JP2017125178A - COMPOSITION AND Temporary fixing method of member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition excellent in workability and environment property.SOLUTION: There is provided a composition containing (1) a polymerizable vinyl derivative containing (1-1) imide (meth)acrylate and/or cyclic trimethylol propane formal (meth)acrylate, (1-2) urethane (meth)acrylate, (1-3) polyfunctional (meth)acrylate other than (1-2), (1-4) alkyl (meth)acrylate, (2) a radical polymerization initiator, (3) an organic thermal expansion particle, (4) a particulate material with the (1-4) alkyl (meth)acrylate of 3 to 20 pts.mass in 100 pts.mass of the (1) polymerizable vinyl derivative.SELECTED DRAWING: None

Description

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

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

However, in the case of a double-sided tape, it is difficult to obtain dimensional accuracy, the chipping property is inferior when parts are processed due to low adhesiveness, and it cannot be peeled off without applying heat of 100 ° C. or higher. There was a problem. Further, in the case of peeling by ultraviolet irradiation, there is a problem that peeling cannot be performed if the adherend has poor permeability.

In the case of a hot-melt adhesive, it is necessary to use an organic solvent at the time of cleaning after peeling, which is problematic from the viewpoint of protecting the global environment, and furthermore, the cleaning process is complicated, It was an issue.

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

In Patent Document 2, a monofunctional monomer having a specific ethylenic double bond and a polymer substance that does not have a polymerizable double bond in a specific molecule and is water-soluble or swellable by water absorption. There has been proposed a temporary fixing method in which a small article is temporarily fixed using an adhesive composition for temporary fixing and then removed by being immersed in water. However, the temporary fixing method using these adhesives has a problem that the working time becomes long in a large-area member because the dissolution rate and swelling rate of the adhesive when removing are slow.

Further, Patent Document 3 discloses a heat-peelable adhesive that can be easily self-peeled after the adhesion is significantly reduced by heat treatment after adding organic heat-expandable particles at a specific ratio in the adhesive. It has been reported. However, since these adhesives have too strong adhesiveness, there is a problem that a large-area member cannot be put into practical use because it cannot be peeled off even by heat treatment.

Patent Document 4 includes (a) a mono (meth) acrylate having no hydroxyl group, a carboxyl group and an epoxy group and having an aromatic ring, and (b) no hydroxyl group, a carboxyl group and an epoxy group, and an alicyclic ring. Adhesion by adding a specific proportion of organic heat-expandable particles in an adhesive containing at least one of the mono (meth) acrylates having a structure, the adhesiveness is significantly reduced by heat treatment, and self-peeling easily Possible heat-peelable adhesives have been reported. However, these adhesives have a low modulus of elasticity at the processing temperature, low dimensional accuracy, and no granular material is added to control the thickness of the adhesive during bonding. Depending on the particle size of the expandable particles, the dimensional accuracy during processing is low, the chipping property is inferior, and there is a problem that it cannot be put into practical use.

Patent Document 5 and Patent Document 6 include (a) an organic peroxide, a reaction with the organic peroxide to promote polymerization of a monomer, (b) a curing accelerator, and (c) a monofunctional (meth). A curable composition comprising an acrylate and (d) a polyfunctional (meth) acrylate, wherein the (a) organic peroxide is encapsulated in a microcapsule, is reported. Has been. However, these adhesives are hardened by components other than those encapsulated in the microcapsule by releasing the encapsulated liquid containing the organic peroxide by compressing and destroying the contained microcapsule by an external force or the like. Since it reacts with the base of the composition and proceeds with curing, it cannot be peeled 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 after processing. However, the illustrated photocurable fixing material fixing material 2 needs to ensure safety during storage because isobutane gas, which is a combustible gas contained in organic thermally expandable particles, leaks during storage. There is. In addition, the organic heat-expandable particles are not added to the fixing material 1, the fixing material 3, and the fixing material 4 which are exemplified. There is no description that a large-area member can be easily peeled off by adding organic heat-expandable particles.

Patent Document 8 reports a photocurable and room temperature curable two-component adhesive composition containing organic thermally 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 processed. Patent Document 8 does not describe leakage suppression of combustible 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 JP 2008-174707 A 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, a member having a large area or a member having a thickness of 200 μm or less, which is difficult to perform precision processing, can be applied, and further, workability such that there is no adhesive residue on the member after peeling. There has been a demand for an adhesive composition for temporary fixing that is excellent in environmental properties and safety during storage.

