JP4480641B2 - Composition and method for temporarily fixing member using the same - Google Patents

Description

The present invention relates to a temporary fixing method for processing various members, and relates to a composition and an adhesive suitable for the method, and more particularly, to temporarily fix the member to a jig or the like when processing an optical member. And a photocurable adhesive suitable for the application.

Double-sided tape and hot-melt adhesives are used as temporary fixing adhesives for optical lenses, prisms, arrays, silicon wafers, semiconductor mounting components, etc., and members bonded or laminated with these adhesives After cutting into a predetermined shape, the adhesive is removed and a processed member is manufactured. For example, in semiconductor mounting parts, these parts are fixed to a base material such as a jig with double-sided tape, then the desired parts are cut, and further, the double-sided tape is irradiated with ultraviolet rays to be peeled off from the parts. Do. In the case of a hot-melt adhesive, after joining the members, the adhesive is infiltrated into the gap by heating, and then a desired part is cut and the adhesive is peeled off in an organic solvent.

However, in the case of double-sided tape, it is difficult to obtain thickness accuracy, the adhesive strength is weak, so chipping properties are inferior when parts are processed, and it cannot be peeled off unless it is heated to 100 ° C or higher. In the case of peeling by irradiation, there is a problem that peeling is not possible when the adherend has poor permeability.

In the case of a hot melt adhesive, it cannot be applied unless heat of 100 ° C. or higher is applied during bonding, and there are restrictions on the members that can be used. In addition, it is necessary to use an organic solvent at the time of peeling, and the cleaning process of the alkali solvent or the halogen-based organic solvent is complicated, and there has been a problem in the working environment.

In order to solve these disadvantages, photo-setting or heating adhesives for temporary fixing containing a water-soluble compound such as a water-soluble vinyl monomer have been proposed. However, there is a problem that the adhesive strength at the time of component fixing is low and the dimensional accuracy of the member after cutting is poor. In addition, adhesives for temporary fixing that have improved adhesion by using specific (meth) acrylates with high hydrophilicity and improved releasability by swelling and partial dissolution have also been proposed. Since this generates heat of friction between the blade and a cutting jig such as a blade or diamond cutter, which is cooled with a large amount of water, the above-mentioned highly hydrophilic composition swells and becomes flexible during cutting. Higher dimensional accuracy cannot be reached. Further, since the cured product was partially dissolved in peeled member is remaining glue, that has also become an appearance problem (see Patent Documents 1, 2 and 3).
JP-A-6-116534 Japanese Patent Laid-Open No. 11-71553 Japanese Patent Laid-Open No. 2001-226641

In order to improve the dimensional accuracy of parts after cutting, it is hydrophobic, has high adhesive strength, has excellent peelability in water, and has no adhesive residue on the parts after peeling, making it environmentally workable. An excellent photo-curing adhesive is desired.

As a result of various investigations to solve the problems of the prior art, the present inventor combined with a specific (meth) acrylic monomer and added a specific component to achieve high adhesive strength and peeling in warm water. An adhesive composition having good properties is obtained, and the inventors have obtained the knowledge that this achieves the above-mentioned purpose and have completed the invention.

