1 to 5 parts by mass with respect to (1) 100 parts by mass, and is 0.2 to 0, in terms of dimensional accuracy, chipping property, and peelability during processing. 8.8 parts by mass is more preferable.

In the present invention, when (2-2) a thermal radical polymerization initiator is used, it is preferable to use (5) a reducing agent in combination.

The (5) reducing agent is preferably one that reacts with the (2-2) thermal radical polymerization initiator to generate radicals.

Examples of the reducing agent include transition metal salts such as copper naphthenate, vanadium acetylacetonate, cobalt octylate and copper acetate, tertiary amines such as N, N-dimethylaniline and N, N-dimethyl-p-toluidine, and thiourea. , Ethylene thiourea, organic thiourea such as acetyl thiourea, and the like. Of these, transition metal salts are preferred. Among the transition metal salts, one or more of the group consisting of vanadium acetylacetonate, copper naphthenate, and cobalt octylate is preferable, and vanadium acetylacetonate and / or cobalt octylate is more preferable.

(5) The amount of the reducing agent used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to (1) 100 parts by mass. If it is 0.1 part by mass or more, curability can be surely obtained, and if it is 5 parts by mass or less, sufficient storage stability can be obtained.

In the present invention, (6) a polymerization inhibitor may be used in order to improve storage stability. Polymerization inhibitors include methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-terrary butylphenol), catechol, hydroquinone monomethyl ether, monoterrical butyl hydroquinone, 2,5-ditercious butyl hydroquinone. , P-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditershally butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butyl catechol, 2-butyl-4-hydroxyanisole and 2 , 6-Ditercious butyl-p-cresol and the like. Among these, 2,2-methylene-bis (4-methyl-6-terrary butylphenol) and / or citric acid are preferable in terms of their large effect.

The amount of the polymerization inhibitor used is preferably 0.001 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and most preferably 0.1 to 0.3 parts by mass with respect to (1) 100 parts by mass. preferable. If it is 0.001 part by mass or more, storage stability is ensured, and if it is 3 parts by mass or less, good adhesiveness is obtained and it does not become uncured.

The viscosity of the composition of the present invention is preferably 500 to 50,000 mPa · s, and more preferably 1500 to 30,000 mPa · s, in terms of storage stability, as measured by a B-type viscometer at 25 ° C. It is preferably 2000 to 15000 mPa · s, and even more preferably 2500 to 15000 mPa · s. Within this range, the organic heat-expandable particles in the composition will not separate during storage and will not become unusable.

The composition of the present invention contains various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, solvents such as polar organic solvents, extenders, and reinforcements, which are generally used, as long as the object of the present invention is not impaired. Additives such as materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.

The present invention can be used as a temporary fixing adhesive composition.

When the temporary fixing adhesive composition of the present invention contains (2-2) a thermal radical polymerization initiator and (5) a reducing agent, the first agent contains at least (2-2) a thermal radical polymerization initiator. , It is preferable to use it as a two-part type temporary fixing adhesive composition containing at least (5) a reducing agent in the second agent. For the two-dosage form, all the essential components of the temporary fixing adhesive composition of the present invention may not be mixed during storage, and the temporary fixing adhesive composition may be stored separately as the first agent and the second agent. preferable. In this case, both agents can be applied to the members at the same time or separately, contacted and cured, so that they can be used as a two-agent type temporary fixing adhesive composition. When used as a two-dosage form, (2-1) photoradical polymerization initiator, (3) organic heat-expandable particles, and (4) particulate matter can be used in either or both of the first agent and the second agent. May contain. In the two-agent type temporary fixing adhesive composition, the composition can be cured only by mixing the two agents.

The method of using the two-agent type temporary fixing adhesive composition is as follows. As a method of using the two-agent type temporary fixing adhesive composition, an appropriate amount of the temporary fixing adhesive composition is applied to the adhesive surface of one member to be fixed, and then the other member is overlapped. , A large number of members to be temporarily fixed are laminated in advance, and the temporary fixing adhesive composition is applied by a method of permeating the temporary fixing adhesive composition into the gap and applying the temporary fixing adhesive composition. Examples thereof include a method of curing and temporarily fixing the members to each other.

The two-dose temporary fixing adhesive composition does not require accurate weighing of the two agents and cures at room temperature even with incomplete weighing and mixing, and sometimes even contact between the two agents. The temporary fixing adhesive composition of the present invention is excellent in workability.

When both agents are applied to the members simultaneously or separately, contacted and cured, and the members are temporarily fixed to each other, the two agents are mixed and applied to the members, and then allowed to stand at room temperature for 0.5 to 500 hours, for example. Therefore, it is preferable to bond the members together. If it is 0.5 hours or more, the temporary fixing adhesive composition is cured and sufficient adhesiveness is obtained, and if it is 500 hours or less, sufficient adhesiveness is obtained. The standing time for temporarily fixing the members is more preferably 4 to 300 hours, further preferably 24 to 200 hours, and most preferably 50 to 100 hours. The normal temperature means, for example, 10 to 40 ° C.