That is, the present invention provides (1) (1-1) imide (meth) acrylate and / or cyclic trimethylolpropane formal (meth) acrylate, (1-2) urethane (meth) acrylate, (1-3) (1 -2) polyfunctional (meth) acrylates other than (1-4) polymerizable vinyl derivatives containing alkyl (meth) acrylates,
(2) radical polymerization initiator,
(3) Organic thermally expandable particles,
(4) A composition containing particulate matter,
(1) A composition containing 3 to 20 parts by mass of (1-4) alkyl (meth) acrylate in 100 parts by mass of the polymerizable vinyl derivative. (1) In 100 parts by mass of the polymerizable vinyl derivative, 1) 30-75 parts by mass, (1-2) 10-50 parts by mass, (1-3) 3-20 parts by mass, (1-4) 3-20 parts by mass (1) The polymerizable vinyl derivative is a composition containing a monofunctional (meth) acrylate other than (1-5) (1-1) and (1-4), and (1) the polymerizable vinyl derivative 100 mass parts, (1-1) 30-75 mass parts, (1-2) 10-50 mass parts, (1-3) 3-20 mass parts, (1-4) 3-20 mass parts, 1-5) The composition containing 1 to 15 parts by mass, and (3) in the organic thermally expandable particles, the volume expands three times or more. The composition is such that the temperature is 80 ° C. to 120 ° C., and (3) the organic thermal expandable particles have a temperature capable of volume expansion of 3 times or more is 85 ° C. to 95 ° C. And (4) the composition having an average particle size of 15 to 80 μm, and (1-4) the alkyl (meth) acrylate is lauryl (meth) acrylate. It is a composition, (2) the radical polymerization initiator is (2-1) the composition containing a photo radical polymerization initiator, and (2) the radical polymerization initiator is (2-2) a thermal radical polymerization initiator. (2) The radical polymerization initiator is a composition containing (2-1) a photoradical polymerization initiator and (2-2) a thermal radical polymerization initiator, and (5) ) The composition containing a reducing agent, and the composition is in two parts It is a two-component composition containing (2-2) a thermal radical polymerization initiator in the first agent and (5) a reducing agent in the second agent, and the first agent and / or the second agent. The composition contains (2-1) a radical photopolymerization initiator, and the cured product of the composition has a tensile storage elastic modulus at 23 ° C. of 40 to 4500 MPa and a tensile storage elastic modulus at 90 ° C. It is this composition which is 0.5-10 Mpa, It is an adhesive composition containing this composition, and 1 or more types of the group which uses for quartz bonding, ceramics bonding, silicon bonding, and glass bonding The adhesive composition for adhering adherends of the present invention, the adhesive composition for use in adhering adherends having a thickness of 200 μm or less, and the use for temporary fixing Adhesive composition, using the adhesive composition for temporary fixing Temporarily fixing the member, curing the temporary fixing adhesive composition, processing the temporarily fixed member, and immersing the processed adhesive in water, the temporary fixing adhesive composition A method for temporarily fixing a member from which a cured body is removed, using the temporary fixing adhesive composition, temporarily fixing the member, curing the temporary fixing adhesive composition, and processing the temporarily fixed member Then, by heating the processed adhesive body to 80 to 300 ° C., the temporary fixing method of the member for removing the cured body of the temporary fixing adhesive composition, and using the temporary fixing adhesive composition, A method for producing a member for removing an adhesive body by temporarily fixing 2 to 100 workpieces, immersing the adhesive body in water after processing, and removing the adhesive member through the temporary fixing adhesive composition. A joined body to be joined, and the members are quartz, ceramics, silicon and glass. It is this joined body which is 1 or more types of the group which consists of this, a member is this joined body which has a thickness of 200 micrometers or less, and this joined body whose area of the member after a process is 60 cm < ² > or more.

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

The present invention will be described below. Monofunctional (meth) acrylate refers to (meth) acrylate having one (meth) acryloyl group. The polyfunctional (meth) acrylate refers to (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-component temporary fixing adhesive composition, (1) 100 parts by mass refers to (1) 100 parts by mass of the total of the first agent and the second agent.

(1) Polymerizable vinyl derivatives are (1-1) imide (meth) acrylate and / or cyclic trimethylolpropane formal (meth) acrylate, (1-2) urethane (meth) acrylate, (1-3) (1 -2) Polyfunctional (meth) acrylate other than (1-4) alkyl (meth) acrylate is contained. Furthermore, (1) the polymerizable vinyl derivative may contain a monofunctional (meth) acrylate other than (1-5) (1-1) and (1-4).

(1-1) Imido (meth) acrylate and / or 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.

R ¹ is preferably hydrogen. 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, and more preferably 1 to 3. In the formula (1), 2- (1,2-cyclohexanedicarboximido) ethyl (meth) acrylate is preferable.

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

(1-2) Urethane (meth) acrylate refers to (meth) acrylate having a urethane bond. The urethane (meth) acrylate is preferably a urethane (meth) acrylate having two or more (meth) acryloyl groups at the molecular end or side chain. The urethane (meth) acrylate is 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 preferred. The production method of 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 alcohol, polyether polyol, and polyester polyol.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 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, Polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polybutadiene polyol, hydrogenated polybutadiene poly Lumpur, and the like. The polybutadiene polyol refers to polybutadiene having two or more hydroxyl groups, for example, polybutadiene having hydroxyl groups at both ends. The hydrogenated polybutadiene polyol refers to a hydrogenated polybutadiene having two or more hydroxyl groups, for example, a hydrogenated polybutadiene having hydroxyl groups at both ends. Among the polyhydric alcohols, ethylene glycol and / or 1,4-butanediol are preferable.

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

Examples of the polyester polyol include a polyester polyol that is a condensate of polyhydric alcohol or polyether polyol and a polybasic acid. Examples of the polyhydric alcohol or polyether polyol used for the production of the polyester polyol include the aforementioned compounds. Examples of the polybasic acid include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid and the like. Of the polybasic acids, adipic acid is preferred.

The organic polyisocyanate compound (Y) is not particularly limited. For example, aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates can be used. 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 diiso Polyisocyanates such as anate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), trimer compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, etc. Preferably used. In these, 1 or more types of the group which consists of tolylene diisocyanate (TDI), hydrogenated xylylene diisocyanate (H-XDI), and isophorone diisocyanate (IPDI) are preferable, and isophorone diisocyanate is more preferable.

Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 2-hydroxybutyl (meth) acrylate, 2- Hydroxyethyl (meth) acryloyl phosphate, 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acrylate Examples include leuoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified 2-hydroxyethyl (meth) acrylate.Of these, hydroxyalkyl (meth) acrylate is preferred. Among the hydroxyalkyl (meth) acrylates, one or more members selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferable. (Meth) acrylate is more preferred.

Among urethane (meth) acrylates, polyester-based urethane (meth) acrylate and / or polyether-based urethane (meth) acrylate are preferred because of low viscosity and good workability, and polyether-based urethane (meth). 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.

Polyester 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. Polyester urethane (meth) acrylate is a reaction between a polyester polyol compound (hereinafter referred to as X), an organic polyisocyanate compound (hereinafter referred to as Y), and hydroxy (meth) acrylate (hereinafter referred to as Z). The urethane (meth) acrylate obtained by this.

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

Examples of the polyester urethane (meth) acrylate include “UV-3000B” manufactured by Nihon Gosei Co., Ltd.

The polyether-based urethane (meth) acrylate has two or more (meth) acryloyl groups at the end or side chain of the molecule, and has a polyether structure in the molecule. The polyether-based 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). The urethane (meth) acrylate obtained by making it let it be said.

Examples of the polyether polyol compound (X) include the aforementioned polyether polyols. Among the polyether polyols, polyalkylene glycol is preferable. Of the polyalkylene glycols, polypropylene glycol is preferred.