That is, the present invention provides (A) a polyfunctional (meth) acrylate consisting of one or more members selected from the group consisting of 1,2-polybutadiene-terminated urethane methacrylate and dicyclopentanyl diacrylate, (B) methyl (meth) Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (Meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl ( (Meth) acrylate, phenol ethylene oxide modified acrylate, phenol (ethylene oxide 2 mol modified) acrylate, phenol (ethylene oxide 4 mol modified) acrylate, paracumylphenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol (ethylene oxide 4 mol) Modified) acrylate, nonylphenol (8 mole modified ethylene oxide) acrylate, nonylphenol (2.5 mole modified propylene oxide) acrylate, 2-ethylhexyl carbitol acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meta ) Acrylate, trifluoroethyl (meth) acrylate, acrylic Acid, methacrylic acid, maleic acid, fumaric acid, ω-carboxy-polycaprolactone mono (meth) acrylate, phthalate monohydroxyethyl (meth) acrylate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydro From one or more of the group consisting of gensuccinate, n- (meth) acryloyloxyalkylhexahydrophthalimide, benzyl methacrylate, dicyclopentenyloxyethyl methacrylate and 2- (1,2-cyclohexacarboximido) ethyl acrylate The monofunctional (meth) acrylate, (C) 0.1 to 10 parts by mass of polysaccharide and (D) photopolymerization initiator with respect to 100 parts by mass of the total amount of (A) and (B). (A) 1,2-polybutadiene powder A polyfunctional (meth) acrylate consisting of one or more of the group consisting of urethane methacrylate and dicyclopentanyl diacrylate, (B) benzyl methacrylate, isobornyl methacrylate, dicyclopentenyloxyethyl methacrylate and 2- (1 , 2-Cyclohexacarboximido) ethyl acrylate, 0.1% with respect to 100 parts by mass of the total amount of monofunctional (meth) acrylates consisting of one or more of (C) (A) and (B). It is a composition characterized in that it contains 10 parts by mass of a polysaccharide and (D) a photopolymerization initiator, and (C) is a composition containing potato starch, and contains a polymerization inhibitor. This composition is characterized in that (C) swells or dissolves upon contact with water at 30 to 90 ° C. (A) is 1 to 50 parts by mass in 100 parts by mass of the total amount of (A) and (B), and (B) is 5 to 95 parts by mass in 100 parts by mass of the total amount of (A) and (B). , (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B), and (D) is 0 with respect to 100 parts by mass of the total amount of (A) and (B). 0.1-20 parts by mass of the composition, the adhesive comprising the composition, and temporarily fixing a member using the composition, After the processed member is processed, the processed member is immersed in warm water of 30 to 90 ° C., and the cured body of the composition is removed .

The composition of the present invention is photocurable due to its composition and is cured by visible light or ultraviolet light. For this reason, compared with the conventional hot melt adhesive, a remarkable effect is acquired in terms of labor saving, energy saving, and work shortening. In addition, since the cured body can exhibit high adhesive strength without affecting the cutting water used at the time of processing, there is an effect that a member excellent in dimensional accuracy can be easily obtained without being displaced during the processing of the member. can get. Further, the cured body has a feature that the member can be easily recovered because it lowers the adhesive strength by contacting with warm water of 30 ° C. or more and decreases the bonding force between the members or between the member and the jig. Thus, it is possible to obtain a remarkable effect that it is not necessary to use an organic solvent that is expensive, strong in ignitable, or generates a gas harmful to the human body, which is necessary in the case of a conventional adhesive. Furthermore, in the resin composition having a specific preferable composition range, the cured body comes into contact with hot water of 30 ° C. or more and swells and can be recovered from the member in the form of a film, so that an effect of excellent workability can be obtained.

As described above, the method for temporarily fixing the member of the present invention uses a composition that reduces the adhesive strength by contacting with hot water of 30 ° C. or more and 90 ° C. or less. As compared with the case of conventional adhesives, it is possible to obtain a remarkable effect that it is not necessary to use an organic solvent that is expensive, strongly ignitable, or generates a gas harmful to the human body.

The (A) polyfunctional (meth) acrylate used in the present invention is a polyfunctional (meth) acrylate oligomer / polymer having 2 or more (meth) acroylated terminals or side chains of the oligomer / polymer, or 2 or more A monomer having a (meth) acryloyl group can be used. For example, as the polyfunctional (meth) acrylate oligomer / polymer, 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, TE-2000, TEA-1000 manufactured by Nippon Soda Co., Ltd.), the hydrogenated product (for example, Nippon Soda) TEAI-1000), 1,4-polybutadiene-terminated urethane (meth) acrylate (for example, BAC-45 manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene-terminated (meth) acrylate, polyester-based urethane (meth) acrylate, polyether-based Examples thereof include urethane (meth) acrylate, polyester (meth) acrylate, and bis A type epoxy (meth) acrylate (for example, Biscoat # 540 manufactured by Osaka Organic Chemical Co., Ltd., and Biscoat VR-77 manufactured by Showa High Polymer Co., Ltd.).

