JP6275375B2 - Temporary fixing method of member using composition - Google Patents

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 and a peeling method for temporarily fixing a member having a rough surface or a large area member, 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 double-sided tape, it is difficult to obtain dimensional accuracy, the chipping property is inferior when parts are processed due to low adhesive strength, and it cannot be peeled off unless heated to 100 ° C or higher. was there. In the case of peeling by ultraviolet irradiation, there is a problem that peeling is not possible 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 a problem.

  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 about organic heat-expandable particles.

In Patent Document 2, a carbon-functional 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 is then immersed in water and removed. However, the temporary fixing method using these adhesives has a problem that the working time becomes long with a large-area member because the dissolution and swelling speed of the adhesive when removing is slow.

In Patent Documents 3 and 4, a heat-peelable adhesive that can be easily self-peeled after the adhesion is significantly reduced by heat treatment after adding organic thermal expandable particles at a specific ratio in the adhesive. 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.

International Publication No. 2008/018252 Pamphlet Japanese Patent No. 2973991 Japanese Patent No. 3629021 Japanese Patent No. 4886369

In order to solve these problems of the prior art, for example, it is possible to apply even members with rough surfaces or members with a large area, and there is no adhesive residue on the member after peeling, which is excellent in workability and environment. There has been a need for a temporary fixing adhesive composition.

That is, the present invention relates to (1) a polyester-based urethane (meta) having two or more (meth) acryloyl groups at the molecular end or side chain in 100 parts by mass of (1), (2), and (6). ) 20-60 parts by mass of acrylate, (2) 20-60 parts by mass of a monofunctional (meth) acrylate having a polyalkylene oxide structure, (3) a radical polymerization initiator, (4) particulate material having an average particle size of 80-300 μm 0 .1-30 parts by mass, (5) 1-30 parts by mass of organic thermal expandable particles encapsulating butane and / or isobutane, (6) provisional containing 0-30 parts by mass of polyfunctional acrylate other than (1) The fixing adhesive composition is used to temporarily fix the member by allowing it to stand at room temperature for 0.5 to 500 hours, to cure the temporary fixing adhesive composition, and to process the temporarily fixed member The processed adhesive By immersion in, the a temporary fixing method for members to remove the cured product of the temporary fixing adhesive composition.
The temporary fixing method in which the temperature of water when removing the cured body is higher than 40 ° C. and 100 ° C. or lower and the immersion time is 1 to 240 minutes is preferable.
(1) In a total of 100 parts by mass of (2) and (6), (1) Polyester urethane (meth) acrylate having 2 or more (meth) acryloyl groups at the terminal or side chain of the molecule 20 to 60 masses Parts, (2) monofunctional (meth) acrylate having a polyalkylene oxide structure 20 to 60 parts by mass, (3) radical polymerization initiator, (4) 0.1 to 30 parts by mass of a granular material having an average particle size of 80 to 300 μm (5) Temporary fixing adhesive composition containing 1 to 30 parts by mass of organic heat-expandable particles containing butane and / or isobutane, and (6) 0 to 30 parts by mass of polyfunctional acrylate other than (1) with a member bonded temporarily fixed by 0.5 to 500 hours standing at room temperature, curing the temporary fixing adhesive composition, processing the tentative fixed member was processed adhesion 100-200 ° C body By heat treatment, a provisional fixing method member to remove the cured product of the temporary fixing adhesive composition.
The temporary fixing method in which the heating time for removing the cured body is 1 to 240 minutes is preferable.
It is preferably used for temporarily fixing a member having a bonded area after processing of 225 cm ² or more.
It is preferably used for temporarily fixing a member having a surface roughness Ra of 0.2 μm or more.
The (1) is a polyester urethane (meth) acrylate oligomer having a molecular weight of 10,000 to 50,000, the (2) is a monofunctional (meth) acrylate having a polyethylene oxide structure, the (5) butane and / or Or the polymer which consists of 1 type or 2 or more types in the group which the organic type thermally expansible particle | grains which include isobutane comprise butane and / or isobutane from vinylidene chloride, (meth) acrylonitrile, methyl (meth) acrylate. Or a thermally expandable microcapsule encapsulated with a thermoplastic resin which is a copolymer, wherein (6) the polyfunctional acrylate is tripropylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1 One of the group consisting of, 6-hexanediol di (meth) acrylate Or preferably consists of two or more.
The (1) is preferably a polyester urethane (meth) acrylate oligomer having a molecular weight of 25,000 to 50,000.
The (1) is a polyester urethane (meth) acrylate obtained by reacting a polyester polyol compound, an organic polyisocyanate compound, and a hydroxy (meth) acrylate, and the polyester polyol compound is a polyhydric alcohol or a polyether polyol. , A polyester polyol that is a condensate with a polybasic acid, and the polyhydric alcohol or polyether polyol is one or more of the group consisting of ethylene glycol, 1,4-butanediol, and hydrogenated polybutadiene polyol The polybasic acid is adipic acid, the organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, is preferably 2-hydroxybutyl (meth) one selected from the group consisting of acrylate or 2 or more kinds.
The (2) monofunctional (meth) acrylate having a polyethylene oxide structure is preferably a monofunctional (meth) acrylate having a structure represented by the following chemical formula (D).
Chemical formula (D)
_{- (- CH 2 -CH 2 -O-} ) n -
(However, n = 2-4)
The (3) polymerization initiator is preferably (3-1) a thermal radical polymerization initiator.
The composition is preferably divided into two parts, and the first part contains a (3-1) thermal radical polymerization initiator and the second part contains a (7) reducing agent. .
The (7) is preferably composed of one or more of the group consisting of vanadium acetylacetonate, copper naphthenate and cobalt octylate.
The amount of (3-1) used is 0.1 to 5 parts by mass and the amount of (7) used is 0.1 to 5 with respect to 100 parts by mass in total of (1), (2) and (6). The said composition which is a mass part is preferable.
The (3) polymerization initiator is preferably (3-2) a radical photopolymerization initiator.
It is preferable that the usage-amount of said (3-2) is 0.1-20 mass parts with respect to 100 mass parts in total of (1), (2), (6).
It is preferable that said (4) is 1 type (s) or 2 or more types in the group which consists of bridge | crosslinking poly (meth) acrylate methyl particle, bridge | crosslinking polystyrene particle, and bridge | crosslinking poly (meth) methyl acrylate polystyrene copolymer particle.
Furthermore, it is preferable to contain 0.001-3 mass parts polymerization inhibitor with respect to 100 mass parts in total of (1), (2), and (6).
The use is preferably one or more of the group consisting of quartz bonding, ceramic bonding, and glass bonding.
Part material is quartz, one or two or more at which the temporary fixing method selected from the group consisting of ceramic and glass are preferred.
The temporary fixing method in which the surface roughness Ra of the member is 0.2 μm or more is preferable. The temporary fixing method in which the bonded area of the processed member is 225 cm ² or more is preferable.
A method for producing a quartz product in which the quartz product is removed by temporarily bonding and fixing 2 to 100 quartz substrates using the adhesive composition for temporary fixing, immersing the adhesive in water after processing, is preferable.
There is provided a method for producing a quartz product in which a quartz product is removed by temporarily bonding and processing 2 to 100 quartz substrates using the adhesive composition for temporary fixing, heating the bonded body to 100 to 200 ° C. after processing. preferable.