Further, in the two-agent type temporary fixing adhesive composition, when the (2-1) photoradical polymerization initiator is contained in either or both of the first agent and the second agent, the two agents are used. After mixing and bonding the members together, a part or all of the members are irradiated with visible light or ultraviolet rays for 1 to 60 seconds to be easily bonded. In this step, since it is not necessary to completely cure, an amount of light energy ^{of 1 to 500 mJ / cm 2 at a wavelength of 365 nm is sufficient.} After this step, the (2-2) thermal radical polymerization initiator and (5) reducing agent react with each other to completely cure and obtain sufficient adhesiveness.

As a temporary fixing method using the temporary fixing adhesive composition of the present invention, the temporary fixing adhesive composition is obtained by immersing the adhesive in water after using the temporary fixing method by mixing the two agents described above. The cured product of the product is softened, whereby the organic heat-expandable particles easily expand, water penetrates into the interface between the member and the temporary fixing adhesive composition, and the cured product can be peeled off more easily. The higher the temperature of the water, the larger the expansion of the organic heat-expandable particles, so that the water easily invades and the cured product can be easily peeled off. The temperature of water when removing the cured product is preferably more than 40 ° C., more preferably 60 ° C. or higher, most preferably 80 to 100 ° C., and even more preferably 90 to 100 ° C. in terms of peelability. The immersion time is preferably 1 to 240 minutes, more preferably 2 to 200 minutes, and most preferably 5 to 180 minutes.

As a temporary fixing method using the temporary fixing adhesive composition of the present invention, after using the temporary fixing method by mixing the two agents described above, the adhesive is heated to 80 to 300 ° C. for temporary fixing. The cured product of the adhesive composition softens, which easily expands the organic heat-expandable particles, creating voids at the interface between the member and the cured product of the temporary fixing adhesive composition, making the cured product easier. Can be peeled off. When the heating temperature is high, the expansion of the organic heat-expandable particles is large, so that the cured product can be easily peeled off. The heating temperature at the time of removing the cured product is more preferably 100 to 260 ° C., most preferably 130 to 200 ° C. in terms of peelability. The heating time is preferably 1 to 240 minutes, more preferably 10 to 120 minutes, and most preferably 15 to 60 minutes.

Lamination is performed, for example, by bonding each member coated with the temporary fixing adhesive composition to one bonding surface or both bonding surfaces, and then spreading between the two members. It can be carried out by allowing the composition to cure at room temperature. By repeating this a desired number of times, a laminated body in which a desired number of members are laminated can be produced. The standing at room temperature may be carried out every time one member is laminated, or may be carried out collectively after laminating a plurality of members. From the viewpoint of workability, the number of laminated sheets is preferably 2 to 100, more preferably 3 to 50, and most preferably 4 to 20.

(2-1) When a photoradical polymerization initiator is used, the composition is cured by irradiating it with visible light or ultraviolet rays. Examples of the method of adhering the members to each other include an adhering method of irradiating the temporary fixing adhesive composition with at least one of visible light and ultraviolet rays to enhance the adhesiveness. Examples of the energy irradiation source for irradiating such visible light or ultraviolet rays include deuterium lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, low-pressure mercury lamps, xenon lamps, xenon-mercury mixed lamps, halogen lamps, excimer lamps, and the like. Examples include energy irradiation sources such as indium lamps, tallium lamps, LED lamps, and electrodeless discharge lamps.

(2-1) The method of using the temporary fixing adhesive composition (one-agent type temporary fixing adhesive composition) containing a photoradical polymerization initiator is as follows.

When the temporary fixing adhesive composition is cured by irradiating visible light or ultraviolet rays to temporarily fix the member, a light energy amount of 10 to ^{15000 mJ / cm 2 is applied to the temporary fixing adhesive composition at a wavelength of 365 nm.} It is preferable to irradiate and bond the members to each other. If it is 10 mJ / cm ² or more, the temporary fixing adhesive composition is sufficiently cured, ^{and if it is 15000 mJ / cm 2} or less, there is no curing distortion and the adhesiveness is improved. Light energy at the time of temporarily fixed member each other, in terms of adhesion, more preferably ^{1000~10000mJ / cm 2, 2000~4000mJ / cm} 2 being most preferred.