As bifunctional (meth) acrylate monomers, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, 1,9-nonane Diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (Meth) acrylate, stearic acid modified pentaerythritol diacrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- ( (Meta) acryloxypropoxy Phenyl) propane, 2,2-bis (4- (meth) acryloxy-tetra-ethoxyphenyl) propane, and the like, trifunctional (meth) acrylate monomer, preparative trimethylolpropane tri (meth) acrylate, tris [( (Meth) acryloxyethyl] isocyanurate and the like, and tetrafunctional or higher (meth) acrylate monomers include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) Examples include acrylate, dipentaerystol penta (meth) acrylate, and dipentaerystol hexa (meth) acrylate .

(A) The polyfunctional (meth) acrylate is more preferably hydrophobic. However, it is possible to prevent the problem that the processing accuracy is inferior due to the displacement due to the swelling of the cured body of the resin composition during cutting, which may occur in the case of water solubility. Even if it is hydrophilic, it can be used as long as the cured product of the composition is not greatly swollen or partially dissolved by water.

(A) As for the addition amount of polyfunctional (meth) acrylate, 1-50 mass parts is preferable in 100 mass parts of total amounts of (A) and (B). If it is 1 part by mass or more, the property that the cured product peels from the adherend when the cured product of the composition is immersed in warm water (hereinafter simply referred to as “peelability”) is sufficiently promoted. It can be ensured that the cured body peels into a film. Moreover, if it is 50 mass parts or less, there is no possibility that initial adhesiveness may fall.

(B) Monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate , Isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate , Caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butyl Aminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified acrylate, phenol (ethylene oxide 2 mol modified) acrylate, Nord (ethylene oxide 4 mol modified) acrylate, paracumylphenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol (ethylene oxide 4 mol modified) acrylate, nonylphenol (ethylene oxide 8 mol modified) acrylate, nonylphenol (propylene oxide 2. 5 mol modified) acrylate, 2-ethylhexyl carbitol acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate, acrylic acid, methacrylic acid, maleic acid, Fumaric acid, ω-carboxy-polycaprolactone mono (meth) acrylate, phthalic acid monohydroxy ester Le (meth) acrylate, (meth) acrylic acid dimer, beta-(meth) acryloyloxyethyl hydrogen succinate, n-(meth) acryloyloxy alkyl hexahydrophthalimide and the like.

(B) Monofunctional (meth) acrylate is more preferably hydrophobic as in (A). However, it is possible to prevent the problem that the processing accuracy is inferior due to the displacement due to the swelling of the cured body of the resin composition during cutting, which may occur in the case of water solubility. Even if it is hydrophilic, it can be used if the cured product of the resin composition does not swell or partially dissolve with water.

(B) As for the addition amount of monofunctional (meth) acrylate, 5-95 mass parts is preferable in the total amount of 100 mass parts of (A) and (B). If it is 5 parts by mass or more, there is no fear that the initial adhesiveness is lowered, and if it is 95 parts by mass or less, the peelability can be secured, and the cured product of the composition peels into a film.

In addition, (Meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, dioctyl 2- (meth) acryloyloxyethyl phosphate are added to the blended compositions of (A) and (B). , Diphenyl 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl polyethylene glycol acid phosphate, etc. The property can be further improved.

In the present invention, the (C) polysaccharide is used together with (A) and (B), whereby the cured composition comes into contact with warm water and easily swells or dissolves to adhere. A phenomenon in which the strength decreases can be surely expressed.