The present invention is excellent in workability and environmental performance, for example. The present invention, for example, is excellent in the property (hereinafter simply referred to as “peelability”) that the cured body of the temporary fixing adhesive composition is peeled off from the adherend even if the surface is rough and has a large area. There is no adhesive residue afterward, and a processed member can be obtained with high dimensional accuracy.

The present invention will be described below.

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. In the case of a two-component temporary fixing adhesive composition, the total of 100 parts by mass of (1), (2), and (6) used as necessary is the sum of the first agent and the second agent ( The sum of (1), (2) and (6) used as necessary.

(1) 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. In (1), it is preferable to have two or more (meth) acryloyl groups at the end of the molecule.

Here, the polyester-based urethane (meth) acrylate is 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). This refers to urethane (meth) acrylate obtained by reacting.

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. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, polybutylene glycol, 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, polytrimethyl Rupuropan, pentaerythritol, poly pentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, polybutadiene polyol, hydrogenated polybutadiene polyol, 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. Examples of the polyether polyol include a polyether polyol having at least one structure of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization. Among the polyhydric alcohols or polyether polyols, polyether polyols are preferred, and one or more of the group consisting of ethylene glycol, 1,4-butanediol, and hydrogenated polybutadiene polyol are preferred. 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.

As the organic polyisocyanate compound (Y), need not be particularly limited, aromatic For example, aliphatic, cycloaliphatic series, can polyisocyanate use of alicyclic. Among these birds 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 Polyisocyanates such as nate (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, hydrogenated xylylene diisocyanate (H-XDI) and / or 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, 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) acryloyloxypropyl (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified 2-hydroxyethyl (meth) acrylate. In these, the 1 type (s) or 2 or more types in the group which consists of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate is preferable.

(1) Among polyester urethane (meth) acrylates having two or more (meth) acryloyl groups at the molecular ends or side chains, polyester urethane (meth) acrylate oligomers having a molecular weight of 10,000 to 50,000 are preferred. Examples of the polyester-based urethane (meth) acrylate oligomer include polyfunctional (meth) acrylate oligomers / polymers that are two or more (meth) acryloylated at the oligomer / polymer terminal or side chain. Here, the molecular weight refers to the weight average molecular weight. Among these, the weight-average molecular weight of the polyester-based urethane (meth) acrylate oligomer is more preferably 15000 to 45000 in that the effect is great. 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 mm ID × 4.0 cm 1 and “TSK-GEL MULTIPIOREHXL-M” manufactured by Tosoh Corporation 7.8 mm ID × 30.0 cm (theoretical plate number 16,000 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

Examples of such a polyester urethane (meth) acrylate oligomer include “UV-2000B” (UV-2000B weight average molecular weight: 13000) and “UV-3000B” (UV-3000B weight average molecular weight) manufactured by Nihon Gosei Co., Ltd. : 18000), “KHP-11” (KHP-11 weight average molecular weight: 25000), “KHP-17” (KHP-17 weight average molecular weight: 40000), and the like manufactured by Negami Kogyo Co., Ltd. In these, the polyester-type urethane (meth) acrylate oligomer which has a structure represented by following Chemical formula (A) is preferable.