As a temporary fixing method using the temporary fixing adhesive composition of the present invention, the temporary fixing adhesive composition is prepared by immersing the adhesive in water after using the above-mentioned temporary fixing method using light energy. The cured product is softened, whereby the organic heat-expandable particles easily expand, and water penetrates into the interface between the member and the temporarily fixed adhesive composition cured product, so that the cured product can be peeled off more easily. When the temperature of water is high, the expansion of the organic heat-expandable particles is large, so that water easily invades and the cured product can be easily peeled off. The temperature of water when removing the cured product is preferably more than 40 ° C., more preferably 60 ° C. or higher, most preferably 80 to 100 ° C., and even more preferably 90 to 100 ° C. in terms of peelability. The immersion time is preferably 1 to 240 minutes, more preferably 2 to 200 minutes, and most preferably 5 to 180 minutes.

As a temporary fixing method using the temporary fixing adhesive composition of the present invention, a temporary fixing adhesive is used by heating the adhesive body to 80 to 300 ° C. after using the above-mentioned temporary fixing method using light energy. The cured product of the composition is softened, whereby the organic heat-expandable particles easily expand, and voids are formed at the interface between the cured product and the temporary fixing adhesive composition, so that the cured product can be peeled off more easily. The higher the heating temperature, the larger the expansion of the organic heat-expandable particles, so that the cured product can be easily peeled off. The heating temperature at the time of removing the cured product is more preferably 100 to 260 ° C., most preferably 130 to 200 ° C. in terms of peelability. The heating time is preferably 1 to 240 minutes, more preferably 10 to 120 minutes, and most preferably 15 to 60 minutes.

Lamination is performed, for example, by bonding each member coated with the temporary fixing adhesive composition to one bonding surface or both bonding surfaces, and then spreading between the two members. It can be carried out by irradiating light to cure the composition. By repeating this a desired number of times, a laminated body in which a desired number of members are laminated can be produced. The light irradiation may be carried out every time one member is laminated, or may be carried out collectively after laminating a plurality of members as long as the light reaches the temporary fixing adhesive composition. From the viewpoint of workability, the number of laminated sheets is preferably 2 to 100, more preferably 3 to 50, and most preferably 4 to 20.

In the present invention, the material of the member used for temporary fixing is not particularly limited, and examples thereof include quartz, ceramics, silicon, quartz, glass, and plastic. Among these, one or more of the group consisting of quartz, ceramics, silicon and glass is preferable.

The thickness of the member is preferably 3000 μm or less, more preferably 2000 μm or less, most preferably 500 μm or less, and even more preferably 200 μm or less. The thickness of the member is preferably 50 μm or more, more preferably 100 μm or more.

Such a member has a problem that it is easily cracked and chipping is likely to occur. Even such a member can be processed and peeled by the temporary fixing method of the present invention. Even if the member has a thickness of 200 μm or less, which is difficult to be precision machined, or the member has an adhesive area of 60 cm ² or more, which is difficult to peel off, the temporary fixing method of the present invention can be used for processing and peeling. It is possible.

The temporarily fixed member is subjected to processing such as cutting, grinding, polishing, and drilling in order to obtain a desired shape, and then the member is immersed in water, preferably warm water, or heated. , The cured product of the temporary fixing adhesive composition can be peeled off from the member.

In the present invention, the tensile storage elastic modulus at 23 ° C. is 40 to 4500 MPa, and the tensile storage elastic modulus at 90 ° C. is 0.5 to 10 MPa. The tensile storage elastic modulus is the tensile storage elastic modulus of the cured product obtained from the matrix composition. The tensile storage elastic modulus is measured by dynamic viscoelasticity measurement.

The matrix composition refers to (3) a composition that does not contain organic heat-expandable particles. The matrix composition is a composition containing (1) and (2). When (1) of the matrix composition contains (1-5), it contains (1-5). When the matrix composition contains (4) to (6), it contains (4) to (6).

If the tensile storage elastic modulus at 23 ° C is in the range of 40 to 4500 MPa, the dimensional accuracy and chipping property during processing are excellent, and if the tensile storage elastic modulus at 90 ° C is in the range of 0.5 to 10 MPa, the adhesive for temporary fixing is adhered. When the cured product of the agent composition is peeled from the member, the organic heat-expandable particles expand and have excellent peelability. The tensile storage elastic modulus at 23 ° C. is more preferably 300 to 3500 MPa in terms of dimensional accuracy and chipping property during processing, and the tensile storage elastic modulus at 90 ° C. is preferably 0.5 to 10 MPa in terms of peelability. ~ 7 MPa is more preferable. If the tensile storage elastic modulus at 90 ° C. is less than 0.5 MPa, the matrix cannot follow the expansion of the organic heat-expandable particles at the time of peeling, and only the organic heat-expandable particles expand, and the cured product obtained from the composition. May be inferior in peelability because it does not expand. If the tensile storage elastic modulus of the cured product at 90 ° C. exceeds 10 MPa, the expansion of the organic heat-expandable particles may be hindered at the time of peeling, resulting in poor peelability.