Examples of (C) polysaccharides include starch , cellulose, inulin, agar, glucomannan, hyaluronic acid, chondroitin, chondroitin sulfate A, chondroitin sulfate C dermatan sulfate, and kerato sulfate. Further, among the polysaccharides, starch having a temperature of 30 ° C. to 150 ° C. that swells and dissolves upon contact with water is even more preferable.

In the present invention, when the polysaccharide (C) is selected such that the polysaccharide swells or dissolves upon contact with water at 30 to 90 ° C., the cured composition comes into contact with warm water and has an adhesive strength. This is preferable because the phenomenon of decreasing can be expressed more reliably. In addition, examples of such polysaccharides include homopolysaccharides, heteropolysaccharides, mucopolysaccharides, and the like. Of these, homopolysaccharides are preferably selected according to the results of studies by the inventors.

(C) 0.1-10 mass parts is preferable with respect to 100 mass parts of total amounts of (A) and (B). If it is 0.1 parts by mass or more, the peelability can be ensured, and if it is 10 parts by mass or less, the initial adhesiveness is not lowered, and the cured product of the composition is peeled into a film.

(D) As a photoinitiator, it mix | blends in order to accelerate | stimulate the photocuring of a composition by sensitizing with visible light or an active ray of an ultraviolet-ray, and various well-known photoinitiators can be used. . Specifically, benzophenone and derivatives thereof, benzyl and derivatives thereof, entraquinone and derivatives thereof, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin derivatives such as benzyl dimethyl ketal, diethoxyacetophenone, Acetophenone derivatives such as 4-t-butyltrichloroacetophenone, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and derivatives thereof, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] Heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2 Bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2 2.1] Camphorquinone derivatives such as heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Α-aminoalkylphenone derivatives such as amino-1- (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2, 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2 Acylphosphine oxide derivatives such as 4,6-trimethylbenzoyl dichloride ethoxyphenyl phosphine oxide. A photoinitiator can be used 1 type or in combination of 2 or more types.

As for the addition amount of a photoinitiator, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of (A) and (B). More preferably, 3-20 mass parts is preferable. If it is 0.1 mass part or more, the effect of hardening acceleration | stimulation will be acquired reliably, and sufficient curing rate can be obtained if it is 20 mass parts or less. As a more preferred embodiment, when 3 parts by mass or more of (D) is added, the composition can be cured without depending on the amount of light irradiation, and the degree of cross-linking of the cured product of the composition is increased, so that no misalignment or the like occurs during cutting. A more preferable effect of improving the point and peelability can be obtained.

The composition of the present invention can use a small amount of a polymerization inhibitor in order to improve its storage stability. For example, polymerization inhibitors include methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, monotertiarybutylhydroquinone, 2,5-ditertiarybutyl. 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 Examples include 2,6-ditertiary butyl-p-cresol.

The amount of these polymerization inhibitors used is preferably 0.001 to 3 parts by mass and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). Storage stability is ensured at 0.001 part by mass or more, good adhesiveness is obtained at 3 parts by mass or less, and it does not become uncured.

The composition of the present invention includes various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic fillers, solvents, fillers, reinforcing materials, Additives such as plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.

Next, in the present invention, a member is bonded using a resin composition that is brought into contact with warm water of 90 ° C. or lower to lower the adhesive strength, the composition is cured, temporarily fixed, and the temporarily fixed member is This is a method of temporarily fixing a member that removes the cured adhesive by immersing the processed member in warm water after processing, thereby allowing various members such as optical members to be processed with high accuracy without using an organic solvent. Can be processed.

Further, according to a preferred embodiment of the present invention, when removing the cured body of the composition, the cured body swells in contact with hot water of 90 ° C. or less, and can be recovered from the member in the form of a film. The effect of excellent workability can be obtained.

When the adhesive comprising the composition of the present invention is used in the temporary fixing method of the present invention, the effects of the present invention can be obtained with certainty.