Chemical formula (A)
P-R-P
(Where P is the main skeleton P, R is the R component)

Among these, a polyester urethane (meth) acrylate oligomer having a structure represented by the following chemical formula (B) and / or a polyester urethane (meth) acrylate oligomer having a structure represented by the chemical formula (C) are preferable. The polyester-based urethane (meth) acrylate oligomer having a structure represented by the following chemical formula (B), the polyester polyol compound (X) is a condensate of ethylene glycol or 1,4-butanediol and adipic acid, The organic polyisocyanate compound (Y) is isophorone diisocyanate, and the hydroxy (meth) acrylate (Z) is 2-hydroxyethyl (meth) acrylate. In the polyester-based urethane (meth) acrylate oligomer having a structure represented by the following chemical formula (C), the polyester polyol compound (X) is a condensate of hydrogenated polybutadiene polyol and adipic acid, and an organic polyisocyanate compound ( Y) is isophorone diisocyanate, and hydroxy (meth) acrylate (Z) is 2-hydroxybutyl (meth) acrylate.

Examples of the polyester urethane (meth) acrylate oligomer having a structure represented by the chemical formula (B) include “UV-3000B” (provided that R ′ is H) manufactured by Nihon Gosei Co., Ltd. Examples of the polyester-based urethane (meth) acrylate oligomer having a structure represented by the chemical formula (C) include “KHP-11” and “KHP-17” (R ′ ′ is H) manufactured by Negami Kogyo Co., Ltd.

As for the usage-amount of (1), 20-60 mass parts is preferable in 100 mass parts for the sum total of (1), (2), and (6) used as needed. If it is less than 20 parts by mass, peelability may not be obtained, and if it exceeds 60 parts by mass, the temporary fixing adhesive composition may have high viscosity and workability may not be obtained. From a viewpoint of peelability and workability, 30 to 50 parts by mass is more preferable, and 35 to 45 parts by mass is most preferable.

(2) The monofunctional (meth) acrylate having a polyalkylene oxide structure is preferably a monofunctional (meth) acrylate having a polyethylene oxide structure. The monofunctional (meth) acrylate having a polyethylene oxide structure is preferably a monofunctional (meth) acrylate having a structure represented by the following chemical formula (D).

Chemical formula (D)
_{- (- CH 2 -CH 2 -O-} ) n -
(However, n = 2-4)

(2) Monofunctional (meth) acrylates having a structure represented by chemical formula (D) include methoxy (ethylene oxide 2 mol modified) (meth) acrylate, methoxy (ethylene oxide 3 mol modified) (meth) acrylate, methoxy (Ethylene oxide 4 mol modified) (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, phenol (ethylene oxide 2 mol modified) (meth) acrylate, phenol (ethylene oxide 3 mol modified) (meth) acrylate, phenol (ethylene Oxide 4 mol modified) (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) (meth) acrylate, and the like. Among them, phenol (ethylene oxide 2 mol modified) (meth) acrylate, phenol (ethylene oxide 3 mol modified) (meth) acrylate, phenol (ethylene oxide 4 mol modified) (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) ( 1 type or 2 or more types in the group which consists of a meth) acrylate are preferable, and a phenol (ethylene oxide 2 mol modification | denaturation) (meth) acrylate is more preferable. Monofunctional (meth) acrylate refers to a compound having one (meth) acryloyl group in the molecule.

As for the usage-amount of (2), 20-60 mass parts is preferable in 100 mass parts for the sum total of (1), (2), and (6) used as needed. If the amount is less than 20 parts by mass, the peelability may not be obtained. If the amount exceeds 60 parts by mass, the hardness of the temporarily fixing adhesive composition is lowered. Accuracy may not be obtained. From the viewpoint of peelability and dimensional accuracy, 25 to 55 parts by mass are more preferable, and 30 to 45 parts by mass are most preferable.

(3) As a polymerization initiator, 1 type or 2 types selected from the group which consists of (3-1) thermal radical polymerization initiator and (3-2) radical photopolymerization initiator are preferable.

(3-1) The thermal radical polymerization initiator is preferably an organic or inorganic peroxide, and more preferably an organic peroxide. 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, hydroperoxides are more preferable, and cumene hydroperoxide is most preferable.

(3-1) The usage amount of the thermal radical polymerization initiator is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight in total of (1), (2) and (6) used as necessary. 1 to 3 parts by mass 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.

In the temporary fixing adhesive composition of the present invention, when (3-1) a thermal radical polymerization initiator is used, (7) a reducing agent can be used in combination. Examples of the reducing agent include transition metal salts such as copper naphthenate, vanadium acetylacetonate, and cobalt octylate. Of these, cobalt octylate is preferred.

The amount of the (7) reducing agent used in the present invention is preferably 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of (1), (2) and (6) used as necessary. -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.