The method for measuring the glass transition temperature of the cured product obtained from the matrix composition of the present invention is not particularly limited, but it is measured by a known method such as DSC or dynamic viscoelastic spectrum. A preferred method is a dynamic viscoelastic spectrum method.

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

(Examples 1 to 8, Comparative Examples 1 to 4)
It was evaluated by the following method.

(Preparation of adhesive composition)
The materials used in Table 1 were used. Each material used was mixed with the compositions shown in Tables 2 to 3 to prepare an adhesive composition consisting of a first agent and a second agent (the two agents may be referred to as two liquids). Using the obtained adhesive composition, from the B-type viscosity, the tensile storage elastic modulus (23 ° C.) (two-component curing) of the cured product obtained from the matrix composition, and the matrix composition by the evaluation method shown below. Tension storage elastic modulus (90 ° C.) (two-component curing), adhesive strength (two-component curing), D hardness (two-component curing), fixing time (5 mW / cm ² ), isobutane gas during storage of the obtained cured product The concentration, adhesion / peeling test (A), adhesion / peeling test (B), adhesion / peeling test (C), and laminated adhesion / processing / peeling test (A) were measured. The results are shown in Tables 4-5. The abbreviations shown in Table 1 were used for the composition names in Tables 2 and 3.

(Evaluation method)

Integrated light intensity and illuminance: The integrated light intensity and illuminance were measured by an ultraviolet integrated illuminance meter (manufactured by Eye Graphics Co., Ltd .: EYE UVMETER UVPF-A1 (using a 365 nm receiver)).

B-type viscosity: Refers to the viscosity measured using a B-type viscometer under the conditions of 25 ° C. and a rotation speed of 10 rpm.
Adhesive by two-component curing D hardness of cured product (“D hardness (two-component curing)” in the table): An adhesive composition in which equal amounts of the first agent and the second agent are mixed, and a 5 mm thick silicon sheet is molded. It was used as a frame and sandwiched between PET films. The adhesive composition was cured at 23 ° C. for 24 hours to prepare a cured product of the adhesive composition having a thickness of 5 mm. The prepared cured product was cut into a cylinder having a diameter of 30 mm with a cutter to obtain a cured product for measuring Shore D hardness. The value of the obtained cured product was measured by ASTM D-2240 using a D-type shore hardness tester.

Tension-shear adhesive strength by two-component curing (“Adhesive strength (two-component curing)” in the table): Measured according to JIS K 6850. Specifically, using heat-resistant glass (trade name "heat-resistant Pyrex (registered trademark) glass", length 25 mm x width 25 mm x thickness 2.0 mm) as an adherend, the adhesive portion is made into a circle with a diameter of 8 mm. Two heat-resistant glasses are bonded together with an adhesive composition obtained by mixing equal amounts of the first agent and the second agent, cured at 23 ° C. for 24 hours, and then cured to prepare a tensile shear adhesive strength test piece. did. The prepared test piece was measured for tensile shear adhesion strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.

Tension storage elastic modulus (23 ° C.) of the cured product obtained from the matrix composition by two-component curing (“Tension storage elastic modulus (23 ° C.) (two-component curing) of the cured product obtained from the matrix composition” in the table) and Tension storage elastic modulus of the cured product obtained from the matrix composition (90 ° C.) (Table "Tension storage elastic modulus of the cured product obtained from the matrix composition (90 ° C.) (two-component curing)"): Tables 2-3 Of the compositions of Tables 2 and 3, the materials used of (1), (2), (4), and (6) were mixed to prepare the matrix composition of the first agent, and among the compositions of Tables 2 and 3, ( The materials used of 1), (2), (4), (5), and (6) are mixed to prepare a matrix composition of the second agent, and the matrix composition of the first agent and the matrix of the second agent are prepared. A mixture of matrix compositions in which equal amounts of the compositions were mixed was sandwiched between PET films using a 1 mm thick silicon sheet as a mold. When the second agent did not contain (2) and (4), (2) and (4) were not used in the matrix composition of the second agent. The mixture was cured at 23 ° C. for 24 hours to prepare a cured product of a composition having a thickness of 5 mm. The prepared cured product was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured product for measuring the glass transition temperature. The obtained cured product is subjected to stress and strain in the tensile direction of 1 Hz in a nitrogen atmosphere by a dynamic viscoelasticity measuring device "DMS210" manufactured by Seiko Denshi Sangyo Co., Ltd., and the temperature rise rate is 2 ° C. per minute. The tensile storage elastic modulus was measured while raising the temperature at the rate of, and the measured values of the tensile storage elastic modulus at 23 ° C. and 90 ° C. were respectively obtained from the matrix composition by two-component curing. ° C.) and the tensile storage elastic modulus (90 ° C.) of the cured product obtained from the matrix composition.