In the present invention, when warm water heated moderately, specifically, hot water of 90 ° C. or less is used, the releasability in water can be achieved in a short time, which is preferable from the viewpoint of productivity. Regarding the temperature of the hot water, when using hot water of 30 ° C. to 90 ° C., preferably 40 to 90 ° C., the cured product of the adhesive swells in a short time and the residual strain stress generated when the composition is cured is Since it is released, the adhesive strength is reduced, and in addition, (C) the polysaccharide is swollen or dissolved in contact with water to act as a peeling force between the member and the cured product of the composition, and the cured product of the composition Is preferable because it can be removed in the form of a film. In addition, about the method of contact with a hardening body and water, since the method of immersing the whole joined body in water is simple, it is recommended. The upper limit of the temperature of the hot water has no particular technical significance. However, in hot water exceeding 90 ° C., there is difficulty in handling during work. Determined as ° C.

In the present invention, there are no particular restrictions on the material of the member such as a jig or workpiece to be used for temporary fixing, and a member made of a material that can transmit ultraviolet rays is preferable when used as an ultraviolet curable adhesive. . Examples of such a material include a crystal member, a glass member, and a plastic member. Therefore, the temporary fixing method of the present invention can be applied to temporary fixing in processing of a crystal resonator, a glass lens, a plastic lens, and an optical disk. .

In the temporary fixing method, with respect to the method of using the adhesive, assuming that a photocurable adhesive is used as the adhesive, for example, an appropriate amount of adhesive is applied to the adhesive surface of one member to be fixed or the support substrate, followed by Then, after applying the adhesive by a method of superimposing the other member or by previously laminating a number of members to be temporarily fixed and applying the adhesive by infiltrating the adhesive into the gap, Examples include a method of irradiating ultraviolet rays to cure the photocurable adhesive and temporarily fix the members together.

Thereafter, the temporarily fixed member is cut into a desired shape, ground, polished, drilled, etc., and then the cured product of the adhesive is peeled off from the member by immersing the member in water, preferably warm water. can do.

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.

(Reference Example 1) as (A) a polyfunctional (meth) acrylate, manufactured by Nippon Soda Co., Ltd. TE-2000 (1,2-polybutadiene-terminated urethane methacrylate hereinafter abbreviated as "TE-2000") 50 parts by weight, dicyclohexyl Bae Ntaniruji 5 parts by mass of acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARADR-684, hereinafter abbreviated as “R-684”), (B) 30 parts by mass of BZ: benzyl methacrylate (light ester BZ made by Kyoeisha Chemical Co., Ltd.) as monofunctional (meth) acrylate , IBX: isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester IB-X) 15 parts by mass, (C) 2 parts by mass of glucose as a polysaccharide, (D) benzyldimethyl as a photopolymerization initiator 5 parts by mass of a ketal (hereinafter abbreviated as “BDK”), 2,2-methylene-bis (4-methyl-) as a polymerization inhibitor - creating the tertiary butylphenol) (hereinafter abbreviated as "MDP") was added 0.1 parts by mass of the resin composition. Using the obtained resin composition, the tensile shear bond strength was measured and a peel test was performed by the following evaluation method. The results are shown in Table 1.

(Evaluation methods)
Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, heat-resistant Pyrex (registered trademark) glass (25 mm × 25 mm × thickness 2.0 mm) was used as an adherend, and the bonded portion was 8 mm in diameter. Pyrex (registered trademark) glass is laminated and cured with a fusion device using an electrodeless discharge lamp, and cured under conditions of an integrated light quantity of 2000 mJ / cm ² at a wavelength of 365 nm, and a tensile shear bond strength test piece is created. did. The prepared test piece was measured for tensile shear bond strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.

Peel test: Resin composition prepared under the same conditions as above except that the composition was applied to the above heat-resistant Pyrex (registered trademark) glass and bonded to blue plate glass (150 mm × 150 mm × thickness 1.7 mm) as a support. The product was cured to produce a peel test specimen. The obtained specimen was immersed in warm water (80 ° C.), the time for the heat-resistant Pyrex (registered trademark) glass to peel was measured, and the peeled state was also observed.