The adhesive composition for temporary fixing of the present invention includes a two-component type temporary fixing in which the first agent contains at least (3-1) a thermal radical polymerization initiator and the second agent contains at least (7) a reducing agent. It is preferably used as an adhesive composition. 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. In this case, (4) particulate matter, (5) organic heat-expandable particles encapsulating butane and / or isobutane, and (3-2) photoradical polymerization initiator are either the first agent or the second agent or It may be contained in both. 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, an appropriate amount of adhesive is applied to the bonding surface of one member to be fixed, and then the other member is superposed, or temporarily fixed. Examples include a method in which a large number of members are stacked, an adhesive is applied by infiltrating an adhesive into a gap, and the like, the adhesive composition for temporary fixing is cured, and members are temporarily fixed.

The adhesive composition for temporary fixing according to the present invention does not require accurate metering of the two agents, and is cured at room temperature even by incomplete metering or mixing, or sometimes only by contact of 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 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 adhesive strength is obtained, and if it is 500 hours or less, sufficient adhesive strength 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.

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 hardened body of the product is softened, so that the organic thermally expandable particles containing butane and / or isobutane easily expand, and water is formed at the interface between the cured body (adhesive substrate) and the temporary fixing adhesive composition. Penetrates and the cured body can be peeled off more easily. The higher the temperature of the water, the greater the expansion of the organic thermally expandable particles encapsulating butane and / or isobutane, so that water easily enters and the cured product 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, and most preferably 80 to 100 ° C. in terms of peelability and deterioration of the adhesive substrate due to warm water. 100 ° C. is more preferable. 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 100 to 200 ° C. for temporary fixing. The cured body of the adhesive composition is softened, whereby the organic thermally expandable particles containing butane and / or isobutane easily expand, and the cured body (adhesive base material) and the temporary fixing adhesive composition A space is generated at the interface, and the cured body can be more easily peeled off. When the heating temperature is higher, the organic thermally expandable particles encapsulating butane and / or isobutane have a larger expansion, so that the cured product can be easily peeled off. The heating temperature when removing the cured body is more preferably 130 to 200 ° C, and most preferably 150 to 260 ° C, in terms of peelability and deterioration of the adhesive substrate. 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 stacked layers is preferably 2 to 100, more preferably 3 to 50, and most preferably 4 to 20 from the viewpoint of workability.

(3-2) The radical photopolymerization initiator is used for sensitization with visible light or ultraviolet actinic light to promote photocuring of the resin 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. A radical photopolymerization initiator can be used alone or in combination of two or more. Among these, benzyldimethyl ketal and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one are particularly effective. One or two of the groups are preferred.

(3-2) The amount of the radical photopolymerization initiator used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of (1), (2) and (6) used as necessary. 1-10 mass parts is more preferable. If it is 0.1 mass part or more, the effect of hardening acceleration will be acquired reliably, and sufficient peelability can be obtained if it is 20 mass parts or less.

(3-2) When a radical photopolymerization initiator is used, the composition is cured by irradiation with visible light or ultraviolet rays. Examples of a method for adhering members include an adhesion method for increasing adhesive strength 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.

The method of using the 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, the adhesive composition for temporary fixing is irradiated with energy of 1 to 10,000 mJ / cm ^{2 at} a wavelength of 365 nm. It is preferable to bond the adhesive substrates together. If it is 1-10000mJ / cm < ² >, the adhesive composition for temporary fixing will harden | cure and sufficient adhesive strength will be obtained. If it is 1 mJ / cm ² or more, the adhesive composition for temporary fixing is sufficiently cured, and if it is 10000 mJ / cm ² or less, there is no curing distortion and the adhesive strength is improved. Energy at the time of temporarily fixed member each other in terms of bond strength, more preferably ^{10~5000mJ / cm 2, 1500~3000mJ / 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 hardened body is softened, so that the organic thermally expandable particles containing butane and / or isobutane easily expand, and water enters the interface between the hardened body (adhesive substrate) and the temporary fixing adhesive composition. In addition, the cured body can be peeled off more easily. The higher the temperature of the water, the greater the expansion of the organic thermally expandable particles encapsulating butane and / or isobutane, so that water easily enters and the cured product 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, and most preferably 80 to 100 ° C. in terms of peelability and deterioration of the adhesive substrate due to warm water. 100 ° C. is more preferable. 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 using light energy described above is used, and then the adhesive body is heated to 100 to 200 ° C., thereby temporarily fixing the adhesive. The hardened body of the composition is softened, so that the organic thermally expandable particles encapsulating butane and / or isobutane easily expand, and at the interface between the hardened body (adhesive base material) and the temporary fixing adhesive composition. A space | gap arises and it can peel a hardening body more easily. When the heating temperature is higher, the cured body can be peeled off more easily because the expansion of the organic thermally expandable particles containing butane and / or isobutane is larger. The heating temperature when removing the cured body is more preferably 130 to 200 ° C, and most preferably 150 to 260 ° C, in terms of peelability and deterioration of the adhesive substrate. The heating time is preferably 1 to 240 minutes, more preferably 10 to 120 minutes, and most preferably 15 to 60 minutes.

When removing the cured product of the temporary fixing adhesive composition, the temporary fixing adhesive composition is irradiated with visible light or ultraviolet light at an energy of preferably 40,000 mJ / cm ² at a wavelength of 365 nm. Since the radical is generated from 3-2), a large curing strain is generated, the cured body itself is greatly swelled, the adhesion area is reduced, and the adhesive strength is lowered, so that the cured body can be easily removed.