Fixing time (“Fixing time (5 mW / cm ² )” in the table): Using two slide glasses, add a few drops of an adhesive composition in which equal amounts of the first agent and the second agent are mixed to one glass. Then I layered it on the other glass. Subsequently, the glass was moved by hand while irradiating ultraviolet rays having a wavelength of 365 nm and an illuminance of 5 mW / cm ² , and the time from the start of irradiation until the glass stopped moving was measured and used as the fixing time.

Isobutane gas concentration during storage: A headspace vial having a volume of 30 ml was filled with 10 g of an adhesive composition in which equal amounts of the first agent and the second agent were mixed. The headspace vial was then replaced with nitrogen, sealed and stored at 10 ° C. for 1 month. One month later, the isobutane gas concentration was measured using a headspace gas chromatograph FID (HS / GC-FID) under the following conditions.
Analytical column: GS-Alumina (30 mm x 0.53 mm)
Column temperature: 150 ° C
Injection port temperature: 180 ° C
FID temperature: 180 ° C
Injection volume: 0.1-0.2 ml

(Adhesion / peeling test (A))
7 g of an adhesive composition obtained by mixing equal amounts of the first agent and the second agent is applied onto glass A (length 150 mm × width 150 mm × thickness 2 mm), which is a member, and glass B (length 150 mm × width 150 mm). × Thickness 200 μm) is pasted together, cured at 23 ° C for 24 hours to cure, and after confirming that they are completely adhered, the obtained test piece is immersed in warm water (95 ° C) and the glasses are mixed with each other. The peeling time was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersion in warm water to peeling of the member.

(Adhesion / peeling test (B))
7 g of an adhesive composition obtained by mixing equal amounts of the first agent and the second agent is applied onto glass A (length 150 mm × width 150 mm × thickness 2 mm), which is a member, and glass B (length 150 mm × width 150 mm). × Thickness 200 μm) was bonded, cured at 23 ° C. for 24 hours and cured, and the glasses were adhered to each other. Then, the obtained test piece was heated to 160 ° C. on a hot plate, the time for the glasses to peel off from each other was measured, and the state of the film after the peeling was also confirmed. The peeling time refers to the time from when the test piece is placed on the hot plate heated to 160 ° C. until the member is peeled off.

(Adhesion / peeling test (C))
7 g of an adhesive composition obtained by mixing equal amounts of the first agent and the second agent is applied onto glass A (length 150 mm × width 150 mm × thickness 2 mm), which is a member, and glass B (length 150 mm × width 150 mm). × Thickness 200 μm) is pasted together, cured at 23 ° C for 24 hours to cure, and after confirming that they are completely adhered, the obtained test piece is immersed in warm water (90 ° C), and the glasses are mixed with each other. The peeling time was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersion in warm water to peeling of the member.

(Laminate adhesion / processing / peeling test (A))

1. 1. Twelve pieces of glass (length 150 mm x width 150 mm x thickness 200 μm) are laminated on glass (length 150 mm × width 150 mm × thickness 200 μm), which is a member for producing a glass laminate, via an adhesive composition. A laminated glass was prepared.
In the two-agent type adhesive composition, a laminate prepared through an adhesive composition in which equal amounts of the first agent and the second agent were mixed was cured at 23 ° C. for 24 hours and cured. In the adhesive composition containing a photoradical polymerization initiator (one-agent type adhesive composition), black light is used to irradiate light from the upper surface of the glass under the condition of ^{an integrated light amount of 2000 mJ / cm 2 at a wavelength of 365 nm.} , Hardened. The light irradiation was carried out every time one glass was laminated, and the process was repeated 11 times to prepare a laminated glass.

2. Cutting process of the glass laminate Next, the glass laminate was cut in the thickness direction along a predetermined cutting line by a slicer (slicing machine) to prepare a divided glass laminate. At this time, the glass was divided into a width of 40 mm, a length of 40 mm, and a thickness of 2.4 mm.

3. 3. The obtained glass laminate was immersed in warm water (95 ° C.), the time for the glasses to peel off from each other was measured, and the state of the film after the peeling was also confirmed. The peeling time (time required for peeling all 12 sheets) was defined as the time required for all 12 sheets of glass to be peeled after being immersed in warm water.

(Examples 9 to 10, Comparative Example 5)
It was evaluated by the following method.

(Preparation of adhesive composition)
The materials used in Table 1 were used. Each material used was mixed according to the composition shown in Table 6 to prepare a one-agent adhesive composition (one agent may be referred to as one liquid). Using the obtained adhesive composition, B-type viscosity, tensile storage elastic modulus (23 ° C.) (UV irradiation) obtained from the matrix composition, and tensile storage obtained from the matrix composition by the evaluation method shown below. Elastic modulus (90 ° C) (UV irradiation), adhesion strength (UV irradiation), D hardness (UV irradiation), fixing time (5 mW / cm ² ), adhesion / peeling test (D), adhesion / peeling test (E) , Adhesion / peeling test (F) and laminated adhesion / processing / peeling test (B) were performed. The results are shown in Table 7. The abbreviations shown in Table 1 were used for the composition names in Table 6.