Examples 2 to 22 Compositions were prepared in the same manner as in Reference Example 1 except that raw materials of the types shown in Tables 1 and 2 were used in the compositions shown in Tables 1 and 2. About the obtained composition, the measurement of the tensile shear bond strength and the peel test were performed in the same manner as in Reference Example 1 . The results are shown in Tables 1 and 2.

(Materials used)
QM: dicyclopentenyloxyethyl methacrylate (QM-657 manufactured by Rohm & Haas) 2- (1,2-cyclohexacarboximide) ethyl acrylate (TO-1429 manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “TO-1429”)

(Comparative Examples 1-6) A composition was prepared in the same manner as in Example 1 except that the raw materials of the type shown in Table 3 were used in the composition shown in Table 3. About the obtained composition, the measurement of the tensile shear bond strength and the peel test were performed in the same manner as in Reference Example 1 . The results are shown in Table 3.

(Materials used)
2-HEMA: 2-hydroxyethyl methacrylate MTEGMA: methoxytetraethylene glycol monomethacrylate (NK Nakamura Chemical Co., Ltd. NK ester M-90G)

(Example 23, Comparative Example 7) Using the compositions of Example 8 and Comparative Example 6, respectively, with a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, the integrated light quantity at a wavelength of 365 nm was 500, 1000, 2000. The tensile shear bond strength measurement and peel test were performed in the same manner as in Reference Example 1 except that the adhesive composition was cured by changing to 4000 mJ / cm ² and a peel test specimen and a tensile shear bond strength test piece were prepared. went. The results are shown in Table 4.

(Examples 24 and 25) Using the resin compositions of Examples 8 and 11, peeling test specimens were prepared in the same manner as in Reference Example 1 , and peeling was performed by changing the temperature of hot water at 40 ° C, 50 ° C, 60, and 70 ° C. A test was conducted. The results are shown in Table 5. As a result, it has peelability at any temperature.

Example 26 Using the composition of Example 8, 150 mm × 150 mm × 2 mm heat-resistant Pyrex (registered trademark) glass and blue plate glass used in Example 1 were bonded and cured in the same manner as in Example 1 as dummy glass. . Only the heat-resistant Pyrex (registered trademark) glass part of this adhesion test specimen was cut into 10 mm squares using a dicing machine. During the cutting, heat-resistant Pyrex (registered trademark) glass did not fall off, and good workability was exhibited. When the adhesion test body which cut | disconnected only the heat-resistant Pyrex (trademark) glass part was immersed in 80 degreeC warm water, all peeled in 60 minutes. In addition, 10 pieces of the peeled test specimens were taken out arbitrarily, and each piece on the back surface (the surface temporarily fixed with the composition) of the test specimen was observed using an optical microscope, and the most part where the glass was missing was observed. The large value was measured, and the average value and standard deviation were obtained. The results are shown in Table 6.

(Comparative Example 8) A hot-melt adhesive (Adfix A manufactured by Nikka Seiko Co., Ltd.) was heated to 90 ° C. and dissolved, and used in Example 1 with a heat-resistant Pyrex (registered trademark) glass of 150 mm × 150 mm × 2 mm. Blue plate glass was adhered. Only the heat-resistant Pyrex (registered trademark) glass part of this adhesion test specimen was cut into 10 mm squares using a dicing machine. During the cutting, heat-resistant Pyrex (registered trademark) glass did not fall off, and good workability was exhibited. The test piece was immersed in an N-methylpidrilone solution for 1 day, the cut test piece was collected, and 10 cut test pieces that were peeled off in the same manner as in Example 25 were taken out, and the back side of the cut test piece (hot melt adhesive) Each piece of the surface temporarily fixed with the agent was observed using an optical microscope, the maximum width of the portion where the glass was missing was measured, and the average value and the standard deviation were obtained. The results are shown in Table 6.