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.

(4) The granular material having an average particle size of 80 to 300 μm is preferably a granular material having an average particle size of 80 to 300 μm measured by a laser method. By using a granular material having an average particle size of 80 to 300 μm measured by the laser method (hereinafter sometimes referred to as a granular material), it becomes easy for the cured body to maintain a constant thickness, and dimensional accuracy is improved. It can adhere | attach, can control the thickness of a hardening body, and can obtain the stable peelability.

(4) The particulate material may be either organic particles or inorganic particles. The particulate material means a material excluding (5) organic heat-expandable particles described later. 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. Inorganic particles include ceramic particles such as glass, silica, alumina, titanium and the like.

(4) The granular material is preferably spherical in terms of improving processing accuracy, that is, controlling the thickness of the adhesive. 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 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 diameter 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 granular material used is 0. 0 in terms of adhesive strength, processing accuracy, and peelability with respect to 100 parts by mass in total of (1), (2) and (6) used as necessary. 1-30 mass parts is preferable, 0.5-20 mass parts is more preferable, and 1-5 mass parts is the most preferable.

(5) Organic heat-expandable particles encapsulating butane and / or isobutane (hereinafter sometimes referred to as organic heat-expandable particles) include butane and / or a microcapsule depending on the organic material (polymer) of the outer shell. Alternatively, thermally expandable microcapsules encapsulating isobutane can be given. (5) 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 is expanded. (5) The outer shell of the organic thermally expandable particles is preferably a thermoplastic resin containing a polymer or copolymer composed of vinylidene chloride, (meth) acrylonitrile, methyl (meth) acrylate. In the present invention, a thermally expandable microcapsule in which butane and / or isobutane is wrapped with an outer shell can be preferably used.

(5) The average particle diameter of the organic thermally expandable particles containing butane and / or isobutane is preferably 2 to 50 μm, more 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.

(5) The amount of organic thermally expandable particles used is based on 100 parts by mass in total of (1), (2) and (6) used as needed from the viewpoint of peeling promotion effect and adhesive strength. 1-30 parts by mass, more preferably 5-29.9 parts by mass, and most preferably 10-25 parts by mass. If it is 1 part by mass or more, the effect of promoting peeling can be reliably obtained, and if it is 30 parts by mass or less, sufficient adhesive force can be obtained.

In the present invention, it is further preferable to use (6) polyfunctional (meth) acrylate. (6) 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). (6) 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, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2, 2-bis (4- (meth) acryl Alkoxy tetra ethoxyphenyl) propane, dimethylol - tricyclodecane (meth) acrylate, 1,10-decanediol di (meth) acrylate, and the like isocyanuric acid ethylene oxide-modified di (meth) acrylate. Among these, one of the group consisting of 1,9-nonanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate and tripropylene glycol di (meth) acrylate is highly effective. Two or more species are preferred, and tripropylene glycol di (meth) acrylate is more preferred.

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

As tetrafunctional or higher (meth) acrylate monomers, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerystol penta (meth) acrylate, dipenta Examples include erythrole hexa (meth) acrylate.

As a usage-amount of (6), 0-30 mass parts is preferable in a total of 100 mass parts of (1), (2), and (6) used as needed. When the amount of use of (6) is within this range, the temporarily fixing adhesive composition has a high hardness, so that the temporarily fixed member is hardly displaced during processing, and the dimensional accuracy is excellent. If it exceeds 30 parts by mass, peelability may not be obtained. From a viewpoint of dimensional accuracy and peelability, 5 to 25 parts by mass is more preferable, and 10 to 20 parts by mass is most preferable.

In the composition of the present invention, a polymerization inhibitor can be used to improve the 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 0.001 to 3 parts by mass, more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass in total of (1), (2) and (6). 0.1 to 0.3 parts by mass is most 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 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.

In the present invention, the material of the member used for temporary fixing is not particularly limited, and examples thereof include a quartz member, a ceramic member, a crystal member, a glass member, and a plastic member. Such a member can be processed and peeled by the temporary fixing method of the present invention even if the surface roughness Ra of the member is 0.2 μm or more or the bonded area of the processed member is 60 cm ² or more. It is possible and applicable. The surface roughness Ra of the member is preferably 50 μm or less.

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

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 1-9, Comparative Examples 1-5)
Evaluation was made by the following method.

(Preparation of temporary fixing adhesive composition)
The materials used in Table 1 were used. Each material used is mixed in the composition of Table 2, Table 4, Table 6, and Table 8, and an adhesive composition for temporary fixing composed of a first agent and a second agent (the two agents are sometimes referred to as two liquids) or An adhesive composition for temporary fixing (one agent may be referred to as one liquid) was prepared. Using the obtained adhesive composition, D hardness, tensile shear bond strength measurement, and adhesion / peeling tests (A) to (F) were performed by the following evaluation methods. The results are shown in Table 3, Table 5, Table 7, and Table 9. The abbreviations shown in Table 1 were used for the composition names in Table 2, Table 4, Table 6, and Table 8.