(Evaluation method)
D hardness of the cured adhesive by UV irradiation (“D hardness (UV irradiation)” in the table): The adhesive composition is lighted using black light under the condition of ^{an integrated light amount of 2000 mJ / cm 2 at a wavelength of 365 nm.} Was irradiated and cured from the upper surface, and then light was further ^{irradiated and cured from the lower surface under the condition of an integrated light amount of 2000 mJ / cm 2 having} a wavelength of 365 nm from the lower surface to prepare five cured products having a thickness of 1 mm. The prepared cured product was cut into a cylinder having a diameter of 30 mm with a cutter, and five cured products having a thickness of 1 mm were stacked to prepare a cured product for shore D hardness measurement. The value of the obtained cured product was measured by ASTM D-2240 using a D-type shore hardness tester.

Tension Shear Adhesive Strength by UV Irradiation (“Adhesive Strength (UV Irradiation)” in the table): Measured according to JIS K 6850. An adhesive composition using heat-resistant glass (trade name "heat-resistant Pyrex (registered trademark) glass", length 25 mm x width 25 mm x thickness 2.0 mm) as an adherend, and forming the bonding site into a circle with a diameter of 8 mm. Two heat-resistant glasses are bonded together, and black light is used to irradiate and cure light from the top surface under the condition of ^{an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm, and a tensile shear adhesive strength test piece.} Was produced. The prepared test piece was measured for tensile shear adhesion strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.

Tension storage elastic modulus (23 ° C.) of the cured product obtained from the matrix composition by UV irradiation (“Tension storage elastic modulus (23 ° C.) (UV irradiation) of the cured product obtained from the matrix composition” in the table) and matrix composition Tension storage elastic modulus of the cured product obtained from the product (90 ° C.) (“Tension storage elastic modulus of the cured product obtained from the matrix composition (90 ° C.) (UV irradiation)”): Of the compositions in Table 6, The materials used of (1), (2), (4), and (6) are mixed to prepare a cured product obtained from the matrix composition, and the composition is used as a mold using a 1 mm thick silicon sheet. It was sandwiched between PET films. ^{The composition is irradiated with light from the upper surface under the condition of an integrated light amount of 2000 mJ / cm 2 having} a wavelength of 365 nm using a black light and cured, and then further, an integrated light amount of 2000 mJ / cm ^{2 having} a wavelength of 365 nm from the lower surface. Under the conditions, light was irradiated from the lower surface and cured to prepare a cured product of an adhesive composition having a thickness of 1 mm. The prepared cured product was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured product for measuring the glass transition temperature. The obtained cured product is subjected to stress and strain in the tensile direction of 1 Hz in a nitrogen atmosphere by a dynamic viscoelasticity measuring device "DMS210" manufactured by Seiko Denshi Sangyo Co., Ltd., and the temperature rise rate is 2 ° C. per minute. The tensile storage elastic modulus was measured while raising the temperature at the rate of, and the measured values of the tensile storage elastic modulus at 23 ° C. and 90 ° C. were measured by the tensile storage elastic modulus (23 ° C.) of the cured product obtained from the matrix composition by UV curing, respectively. ) And the tensile storage elastic modulus (90 ° C.) of the cured product obtained from the matrix composition.

Fixing time (“Fixing time (5 mW / cm ² )” in the table): Using two glass slides, a few drops of the adhesive composition was added to one glass and overlaid with the other glass. Subsequently, the glass was moved by hand while irradiating ultraviolet rays having a wavelength of 365 nm and an illuminance of 5 mW / cm ² , and the time from the start of irradiation until the glass stopped moving was measured and used as the fixing time.

(Adhesion / peeling test (D))
7 g of the adhesive composition is applied onto glass A (length 150 mm x width 150 mm x thickness 2 mm), which is a member, and glass B (length 150 mm x width 150 mm x thickness 200 μm) is bonded to black light. The glass was used and irradiated with light from the upper surface of the glass B under the condition of an integrated light amount of 2000 mJ / cm ^{2 having a wavelength of 365 nm and cured to bond the glasses to each other.} Then, the obtained test piece was immersed in warm water (95 ° C.), the time for the glasses to peel off from each other was measured, and the state of the film after the peeling was also confirmed. The peeling time refers to the time from immersion in warm water to peeling of the member.