Examples of the polyether urethane (meth) acrylate include “UV-3700B” manufactured by Nihon Gosei Co., Ltd., “UN-6200” manufactured by Negami Kogyo Co., Ltd., “UN-6202” manufactured by Negami Kogyo Co., Ltd., and the like.

(1-2) The molecular weight of the urethane (meth) acrylate is preferably 1000 to 50000, more preferably 5000 to 45000, and most preferably 15000 to 40000 in terms of a large effect. The weight average molecular weight is determined by using tetrahydrofuran as a solvent, using a GPC system (SC-8010 manufactured by Tosoh Corporation), etc., and creating a calibration curve with commercially available standard polystyrene under the following conditions.

Flow rate: 1.0 ml / min
Set temperature: 40 ° C
Column configuration: “TSK guardcolumn MP (× L)” manufactured by Tosoh Corporation 6.0 mmID × 4.0 cm1 and “TSK-GEL MULTIPIOREHXL-M” manufactured by Tosoh Corporation 7.8 mmID × 30.0 cm (16,000 theoretical plates) 2), 3 in total (32,000 theoretical plates as a whole)
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid feeding 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 in 100 parts by mass in terms of workability and peelability. ˜40 parts by mass is most preferred. If the amount is less than 10 parts by mass, the effect may be small. If the amount 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 Occasionally, the expansion of the organic heat-expandable particles is hindered and the peelability may be poor.

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

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, dicyclopentanyl di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, stearic acid modified pentaerythrodi (meth) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryl Roxypropoxyphe Propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, dimethylol-tricyclodecane di (meth) acrylate, 1,10-decandiol di (meth) acrylate, isocyanuric acid ethylene oxide Examples include modified di (meth) acrylate. Among these, one or more members selected from the group consisting of tripropylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and polypropylene glycol di (meth) acrylate are preferable because of their great effects. Di (meth) acrylate is more preferred.

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

Examples of tetrafunctional or higher functional (meth) acrylate monomers include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Stall hexa (meth) acrylate is exemplified.

The amount of (1-3) used is peelable, and (1) in 100 parts by mass, preferably 3 to 20 parts by mass, more preferably 4 to 18 parts by mass, and most preferably 5 to 15 parts by mass. When the amount is less than 3 parts by mass, the effect may be small. When the amount 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 at the time of peeling is inferior, resulting in poor peelability. There is.

(1-4) As the alkyl (meth) acrylate, for example, a monofunctional (meth) acrylate represented by the following formula (2) can be suitably used. By using alkyl (meth) acrylate, leakage of the combustible gas from the organic heat-expandable particles contained in the adhesive during storage can be suppressed.
^{_{CH 2 = C (R 4)}} COOR 5 ··· formula (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 the number of carbon atoms may be represented as “C1-22”). R ⁴ is preferably a hydrogen atom and R ⁵ is C8 in terms of dimensional accuracy during processing, chipping property, releasability, and suppression of leakage of flammable gas from organic heat-expandable particles contained in the adhesive during storage. A chain alkyl group of -12 is preferred. If R ⁵ is a C8-12 chain alkyl group, leakage of the combustible gas from the organic thermally expandable particles can be suppressed.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl ( (Meth) 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) 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, nonadecyl (meth) acrylate, eicosyl ( Examples include meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and behenyl (meth) acrylate. Examples of the alkyl (meth) acrylate in which R ⁵ is a C8-12 chain alkyl group 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. In these, lauryl (meth) acrylate and / or octyl (meth) acrylate are preferable, and lauryl (meth) acrylate is more preferable.

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

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

(2) The radical polymerization initiator is preferably (2-1) a photoradical polymerization initiator and / or (2-2) a thermal radical polymerization initiator, and (2-1) a photoradical polymerization initiator and (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 and more preferably 1 to 10 parts by mass with respect to (1) 100 parts by mass.

(2-1) The radical photopolymerization initiator is used for sensitization with visible light or ultraviolet actinic light to promote photocuring of the composition.

Examples of radical photopolymerization initiators include benzophenone and derivatives thereof, benzyl and derivatives thereof, anthraquinone and derivatives thereof, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal. Acetophenone derivatives such as ethoxyacetophenone and 4-t-butyltrichloroacetophenone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and derivatives thereof, camphorquinone, 7,7-methyl-2,3- Dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane- -Carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3- Camphorquinone derivatives such as dioxobicyclo [2.2.1] heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl)- Α-Aminoalkylphenone derivatives such as butan-1-one, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphine oxide derivatives such as benzoyldioxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, oxy-phenyl-acetic acid Examples include 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester. One or more kinds of radical photopolymerization initiators can be used in combination. Of these, benzoin derivatives are preferred because of their great effects. Among the benzoin derivatives, benzyldimethyl ketal is preferable because of its large effect.

(2-1) The usage-amount of radical photopolymerization initiator is (1) 0.1-20 mass parts is preferable with respect to 100 mass parts, and 1-10 mass parts is more preferable. If it is this range, the effect of hardening acceleration will be acquired reliably.

In the present invention, (2-2) a 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 hexylperoxide. Alkyl pars such as oxybivalate, t-butyl peroxyisobutyrate, t-butyl peroxybivalate, t-butyl peroxyacetate, t-butyl peroxybenzoate, tertiary butyl peroxy-2-ethylhexanate Oxyesters, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, bis (4-tertiarybutylcyclohexyl) peroxydicarbonate, di-2-ethoxy Peroxydicarbonates such as ethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and diallyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, etc. Peroxycarbonates, di-t-butylperoxycyclohexane, peroxyketals such as di- (t-butylperoxy) butane, dicumyl peroxide, t-butylcumyl peroxide, di-t- Dialkyl peroxides such as butyl peroxide, hydroperoxides such as cumene hydroperoxide, tetramethylbutyl hydroperoxide, ketone peroxides such as ketone peroxide and cyclohexanone peroxide Oxides, and the like. Among these, alkyl peroxyesters and / or hydroperoxides are preferable, and hydroperoxides are more preferable. Of the hydroperoxides, cumene hydroperoxide is most preferred.