(Evaluation method)

Integrated light amount: The integrated light amount was measured with an ultraviolet integrated illuminometer (manufactured by Eye Graphic: EYE UVMETER UVPF-A1 (using 365 nm light receiver)).

D hardness of cured adhesive body for temporary fixing by two-component curing (“D hardness (two-component curing)” in the table): 5 mm of an adhesive composition for temporary fixing in which equal amounts of the first agent and the second agent are mixed A thick silicon sheet was used as a mold and sandwiched between PET films. The temporary fixing adhesive composition was sandwiched between PET films using a 5 mm thick silicon sheet as a mold. The temporary fixing adhesive composition was cured at 23 ° C. for 24 hours to prepare a cured body of the temporary fixing 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.

D hardness of cured adhesive body for temporary fixing by UV irradiation ("D hardness (UV irradiation)" in the table): Using a belt conveyor type metal halide lamp, the temporary fixing adhesive composition is an integrated light quantity at a wavelength of 365 nm. After irradiating and curing light from the upper surface under the condition of 2000 mJ / cm ² , and further irradiating and curing light from the lower surface under the condition of an integrated light amount of 2000 mJ / cm ² with a wavelength of 365 nm from the lower surface, curing with a thickness of 5 mm The body was made. 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 bonding site is a circle with a diameter of 8 mm, Adhesive composition for temporary fixing in which equal amounts of the first agent and the second agent are mixed, two heat-resistant glasses are bonded together, cured at 23 ° C. for 24 hours, and then subjected to a tensile shear bond strength test. A 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 shear adhesive strength by UV irradiation (“Adhesive strength (UV irradiation)” in the table): Measured according to JIS K 6850. Adhesion for temporary fixing, using a heat-resistant glass (trade name “Heat-resistant Pyrex (registered trademark) glass”, length 25 mm × width 25 mm × thickness 2.0 mm) as the adherend, and making the bonding part a circle with a diameter of 8 mm Two heat-resistant glasses are bonded together using the agent composition, a belt conveyor type metal halide lamp is used, light is irradiated and cured from the upper surface under the condition of an integrated light amount of 2000 mJ / cm ² at a wavelength of 365 nm, and tension is applied. A shear bond strength test piece was prepared. 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.

(Adhesion / peeling test (A))
3 g of an adhesive composition obtained by mixing equal amounts of the first agent and the second agent on quartz glass A (length 60 mm × width 60 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive substrate Apply and paste quartz glass B (length 40 mm x width 40 mm x thickness 2 mm, surface roughness Ra: 0.7 μm), cure at 23 ° C. for 24 hours, cure and fully adhere After confirmation, the obtained specimen was immersed in warm water (95 ° C.), the time for separating the quartz glass from each other 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 on quartz glass A (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive substrate. Then, quartz glass B (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) was bonded, cured at 23 ° C. for 24 hours and cured, and the quartz glasses were bonded to each other. Then, the obtained test body was heated at 160 degreeC with the hotplate, the time which quartz glass peeled 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))
3 g of the adhesive composition for temporary fixing was applied to quartz glass A (length 60 mm × width 60 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive base material, and quartz glass B (length 40mm × width 40mm × thickness 2mm, surface roughness Ra: 0.7 μm), using a belt conveyor type metal halide lamp, from the upper surface of quartz glass B under the condition of an integrated light amount of 2000 mJ / cm ² at a wavelength of 365 nm Light was irradiated and cured, and the quartz glasses were bonded together. Then, the obtained test body was immersed in warm water (95 degreeC), the time which quartz glass peeled 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 (D))
7 g of the adhesive composition for temporary fixing was applied to quartz glass A (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 0.7 μm) as an adhesive substrate, and quartz glass B (length 150mm × width 150mm × thickness 2mm, surface roughness Ra: 0.7 μm), using a belt conveyor type metal halide lamp, from the upper surface of quartz glass B under the condition of an integrated light quantity of 2000 mJ / cm ² at a wavelength of 365 nm Light was irradiated and cured, and the quartz glasses were bonded together. Then, the obtained test body was heated at 160 degreeC with the hotplate, the time which quartz glass peeled was measured, and the state of the film after peeling was also confirmed.

(Examples 10 to 18, Comparative Examples 6 to 10)
Evaluation was made by the following method.

(Lamination adhesion / processing / peeling test (A))
1. Production of quartz glass laminate On quartz glass (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 1.5 μm) as an adhesive substrate, quartz glass (length 150 mm) is passed through an adhesive composition. 12 sheets of width 150 mm × thickness 2 mm, surface roughness Ra: 1.5 μm) were bonded together to produce a quartz glass laminate.
In the two-component adhesive composition, the laminate produced through the 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 (single-component adhesive composition), a belt conveyor type metal halide lamp is used, and the quartz glass top surface is used under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm. It was irradiated with light and cured. Light irradiation was performed every time one quartz glass was laminated, and was repeated 11 times to produce a quartz glass laminate.

2. Cutting processing of quartz glass laminate Next, the laminate of plate glass was cut in the thickness direction along a predetermined cutting line with a band saw to produce a divided quartz glass laminate. At this time, the quartz glass was divided into 40 mm wide × 40 mm long × 2 mm thick.