(Adhesion / peeling test (E))
7 g of the adhesive composition is applied onto glass A (length 150 mm x width 150 mm x thickness 2 mm), which is a member, and glass B (length 150 mm x width 150 mm x thickness 200 μm) is bonded to black light. The glass was used and irradiated with light from the upper surface of the glass B under the condition of an integrated light amount of 2000 mJ / cm ^{2 having a wavelength of 365 nm and cured to bond the glasses to each other.} Then, the obtained test piece was immersed in warm water (90 ° C.), the time for the glasses to peel off from each other was measured, and the state of the film after the peeling was also confirmed. The peeling time refers to the time from immersion in warm water to peeling of the member.

(Adhesion / peeling test (F))
7 g of the adhesive composition is applied onto glass A (length 150 mm x width 150 mm x thickness 2 mm), which is a member, and glass B (length 150 mm x width 150 mm x thickness 200 μm) is bonded to black light. It was used, and light was irradiated from the upper surface of the glass B under the condition of an integrated light amount of 2000 mJ / cm ^{2 having a wavelength of 365 nm to cure the glass, and the glasses were adhered to each other.} Then, the obtained test piece was heated to 160 ° C. on a hot plate, the time for the glasses to peel off from each other was measured, and the state of the film after the peeling was also confirmed. The peeling time refers to the time from when the test piece is placed on the hot plate heated to 160 ° C. until the member is peeled off.

(Laminate adhesion / processing / peeling test (B))

1. 1. Twelve pieces of glass (length 150 mm x width 150 mm x thickness 200 μm) are laminated on glass (length 150 mm × width 150 mm × thickness 200 μm), which is a member for producing a glass laminate, via an adhesive composition. A laminated glass was prepared.
In the two-agent type adhesive composition, a laminate prepared through an adhesive composition in which equal amounts of the first agent and the second agent were mixed was cured at 23 ° C. for 24 hours and cured. In the adhesive composition containing a photoradical polymerization initiator (one-agent type adhesive composition), black light is used to irradiate light from the upper surface of the glass under the condition of ^{an integrated light amount of 2000 mJ / cm 2 at a wavelength of 365 nm.} , Hardened. The light irradiation was carried out every time one glass was laminated, and the process was repeated 11 times to prepare a laminated glass.

2. Cutting process of the glass laminate Next, the glass laminate was cut in the thickness direction along a predetermined cutting line by a slicer to prepare a divided glass laminate. At this time, the glass laminate was divided into a width of 75 mm, a length of 75 mm, and a thickness of 2.4 mm.

3. 3. The obtained glass laminate was exposed for 30 minutes in an oven heated to 160 ° C., the time for the glass to peel off was measured, and the state of the film after peeling was also confirmed. The peeling time (time required for peeling all 12 sheets) was the time required for all 12 sheets of glass to be peeled off after the test piece was placed in an oven heated to 160 ° C.

From Tables 1 to 7, it was found that the present invention has an excellent effect. In Comparative Examples 1 to 5, any of the components was outside the scope of the present invention and did not show the effect of the present invention.

Since Comparative Example 1 did not contain the component (4), the member did not peel off. Since the components (1-4) of Comparative Examples 2 and 3 were small, the peeling time was long and isobutane gas leaked a lot during storage. In Comparative Example 4, since the components (1-4) were large, the cured product of the adhesive composition remained on the member, and the peeled state was not good. In the peeling test, when the adhesive remained or the cured product of the adhesive composition remained on the member, it was difficult to recover the member and the workability was not good. Since Comparative Example 5 does not contain the component (1-1), the member may not be peeled off.

The present invention is highly safe because there is little leakage of flammable gas from the organic heat-expandable particles contained in the adhesive composition during storage.

In the present invention, when the adhesive body comes into contact with hot water, the adhesiveness is lowered and the bonding force between the members or between the members and the jig is lowered, so that the members can be easily recovered.

In the present invention, by heating the bonded body, the adhesiveness is lowered and the bonding force between the members or between the members and the jig is lowered, so that the members can be easily recovered.

The temporary fixing method of the member of the present invention is excellent in workability because it is possible to process a member having a thin thickness and difficult to process, there is no adhesive residue on the member even after peeling, and the cured product can be easily recovered from the member.
With the conventional technique, it is difficult to temporarily fix a member having a thin thickness and difficult to process or a member having a large area and to process the member with high accuracy without chipping, and it is difficult to easily peel off the member without adhesive residue after processing. According to the present invention, for example, by controlling the tensile storage elastic modulus at 23 ° C. related to processing and the tensile storage elastic modulus at 90 ° C. related to peeling, even a member having difficulty in processing or a member having a large area can be subjected to a process. Sufficient adhesiveness can be obtained without increasing the amount of water, no deviation occurs during processing, dimensional accuracy and chipping property are improved, and an excellent member can be easily obtained.
According to the present invention, by reducing the average particle size of the particulate matter, the thickness of the adhesive can be reduced, the dimensional accuracy during processing can be improved, and the chipping property is excellent.