(2-2) 0.1-5 mass parts is preferable with respect to (1) 100 mass parts, and, as for the usage-amount of a thermal radical polymerization initiator, 1-3 mass parts is more preferable. If it is 0.1 mass part or more, sclerosis | hardenability will be acquired reliably, and if it is 5 mass parts or less, sufficient storage stability will be acquired and skin irritation will become low.

(3) The organic thermally expandable particles are preferably organic thermally expandable particles containing butane and / or isobutane.

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

(3) Although there is no restriction | limiting in particular in the heat expansibility of organic type | system | group thermally expansible particle | grains, 3 points | pieces of the point of suppression of peelability and leakage of the combustible gas from the organic type | system | group thermally expansible particle contained in an adhesive agent at the time of storage The temperature at which the volume expansion can be doubled or more is preferably 80 ° C to 120 ° C, more preferably 85 ° C to 100 ° C, and still more preferably 85 ° C to 95 ° C. If the temperature at which volume expansion is 3 times or more is less than 80 ° C., there is a risk of being inferior in terms of suppressing leakage of combustible gas, and the organic heat at which temperature expansion is possible at least 3 times is 120 ° C. The expandable particles may be inferior in peelability.

The heat expandability is obtained by mixing ethylene vinyl acetate emulsion and organic heat expandable particles at a solid content ratio of 2: 1 and coating on test paper so that the thickness becomes 100 μm when dried, and 80 ° C., 85 ° C., 90 ° C., 95 ° C. ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ heat foam test in the oven, and after 1 minute, the temperature expanded more than 3 times, the volume expansion more than 3 times Use a possible temperature.

(3) The average particle diameter of the organic thermal expandable particles is preferably 2 to 50 μm, preferably 5 to 30 μm, and most preferably 8 to 20 μm. If it is 2 micrometers or more, it will be excellent in the peelability of a composition, and if it is 100 micrometers or less, the adhesiveness of the composition before peeling will not fall.

(3) The amount of the organic thermally expandable particles used is preferably 1 to 40 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight in terms of peeling promotion and adhesiveness. 8-20 mass parts is the 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) The particulate material is preferably a particulate material having an average particle size of 15 to 80 μm. As the granular material having an average particle diameter of 15 to 80 μm, a granular substance having an average particle diameter of 15 to 80 μm measured by a laser method is preferable. By using a granular material having an average particle size of 15 to 80 μm (hereinafter sometimes referred to as a granular material), it becomes easy for the cured body to maintain a constant thickness, and even if the thickness is 200 μm or less, the dimension Processing can be performed with improved accuracy and chipping, and stable peelability can be obtained by controlling the thickness of the cured product. In terms of dimensional accuracy and chipping properties, the average particle size is more preferably 15 to 40 μm.

(4) The particulate material may be either organic particles or inorganic particles. The particulate material refers to a material 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 polystyrene polystyrene copolymer particles. Examples of inorganic particles include ceramic particles such as glass, silica, alumina, and titanium.

(4) The granular material is preferably spherical in terms of improving processing accuracy, that is, controlling the film thickness of the composition. Among the organic particles, crosslinked poly (meth) acrylate particles, crosslinked polystyrene particles, and crosslinked poly (meth) acrylic acid are small in that the deformation of the particles is small and the variation in the thickness of the cured product due to the variation in particle size is small. One or more members of the group consisting of methylpolystyrene copolymer particles are preferred. Cross-linked poly (meth) acrylate methyl particles, cross-linked polystyrene particles, and cross-linked poly (meth) methyl acrylate polystyrene copolymer particles include, for example, (meth) methyl acrylate monomers and styrene monomers, and cross-linkable monomers. It is obtained as monodisperse particles by polymerizing by the emulsion polymerization method. As the inorganic particles, spherical silica is preferable in that the deformation of the particles is small and the variation in the thickness of the cured product due to the variation in the particle size is small. Among these, organic particles are preferable from the viewpoint of storage stability due to particle sedimentation and the reactivity of the composition.

The particle size in the present invention can be measured by, for example, “Laser diffraction particle size distribution analyzer SALD-2200” manufactured by Shimadzu Corporation.

(4) The amount of the particulate material used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass, and preferably 0.2 to 0 in terms of dimensional accuracy during processing, chipping property, and peelability. More preferably, 8 parts by mass.

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

(5) The reducing agent is preferably one that reacts with (2-2) a 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. And organic thiourea such as ethylenethiourea and acetylthiourea. Of these, transition metal salts are preferred. Among the transition metal salts, one or more members selected from the group consisting of vanadium acetylacetonate, copper naphthenate, and cobalt octylate are preferable, and vanadium acetylacetonate and / or cobalt octylate are more preferable.

(5) 0.05-5 mass parts is preferable with respect to 100 mass parts (1), and, as for the usage-amount of a reducing agent, 0.1-3 mass parts is more preferable. If it is 0.1 mass part or more, sclerosis | hardenability will be obtained reliably, and if it is 5 mass parts or less, sufficient storage stability will be obtained.

In the present invention, (6) a polymerization inhibitor may be used to improve storage stability. Polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone. P-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole and 2 , 6-ditertiary butyl-p-cresol and the like. Among these, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) and / or citric acid are preferable because of their great effects.

The amount of the polymerization inhibitor used is preferably (1) 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 100 parts by mass. preferable. If it is 0.001 mass part or more, storage stability will be ensured, and if it is 3 mass parts or less, favorable adhesiveness will be obtained and it will not become uncured.

The viscosity of the composition of the present invention is preferably 500 to 50000 mPa · s, more preferably 1500 to 30000 mPa · s in terms of storage stability, at 25 ° C., as measured with a B-type viscometer. Preferably, it is 2000-15000 mPa * s, Most preferably, it is 2500-15000 mPa * s. If it is this range, the organic type heat-expandable particle in a composition will not isolate | separate during storage, and it will not become unusable.