3. The obtained quartz glass laminate was immersed in warm water (95 ° C.), the time for the quartz glass to peel off was measured, and the state of the film after peeling was also confirmed. The peeling time was the time required for all 12 quartz glasses to peel after being immersed in warm water. Ten pieces of the peeled test specimens were taken out at random, and each piece on the back surface (the surface temporarily fixed with the temporary fixing adhesive composition) was observed using an optical microscope, and the quartz glass was missing. The maximum width of the spot was measured, and the average value and standard deviation were obtained. The results are shown in Table 3, Table 5, Table 7, Table 9, and Table 10.

(Examples 19 to 27, Comparative Examples 11 to 15)
Evaluation was made by the following method.

(Lamination adhesion / processing / peeling test (B))
1. Fabrication of quartz glass laminate Adhesive mixture of equal amounts of the first agent and the second agent on quartz glass (length 150 mm x width 150 mm x thickness 2 mm, surface roughness Ra: 1.5 μm) as an adhesion base material 12 sheets of quartz glass (length 150 mm × width 150 mm × thickness 2 mm, surface roughness Ra: 1.5 μm) were bonded together through the agent composition to prepare a quartz glass laminate.
In the two-component adhesive composition, the laminate produced through the 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 (single-component adhesive composition), a belt conveyor type metal halide lamp is used, and the quartz glass top surface is used under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm. Light was irradiated and cured. Light irradiation was performed every time one quartz glass was laminated, and was repeated 11 times to produce a quartz glass laminate.

2. Cutting processing of quartz glass laminate Next, the laminate of plate glass was cut in the thickness direction along a predetermined cutting line with a band saw to produce a divided quartz glass laminate. At this time, the quartz glass was divided into a width of 75 mm, a length of 75 mm, and a thickness of 2 mm.

3. The obtained quartz glass laminate was exposed in an oven heated to 160 ° C. for 30 minutes, and the quartz glass was peeled off to observe the peelability. The state of the film after peeling was also confirmed. Ten pieces of the peeled test specimens were taken out at random, and each piece on the back surface (the surface temporarily fixed with the temporary fixing adhesive composition) was observed using an optical microscope, and the quartz glass was missing. The maximum width of the spot was measured, and the average value and standard deviation were obtained. The results are shown in Table 3, Table 5, Table 7, Table 9, and Table 11.

From Tables 1-11, it turned out that this invention has the outstanding effect. Since Comparative Example 1 is different from the present invention in Component (1), Comparative Example 2 is different from the present invention in Component (2), and Comparative Example 3 is different from the present invention in Component (4). Since (5) is different from the present invention, Comparative Example 5 did not contain the component (5), and therefore did not show an effect.

The composition containing a radical photopolymerization initiator has photocurability because of its composition, is cured by visible light or ultraviolet light, and the cured product can exhibit high adhesive strength without being affected by cutting water or the like. .

The composition containing the thermal radical polymerization initiator has room temperature curability because of its composition, is cured at room temperature, and the cured product can exhibit high adhesive strength without being affected by cutting water or the like.

In the prior art, it is difficult to easily peel off a member having a rough surface or a large area member after temporarily fixing and processing, without leaving any adhesive residue. The present invention contains a specific oligomer, a specific monofunctional (meth) acrylate, a radical polymerization initiator, a specific granular material, and a specific organic heat-expandable particle, thereby having a rough surface or a large area member. Even so, sufficient adhesion can be obtained without increasing the number of steps, no deviation occurs during processing, dimensional accuracy is improved, and an excellent member can be easily obtained.

In the present invention, since the adhesive body is brought into contact with warm water, the adhesive strength 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, by heating the adhesive body, the adhesive strength 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.

The method of temporarily fixing the member of the present invention does not require the use of an organic solvent that has been necessary in the prior art, and there is no adhesive residue on the member even after peeling, and the cured product can be easily recovered from the member. Excellent.

Claims (22)