Claims (26)

(1) Many other than (1-1) imide (meth) acrylate and / or cyclic trimethylolpropane formal (meth) acrylate, (1-2) urethane (meth) acrylate, (1-3) and (1-2). 100 parts by mass of (meth) acrylate containing functional (meth) acrylate, (1-4) alkyl (meth) acrylate,
(2) Radical polymerization initiator 0.1 to 20 parts by mass,
(3) 1 to 40 parts by mass of organic heat-expandable particles, which are heat-expandable microcapsules in which butane and / or isobutane are encapsulated in microcapsules by an organic material of an outer shell.
(4) Particulate matter (excluding the above-mentioned (3) organic swelling particles) A composition containing 0.1 to 5 parts by mass.
(1) (meth) acrylate in 100 parts by weight, (1-4) alkyl (meth) acrylate composition containing 3 to 20 parts by weight. (1) Of 100 parts by mass of (meth) acrylate , (1-1) 30 to 75 parts by mass, (1-2) 10 to 50 parts by mass, (1-3) 3 to 20 parts by mass, (1-4) The composition according to claim 1, which contains 3 to 20 parts by mass. The composition according to claim 1, wherein the (1) (meth) acrylate contains a monofunctional (meth) acrylate other than (1-5) (1-1) and (1-4). (1) Of 100 parts by mass of (meth) acrylate , (1-1) 30 to 75 parts by mass, (1-2) 10 to 50 parts by mass, (1-3) 3 to 20 parts by mass, (1-4) The composition according to claim 3, which contains 3 to 20 parts by mass and (1-5) 1 to 15 parts by mass. (3) The composition according to any one of claims 1 to 4, wherein the temperature at which the volume of the organic heat-expandable particles can be expanded three times or more is 80 ° C. to 120 ° C. (3) The composition according to any one of claims 1 to 5, wherein the temperature at which the volume of the organic heat-expandable particles can be expanded three times or more is 85 ° C. to 95 ° C. (4) The composition according to any one of claims 1 to 6, wherein the average particle size of the particulate matter is 15 to 80 μm. (1-4) The composition according to any one of claims 1 to 7, wherein the alkyl (meth) acrylate is lauryl (meth) acrylate. (2) The composition according to any one of claims 1 to 8, wherein the radical polymerization initiator contains (2-1) a photoradical polymerization initiator. (2) The composition according to any one of claims 1 to 8, wherein the radical polymerization initiator is (2-2) a thermal radical polymerization initiator. (2) The composition according to any one of claims 1 to 8, wherein the radical polymerization initiator contains (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator. (5) The composition according to claim 10 or 11, which contains (5) a reducing agent. A two-component composition obtained by dividing the composition according to claim 12 into two agents, the first agent containing (2-2) a thermal radical polymerization initiator, and the second agent containing (5) a reducing agent. The composition according to claim 13, wherein the first agent and / or the second agent contains (2-1) a photoradical polymerization initiator. The composition according to any one of claims 1 to 14, wherein the cured product of the composition has a tensile storage elastic modulus of 40 to 4500 MPa at 23 ° C. and a tensile storage elastic modulus of 0.5 to 10 MPa at 90 ° C. .. An adhesive composition containing the composition according to any one of claims 1 to 15. The adhesive composition according to claim 16, wherein the adhesive composition is used for bonding one or more adherends in the group consisting of quartz bonding, ceramics bonding, silicon bonding, and glass bonding. The adhesive composition according to claim 16, wherein the use is for adhering an adherend having a thickness of 200 μm or less. The adhesive composition for temporary fixing according to claim 16, wherein the use is for temporary fixing. The member is temporarily fixed using the temporary fixing adhesive composition according to claim 19, the temporary fixing adhesive composition is cured, the temporarily fixed member is processed, and the processed adhesive is obtained. A method for temporarily fixing a member for removing a cured product of the temporary fixing adhesive composition by immersing it in water. Using the temporary fixing adhesive composition according to claim 19, the members are temporarily fixed, the temporary fixing adhesive composition is cured, the temporarily fixed member is processed, and the processed adhesive is obtained. A method for temporarily fixing a member for removing a cured product of the temporary fixing adhesive composition by heating to 80 to 300 ° C. A method for manufacturing a member for removing an adhesive body by temporarily fixing 2 to 100 members to be processed using the temporary fixing adhesive composition according to claim 19 and immersing the adhesive body in water after processing. A bonded body for joining members via the temporary fixing adhesive composition according to claim 19. The bonded body according to claim 23, wherein the member is one or more of the group consisting of quartz, ceramics, silicon, and glass. The joined body according to claim 23 or 24, wherein the member has a thickness of 200 μm or less. The joined body according to any one of claims 23 to 25, wherein the processed member has an area of 60 cm ^{2 or more.}