The composition of the present invention is a generally used acrylic rubber, urethane rubber, various elastomers such as acrylonitrile-butadiene-styrene rubber, solvents such as polar organic solvents, fillers, reinforcements, etc., 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 adhesive composition for temporary fixing 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. The second agent is preferably used as a two-component temporary fixing adhesive composition containing at least (5) a reducing agent. For the two-component type, 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, the two agents can be used as a two-component temporary fixing adhesive composition by applying them to the member simultaneously or separately, and contacting and curing them. When used as a two-component type, (2-1) a photo-radical polymerization initiator, (3) an organic thermally expandable particle, and (4) a particulate material are either or both of the first agent and the second agent. May contain. The two-component temporary fixing adhesive composition can be cured only by mixing the two components.

The method of using the two-component temporary fixing adhesive composition is as follows. As a method of using the two-component temporary fixing adhesive composition, a method of applying an appropriate amount of the temporary fixing adhesive composition to the bonding surface of one member to be fixed, and then superimposing the other member, A plurality of members to be temporarily fixed in advance are laminated, and the temporary fixing adhesive composition is applied by a method of infiltrating the temporary fixing adhesive composition into the gap and applying the temporary fixing adhesive composition. Examples of the method include curing and temporarily fixing the members together.

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

When both agents are applied to the members simultaneously or separately to contact and cure and the members are temporarily fixed, after mixing the two agents and applying them to the members, for example, leave at room temperature for 0.5 to 500 hours It is preferable to bond the members together. If it is 0.5 hours or more, the adhesive composition for temporary fixing is cured and sufficient adhesiveness is obtained, and if it is 500 hours or less, sufficient adhesiveness is obtained. The standing time when the members are temporarily fixed is more preferably 4 to 300 hours, further preferably 24 to 200 hours, and most preferably 50 to 100 hours. Room temperature refers to 10 to 40 ° C., for example.

In addition, in the two-component temporary fixing adhesive composition, (2-1) when the radical photopolymerization initiator is contained in one or both of the first agent and the second agent, After mixing and bonding the members together, a part or all of the members can be easily adhered by irradiating visible light or ultraviolet rays for 1 to 60 seconds. In this step, since it is not necessary to completely cure, a light energy amount of 1 to 500 mJ / cm ² is sufficient at a wavelength of 365 nm. After this step, (2-2) the thermal radical polymerization initiator and (5) the reducing agent react with each other and are completely cured, thereby obtaining sufficient adhesiveness.

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-described temporary fixing method by mixing the two components. The cured body of the product is softened, whereby the organic thermally expandable particles easily expand, water enters the interface between the member and the temporary fixing adhesive composition, and the cured body can be more easily peeled off. The higher the temperature of the water, the greater the expansion of the organic thermally expandable particles. Therefore, water easily enters and the cured body can be easily peeled off. The temperature of water when removing the cured body is preferably higher than 40 ° C., more preferably 60 ° C. or higher, most preferably 80 to 100 ° C., and still 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, the temporary fixing method by mixing the two agents described above is used, and then the adhesive is heated to 80 to 300 ° C. for temporary fixing. The hardened body of the adhesive composition softens, whereby the organic thermally expandable particles easily expand, and voids are generated at the interface between the member and the hardened body of the adhesive composition for temporary fixing, making the hardened body easier. Can be peeled off. The higher the heating temperature, the easier the exfoliation of the cured product because the expansion of the organic thermally expandable particles is greater. The heating temperature for removing the cured body is more preferably 100 to 260 ° C, and 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, for example, a temporary fixing adhesive that is sandwiched between both members and then spread after bonding each member coated with the temporary fixing adhesive composition to one bonding surface or both bonding surfaces. In order to cure the composition, it can be carried out by standing at room temperature. By repeating this a desired number of times, a laminate in which a desired number of members are laminated can be produced. The standing at normal temperature may be performed every time one member is stacked, or may be performed collectively after stacking a plurality of members. The number of laminated layers is preferably 2 to 100, more preferably 3 to 50, and most preferably 4 to 20 from the viewpoint of workability.

(2-1) When a radical photopolymerization initiator is used, visible light or ultraviolet light is irradiated to cure the composition. Examples of the method for adhering the members include an adhesive method for improving adhesiveness by irradiating at least one of visible light or ultraviolet light to the temporary fixing adhesive composition. As an energy irradiation source for irradiating such visible light or ultraviolet light, a deuterium lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a xenon-mercury hybrid lamp, a halogen lamp, an excimer lamp, Examples of the energy irradiation source include an indium lamp, a thallium lamp, an LED lamp, and an electrodeless discharge lamp.

(2-1) A method of using a temporary fixing adhesive composition (one-component temporary fixing adhesive composition) containing a photoradical polymerization initiator is as follows.

When the adhesive composition for temporary fixing is cured by irradiating visible light or ultraviolet rays, and the member is temporarily fixed, a light energy amount of 10 to 15000 mJ / cm ^{2 at} a wavelength of 365 nm is applied to the temporary fixing adhesive composition. It is preferable to irradiate and bond the members together. 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, after using the above-described temporary fixing method by light energy, the adhesive composition for temporary fixing is immersed in water. The cured body is softened, whereby the organic thermally expandable particles are easily expanded, water enters the interface between the member and the temporarily fixed adhesive composition cured body, and the cured body can be more easily peeled off. The higher the temperature of the water, the larger the expansion of the organic thermally expandable particles, so that the water easily enters and the cured body can be easily peeled off. The temperature of water when removing the cured body is preferably higher than 40 ° C., more preferably 60 ° C. or higher, most preferably 80 to 100 ° C., and still 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 above-described temporary fixing method by light energy, the adhesive is heated to 80 to 300 ° C., thereby temporarily fixing the adhesive. The cured body of the composition is softened, whereby the organic thermally expandable particles are easily expanded, and a void is formed at the interface between the cured body and the temporary fixing adhesive composition, so that the cured body can be more easily peeled off. The higher the heating temperature, the easier the exfoliation of the cured body is in terms of the larger expansion of the organic thermally expandable particles. The heating temperature for removing the cured body is more preferably 100 to 260 ° C, and 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, for example, a temporary fixing adhesive that is sandwiched between both members and then spread after bonding each member coated with the temporary fixing adhesive composition to one bonding surface or both bonding surfaces. In order to cure the composition, it can be carried out by irradiating with light. By repeating this a desired number of times, a laminate in which a desired number of members are laminated can be produced. The light irradiation may be performed every time one member is stacked, or may be performed collectively after stacking a plurality of sheets as long as light reaches the temporary fixing adhesive composition. The number of stacked layers is preferably 2 to 100, more preferably 3 to 50, and most preferably 4 to 20 from the viewpoint of workability.