(1) In a total of 100 parts by mass of (2) and (6), (1) Polyester urethane (meth) acrylate having 2 or more (meth) acryloyl groups at the terminal or side chain of the molecule 20 to 60 masses Parts, (2) monofunctional (meth) acrylate having a polyalkylene oxide structure 20 to 60 parts by mass, (3) radical polymerization initiator, (4) 0.1 to 30 parts by mass of a granular material having an average particle size of 80 to 300 μm (5) Temporary fixing adhesive composition containing 1 to 30 parts by mass of organic heat-expandable particles containing butane and / or isobutane, and (6) 0 to 30 parts by mass of polyfunctional acrylate other than (1) And then temporarily fixing the member by standing at room temperature for 0.5 to 500 hours, curing the temporary fixing adhesive composition, processing the temporarily fixed member, and processing the bonded Soaking the body in water More, the temporary fixation method of the member to remove the cured product of the temporary fixing adhesive composition. The method for temporarily fixing a member according to claim 1, wherein the temperature of water when removing the cured body is higher than 40 ° C and not higher than 100 ° C, and the immersion time is 1 to 240 minutes. (1) In a total of 100 parts by mass of (2) and (6), (1) Polyester urethane (meth) acrylate having 2 or more (meth) acryloyl groups at the terminal or side chain of the molecule 20 to 60 masses Parts, (2) monofunctional (meth) acrylate having a polyalkylene oxide structure 20 to 60 parts by mass, (3) radical polymerization initiator, (4) 0.1 to 30 parts by mass of a granular material having an average particle size of 80 to 300 μm (5) Temporary fixing adhesive composition containing 1 to 30 parts by mass of organic heat-expandable particles containing butane and / or isobutane, and (6) 0 to 30 parts by mass of polyfunctional acrylate other than (1) with a member bonded temporarily fixed by 0.5 to 500 hours standing at room temperature, curing the temporary fixing adhesive composition, processing the tentative fixed member was processed adhesion 100-200 ° C body By heating, the temporary fixation method of the member to remove the cured product of the temporary fixing adhesive composition. The method for temporarily fixing a member according to claim 3, wherein the heating time for removing the cured body is 1 to 240 minutes. The method for temporarily fixing a member according to any one of claims 1 to 4, which is used for temporarily fixing a member having a bonded area after processing of 225 cm ² or more. The method for temporarily fixing a member according to claim 1, which is used for temporarily fixing a member having a surface roughness Ra of 0.2 μm or more. (1) is a polyester-based urethane (meth) acrylate oligomer having a molecular weight of 10,000 to 50,000, (2) is a monofunctional (meth) acrylate having a polyethylene oxide structure, and (5) butane and / or isobutane. The encapsulated organic thermal expandable particle is a polymer or co-polymer consisting of one or more of the group consisting of butane and / or isobutane, vinylidene chloride, (meth) acrylonitrile, methyl (meth) acrylate. It is a thermally expandable microcapsule encapsulated with a thermoplastic resin that is a coalescence, (6) polyfunctional acrylate is tripropylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexane Is it one or more of the group consisting of diol di (meth) acrylates? Temporary fixing method according to any one of the member of claims 1 to 6 comprising. (1) is the polyester-type urethane (meth) acrylate oligomer which is molecular weight 25000-50000, The temporary fixing method of the member of any one of Claims 1-7. (1) is a polyester-based urethane (meth) acrylate obtained by reacting a polyester polyol compound, an organic polyisocyanate compound, and hydroxy (meth) acrylate, and the polyester polyol compound is a polyhydric alcohol or a polyether polyol; It is a polyester polyol that is a condensate with a polybasic acid, and the polyhydric alcohol or polyether polyol is one or more of the group consisting of ethylene glycol, 1,4-butanediol, and hydrogenated polybutadiene polyol. Yes, the polybasic acid is adipic acid, the organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Rate, temporary fixation method of 2-hydroxybutyl (meth) set forth in any one member of claims 1 to 8 is one or more from among the group consisting of acrylate. (2) The monofunctional (meth) acrylate having a polyethylene oxide structure is a monofunctional (meth) acrylate having a structure represented by the following chemical formula (D): The member according to any one of claims 1 to 9. Temporary fixing method.
Chemical formula (D)
_{- (- CH 2 -CH 2 -O-} ) n -
(However, n = 2-4) The method for temporarily fixing a member according to any one of claims 1 to 10, wherein (3) the polymerization initiator of the temporary fixing adhesive composition is (3-1) a thermal radical polymerization initiator. The composition according to claim 11 is divided into two parts, and the first part contains (3-1) a thermal radical polymerization initiator and the second part contains (7) a reducing agent for two-part temporary fixing A method for temporarily fixing a member using an adhesive composition. The method for temporarily fixing a member according to claim 12, wherein (7) comprises one or more members selected from the group consisting of vanadium acetylacetonate, copper naphthenate and cobalt octylate. The amount of (3-1) used is 0.1 to 5 parts by mass and the amount of (7) used is 0.1 to 5 with respect to 100 parts by mass in total of (1), (2) and (6). It is a mass part, The temporary fixing method of the member of Claim 12 or 13. The method for temporarily fixing a member according to any one of claims 1 to 10, wherein (3) the polymerization initiator of the temporary fixing adhesive composition is (3-2) a radical photopolymerization initiator. The method for temporarily fixing a member according to claim 15, wherein the amount of (3-2) used is 0.1 to 20 parts by mass with respect to 100 parts by mass in total of (1), (2), and (6). (4) is one or more members selected from the group consisting of crosslinked poly (meth) acrylate methyl particles, crosslinked polystyrene particles, and crosslinked poly (meth) methyl methacrylate polystyrene copolymer particles. The temporary fixing method of the member of any one of these. The member according to any one of claims 1 to 17, further comprising 0.001 to 3 parts by mass of a polymerization inhibitor with respect to 100 parts by mass in total of (1), (2) and (6). Temporary fixing method. The method for temporarily fixing a member according to any one of claims 1 to 18, wherein the use is one type or two or more types selected from the group consisting of quartz bonding, ceramic bonding, and glass bonding. The method for temporarily fixing a member according to any one of claims 1 to 19 , wherein the member is one or more members selected from the group consisting of quartz, ceramic and glass. Temporarily fixing method of one of claims member of claims 1 to 20 surface roughness Ra of the member is 0.2μm or more. Temporarily fixing method of one of claims member of the bonded area of the member after processing is 225 cm ² or more claims 1 to 21.