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 members selected from the group consisting of quartz, ceramics, silicon, and glass are 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, and more preferably 100 μm or more.

Such a member has a problem that it easily breaks and chipping easily occurs. Even such a member can be processed and peeled off by the temporary fixing method of the present invention. Even if it is a member having a thickness of 200 μm or less, which is difficult to be precisely processed, or a member having an adhesion area of 60 cm ² or more that is difficult to peel off, the temporary fixing method of the present invention can be used for processing and peeling. Is possible.

The temporarily fixed member is processed by cutting, grinding, polishing, drilling, etc. in order to obtain a desired shape, and then the member is immersed in water, preferably warm water, or heated. The cured body of the temporary fixing adhesive composition can be peeled 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 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 40 to 4500 MPa, the dimensional accuracy and chipping property at the time of processing are excellent, and if the tensile storage elastic modulus at 90 ° C is within the range of 0.5 to 10 MPa, adhesion for temporary fixing When the cured product of the agent composition is peeled from the member, the organic thermally 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. When 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 a cured product obtained from the composition Does not swell, it may be inferior in peelability. If the tensile storage modulus of the cured body at 90 ° C. exceeds 10 MPa, expansion of the organic thermally expandable particles may be hindered at the time of peeling, and the peelability may be poor.

Although there is no restriction | limiting in particular in the measuring method of the glass transition temperature of the hardening body obtained from the matrix composition of this invention, It measures by well-known methods, such as DSC and a dynamic viscoelastic spectrum. A preferable method is a method using a dynamic viscoelastic spectrum.

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 1-8, Comparative Examples 1-4)
Evaluation was made by the following method.

(Preparation of adhesive composition)
The materials used in Table 1 were used. Each use material was mixed with the composition of Tables 2-3, and the adhesive composition which consists of a 1st agent and a 2nd agent (2 agents may be called 2 liquids) was prepared. Using the obtained adhesive composition, the B-type viscosity by the evaluation method shown below, the tensile storage elastic modulus (23 ° C.) of the cured product obtained from the matrix composition (two-component curing), from the matrix composition Tensile 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 Concentration, adhesion / peeling test (A), adhesion / peeling test (B), adhesion / peeling test (C), and laminating 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 2-3.

(Evaluation method)

Integrated light quantity and illuminance: The integrated light quantity and illuminance were measured with an ultraviolet integrated illuminometer (manufactured by Eye Graphics, Inc .: EYE UVMETER UVPF-A1 (using 365 nm light receiver)).

B-type viscosity: A viscosity measured using a B-type viscometer under conditions of 25 ° C. and a rotation speed of 10 rpm.
D hardness of the cured adhesive by two-component curing (“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 as a mold A frame was placed between the 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 produced cured body was cut into a cylindrical shape having a diameter of 30 mm with a cutter to obtain a cured body for Shore D hardness measurement. The value of the obtained cured product was measured by ASTM D-2240 using a D-type shore hardness meter.

Tensile shear adhesive strength by two-component curing (“Adhesive strength (two-component curing)” in the table): Measured according to JIS K 6850. Specifically, using the heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, length 25 mm × width 25 mm × thickness 2.0 mm) as the adherend, the adhesion site was made into a circle with a diameter of 8 mm, After bonding two heat-resistant glasses together and curing them at 23 ° C. for 24 hours with an adhesive composition in which equal amounts of the first and second agents are mixed, a tensile shear bond strength test piece is prepared. did. The prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.

Tensile storage elastic modulus (23 ° C.) of the cured product obtained from the matrix composition by two-component curing (“Tensile storage elastic modulus (23 ° C.) of the cured product obtained from the matrix composition (two-component curing)” in the table) and Tensile storage elastic modulus (90 ° C.) of the cured product obtained from the matrix composition (“Tensile storage elastic modulus (90 ° C.) of the cured product obtained from the matrix composition (two-component curing)” in the table): Tables 2-3 Among the compositions of (1), (2), (4) and (6), the respective use materials are mixed to adjust the matrix composition of the first agent. 1), (2), (4), (5) and (6) are mixed together to prepare a second agent matrix composition. The first agent matrix composition and the second agent matrix A matrix composition mixture in which an equal amount of the composition is mixed, a 1 mm thick silicon sheet as a mold , Sandwiched PET film. 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 produced cured body was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured body for measuring a glass transition temperature. The obtained cured body was subjected to stress and strain in a tensile direction of 1 Hz to the cured body in a nitrogen atmosphere by a dynamic viscoelasticity measuring device “DMS210” manufactured by Seiko Electronics Industry Co., Ltd. The tensile storage elastic modulus was measured while raising the temperature at a rate of 23 ° C., and the measured values of the tensile storage elastic modulus at 23 ° C. and 90 ° C. were obtained from the matrix composition by two-liquid curing, respectively. And the tensile storage 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, several drops of an adhesive composition in which equal amounts of the first agent and the second agent are mixed in one glass And stacked 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 defined as the fixing time.

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

(Adhesion / peeling test (A))
7 g of an adhesive composition in which equal amounts of the first agent and the second agent are mixed is applied onto the member glass A (length 150 mm × width 150 mm × thickness 2 mm), and glass B (length 150 mm × width 150 mm). × 200 μm thickness), cured for 24 hours at 23 ° C., cured, and after confirming that it was completely adhered, the obtained specimen was immersed in warm water (95 ° C.) The time for peeling off was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersing in warm water until the member peels.

(Adhesion / peeling test (B))
7 g of an adhesive composition in which equal amounts of the first agent and the second agent are mixed is applied onto the member glass A (length 150 mm × width 150 mm × thickness 2 mm), 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 bonded together. Then, the obtained test body was heated at 160 degreeC on the hotplate, the time for which glass peels was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from when the test body is placed on a hot plate heated to 160 ° C. until the member peels.

(Adhesion / peeling test (C))
7 g of an adhesive composition in which equal amounts of the first agent and the second agent are mixed is applied onto the member glass A (length 150 mm × width 150 mm × thickness 2 mm), and glass B (length 150 mm × width 150 mm). × 200 μm thickness), cured for 24 hours at 23 ° C. and cured, and after confirming that it was completely adhered, the obtained specimen was immersed in warm water (90 ° C.) The time for peeling off was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersing in warm water until the member peels.

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

1. Twelve pieces of glass (length 150 mm × width 150 mm × thickness 200 μm) are pasted on the glass (length 150 mm × width 150 mm × thickness 200 μm), which is a production member of the glass laminate, via the adhesive composition, A laminated body of glass was produced.
In the two-component adhesive composition, a laminate produced 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 an adhesive composition containing a radical photopolymerization initiator (one-component adhesive composition), black light is used, and light is irradiated from the upper surface of the glass under the condition of an integrated light quantity of 2000 mJ / cm ² at a wavelength of 365 nm. And cured. In addition, light irradiation was implemented whenever it laminated | stacked one sheet of glass, and the laminated body of glass was produced by repeating 11 times.

2. Next, the glass laminate was cut in the thickness direction along a predetermined cutting line with a slicer (slicing machine) to produce a divided glass laminate. At this time, the glass was divided into 40 mm wide × 40 mm long × 2.4 mm thick.

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

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

(Preparation of adhesive composition)
The materials used in Table 1 were used. Each material used was mixed with the composition of Table 6 to prepare an adhesive composition of one agent (one agent may be referred to as one liquid). Using the obtained adhesive composition, the B-type viscosity, the tensile storage elastic modulus (23 ° C.) obtained from the matrix composition (UV irradiation), and the tensile storage obtained from the matrix composition by the evaluation methods shown below. Elastic modulus (90 ° C.) (UV irradiation), adhesive strength (UV irradiation), D hardness (UV irradiation), fixing time (5 mW / cm ² ), adhesion / peeling test (D), adhesion / peeling test (E) The adhesion / peeling test (F) and the laminating 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 cured adhesive body by UV irradiation ("D hardness (UV irradiation)" in the table): Light is used for the adhesive composition using a black light under the condition of an integrated light amount of 2000 mJ / cm ² at a wavelength of 365 nm. Was irradiated from the upper surface and cured, and then further light was irradiated and cured from the lower surface under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm from the lower surface to produce five cured bodies having a thickness of 1 mm. The produced cured body was cut into a cylindrical shape having a diameter of 30 mm with a cutter, and five cured bodies having a thickness of 1 mm were stacked to obtain a cured body for Shore D hardness measurement. The value of the obtained cured product was measured by ASTM D-2240 using a D-type Shore hardness meter.

Tensile shear adhesive strength by UV irradiation (“Adhesive strength (UV irradiation)” in the table): Measured according to JIS K 6850. Adhesive composition using a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, length 25 mm × width 25 mm × thickness 2.0 mm) as an adherend, and a bonding portion having a circular shape with a diameter of 8 mm. Two heat-resistant glass are bonded together using a black light, light is irradiated from the upper surface under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm, and a tensile shear bond strength test piece. Was made. The prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.

Tensile storage modulus (23 ° C.) of a cured product obtained from a matrix composition by UV irradiation (“Tension storage elastic modulus (23 ° C.) of a cured product obtained from a matrix composition (UV irradiation)” in the table) and matrix composition Tensile storage elastic modulus (90 ° C.) of the cured product obtained from the product (“Tension storage elastic modulus of the cured product obtained from the matrix composition (90 ° C.) (UV irradiation)” in the table): (1), (2), (4), (6) each material used is mixed to prepare a cured product obtained from the matrix composition, and the composition is a 1 mm thick silicon sheet as a mold, It was sandwiched between PET films. The composition was irradiated with light from the upper surface using a black light under the condition of an integrated light amount of 2000 mJ / cm ² at a wavelength of 365 nm, and further cured from a lower surface with an integrated light amount of 2000 mJ / cm ² at a wavelength of 365 nm. Light was irradiated from the lower surface under conditions, and cured to produce a cured body of an adhesive composition having a thickness of 1 mm. The produced cured body was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured body for measuring a glass transition temperature. The obtained cured body was subjected to stress and strain in a tensile direction of 1 Hz to the cured body in a nitrogen atmosphere by a dynamic viscoelasticity measuring device “DMS210” manufactured by Seiko Electronics Industry Co., Ltd. The tensile storage elastic modulus was measured while the temperature was raised at a rate of 23 ° C., and the tensile storage elastic modulus (23 ° C. of the cured product obtained from the matrix composition by UV curing was measured respectively at 23 ° C. and 90 ° C. of the tensile storage elastic modulus. ) And the tensile storage 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, several drops of the adhesive composition were added to one glass and overlapped 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 defined as the fixing time.

(Adhesion / peeling test (D))
7 g of the adhesive composition is applied onto the member glass A (length 150 mm × width 150 mm × thickness 2 mm), and glass B (length 150 mm × width 150 mm × thickness 200 μm) is bonded to the black light. Used, light was irradiated and cured from the upper surface of the glass B under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm, and the glasses were bonded together. Then, the obtained test body was immersed in warm water (95 degreeC), the time which glass peels was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersing in warm water until the member peels.

(Adhesion / peeling test (E))
7 g of the adhesive composition is applied onto the member glass A (length 150 mm × width 150 mm × thickness 2 mm), and glass B (length 150 mm × width 150 mm × thickness 200 μm) is bonded to the black light. Used, light was irradiated and cured from the upper surface of the glass B under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm, and the glasses were bonded together. Then, the obtained test body was immersed in warm water (90 degreeC), the time which glass peels was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from immersing in warm water until the member peels.

(Adhesion / peeling test (F))
7 g of the adhesive composition is applied onto the member glass A (length 150 mm × width 150 mm × thickness 2 mm), and glass B (length 150 mm × width 150 mm × thickness 200 μm) is bonded to the black light. Used, light was irradiated and cured from the upper surface of the glass B under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm, and the glasses were bonded together. Then, the obtained test body was heated at 160 degreeC on the hotplate, the time for which glass peels was measured, and the state of the film after peeling was also confirmed. The peeling time refers to the time from when the test body is placed on a hot plate heated to 160 ° C. until the member peels.

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

1. Twelve pieces of glass (length 150 mm × width 150 mm × thickness 200 μm) are pasted on the glass (length 150 mm × width 150 mm × thickness 200 μm), which is a production member of the glass laminate, via the adhesive composition, A laminated body of glass was produced.
In the two-component adhesive composition, a laminate produced 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 an adhesive composition containing a radical photopolymerization initiator (one-component adhesive composition), black light is used, and light is irradiated from the upper surface of the glass under the condition of an integrated light quantity of 2000 mJ / cm ² at a wavelength of 365 nm. And cured. In addition, light irradiation was implemented whenever it laminated | stacked one sheet of glass, and the laminated body of glass was produced by repeating 11 times.

2. Cutting processing of glass laminate Next, the glass laminate was cut in the thickness direction along a predetermined cutting line by a slicer to produce 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. The obtained glass laminate was exposed in an oven heated to 160 ° C. for 30 minutes, the time for separating the glasses was measured, and the state of the film after peeling was also confirmed. The peeling time (the time required for peeling all 12 sheets) was set to the time required for peeling all 12 sheets of glass after placing the specimen in an oven heated to 160 ° C.

From Tables 1-7, it turned out that this invention has the outstanding effect. In Comparative Examples 1 to 5, any component was outside the scope of the present invention, and the effects of the present invention were not exhibited.

Since the comparative example 1 did not contain a component (4), the member did not peel. Since Comparative Examples 2-3 had few components (1-4), peeling time was long and there was much leakage of isobutane gas at the time of storage. Since the comparative example 4 had many components (1-4), the hardening body of adhesive composition remained in the member and the peeling state was not good. In the peel test, when glue remained or a cured product of the adhesive composition remained on the member, it was difficult to recover the member, and workability was not good. Since Comparative Example 5 did not contain the component (1-1), the member sometimes did not peel off.

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

In the present invention, since the adhesive body is brought into contact with warm water, the adhesiveness is reduced, and the bonding force between the members or between the member and the jig is reduced. Therefore, the member can be easily recovered.

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

The method for temporarily fixing a member of the present invention is capable of processing even a member that is thin and difficult to process, has no adhesive residue on the member even after peeling, and can easily recover the cured body from the member, so that the workability is excellent.
In the prior art, it is difficult to temporarily fix a member that is thin and difficult to process or a large-area member, and to accurately process without chipping. After processing, it is difficult to easily peel off without any adhesive residue. 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 if it is a difficult member or a large area member, Adequate adhesiveness can be obtained without increasing the thickness, no deviation occurs during processing, dimensional accuracy and chipping properties are improved, and an excellent member can be easily obtained.
In the present invention, by reducing the average particle size of the granular material, 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) (1-1) Imido (meth) acrylate and / or cyclic trimethylolpropane formal (meth) acrylate, (1-2) urethane (meth) acrylate, (1-3) many other than (1-2) A polymerizable vinyl derivative containing a functional (meth) acrylate, (1-4) alkyl (meth) acrylate,
(2) radical polymerization initiator,
(3) Organic thermally expandable particles,
(4) A composition containing particulate matter,
(1) A composition containing 3 to 20 parts by mass of (1-4) alkyl (meth) acrylate in 100 parts by mass of the polymerizable vinyl derivative. (1) In 100 parts by mass of the polymerizable vinyl derivative, (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, comprising 3 to 20 parts by mass. 2. The composition according to claim 1, wherein (1) the polymerizable vinyl derivative contains a monofunctional (meth) acrylate other than (1-5) (1-1) and (1-4). (1) In 100 parts by mass of the polymerizable vinyl derivative, (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 of Claim 3 containing 3-20 mass parts and (1-5) 1-15 mass parts. (3) The composition according to any one of claims 1 to 4, wherein the organic heat-expandable particles have a temperature capable of volume expansion of 3 times or more, from 80C to 120C. (3) The composition according to any one of claims 1 to 5, wherein the organic heat-expandable particles have a temperature capable of volume expansion of 3 times or more, from 85C to 95C. Furthermore, (4) The average particle diameter of a granular material is 15-80 micrometers, The composition of any one of Claims 1-6. (1-4) Alkyl (meth) acrylate is lauryl (meth) acrylate, The composition of any one of Claims 1-7. (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. The composition according to claim 10 or 11, further comprising (5) a reducing agent. The composition according to claim 12 is divided into two parts, a two-part composition containing (2-2) a thermal radical polymerization initiator in the first part and (5) a reducing agent in the second part. The composition according to claim 13, comprising (2-1) a radical photopolymerization initiator in the first agent and / or the second agent. The composition according to any one of claims 1 to 14, wherein the cured product of the composition has a tensile storage modulus at 23 ° C of 40 to 4500 MPa and a tensile storage modulus at 90 ° C of 0.5 to 10 MPa. . The adhesive composition containing the composition of any one of Claims 1-15. The adhesive composition according to claim 16, wherein the use is for bonding one or more adherends of the group consisting of quartz bonding, ceramic bonding, silicon bonding and glass bonding. The adhesive composition according to claim 16, wherein the adhesive composition is used 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. A 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 body is processed. A method for temporarily fixing a member for removing a cured body of the temporary fixing adhesive composition by immersing in water. A 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 body is processed. A method for temporarily fixing a member for removing a cured body of the adhesive composition for temporary fixing by heating to 80 to 300 ° C. A method for producing a member for removing an adhesive body by temporarily fixing 2 to 100 workpieces using the temporary fixing adhesive composition according to claim 19 and immersing the adhesive body in water after processing. A joined body for joining members through the temporary fixing adhesive composition according to claim 19. The joined body according to claim 23, wherein the member is one or more members selected from 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 an area of the processed member is 60 cm ² or more.