(Comparative Example 9) A heat-resistant Pyrex (registered trademark) glass having a size of 150 mm x 150 mm x 2 mm was adhered using a UV curable PET adhesive tape. Only the heat-resistant Pyrex (registered trademark) glass part of this adhesion test specimen was cut into 10 mm squares using a dicing machine. The adhesive strength was reduced by irradiating the adhesive tape portion of the test piece with ultraviolet rays, and the cut test piece was recovered. Ten pieces of the cut test pieces from which the cut test pieces were peeled in the same manner as in Example 26 were taken out, and each piece on the back surface (the surface temporarily fixed with the adhesive tape) of the cut test piece was observed using an optical microscope. The maximum width of the portion where the glass was missing was measured, and the average value and standard deviation were obtained. The results are shown in Table 6.

(Example 27, Comparative Examples 10 and 11) Using the composition of Example 8 and Comparative Examples 5 and 6, a fusion device made by Fusion Co., Ltd. using an electrodeless discharge lamp, an integrated light amount of 365 nm wavelength was 4000 mJ / The composition was cured to a shape of 30 mm × 10 mm × 1 mm as cm ² . After measuring the initial weight of the cured product, it was immersed in water at 25 ° C. for 24 hours, and the weight of the cured product was measured. Table 7 shows the results of calculating the degree of swelling of each composition by the degree of swelling (%) = (weight of cured product after immersion−weight of initial cured product) / initial cured product weight × 100. As a result, compared with the composition using hydrophilic (meth) acrylate as in the comparative example, the composition of Example 1 has low swelling even when immersed in water at 25 ° C. Insensitive to water.

The composition of the present invention 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. It is difficult to cause displacement, and an effect that a member excellent in terms of dimensional accuracy can be easily obtained is obtained. Furthermore, contact strength with hot water is reduced, and the bonding strength between members or between a member and a jig is reduced. Therefore, it is industrially useful as an adhesive for temporarily fixing optical lenses, prisms, arrays, silicon wafers, semiconductor mounting parts and the like.

The temporary fixing method of the member of the present invention uses the characteristic resin composition, so that it is not necessary to use an organic solvent required in the prior art and can be recovered from the member in the form of a film. Therefore, it is very useful industrially.

Claims (8)

  (A) 1,2-polybutadiene-terminated urethane methacrylate and polyfunctional (meth) acrylate comprising at least one member selected from the group consisting of dicyclopentanyl diacrylate, (B) methyl (meth) acrylate, ethyl (meth) Acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) Acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate Methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate , Phenol ethylene oxide modified acrylate, phenol (ethylene oxide 2 mole modified) acrylate, phenol (ethylene oxide 4 mole modified) acrylate, paracumylphenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol (ethylene oxide 4 mole modified) acrylate Nonylphenol (8 mol modified ethylene oxide) acrylate, Nonylphenol (2.5 mol modified propylene oxide) acrylate, 2-ethylhexyl carbitol acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, Trifluoroethyl (meth) acrylate, acrylic acid, methacryl , Maleic acid, fumaric acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, A monofunctional compound consisting of one or more members selected from the group consisting of n- (meth) acryloyloxyalkylhexahydrophthalimide, benzyl methacrylate, dicyclopentenyloxyethyl methacrylate and 2- (1,2-cyclohexacarboxyimide) ethyl acrylate ( A composition comprising 0.1 to 10 parts by weight of a polysaccharide and (D) a photopolymerization initiator with respect to 100 parts by weight of a total amount of (meth) acrylate, (C) (A) and (B). object.   (A) 1,2-polybutadiene-terminated urethane methacrylate and dicyclopentanyl diacrylate, one or more polyfunctional (meth) acrylates, (B) benzyl methacrylate, isobornyl methacrylate, dicyclo Total amount of monofunctional (meth) acrylate consisting of one or more of the group consisting of pentenyloxyethyl methacrylate and 2- (1,2-cyclohexacarboximido) ethyl acrylate, (C) (A) and (B) The composition characterized by containing 0.1-10 mass parts polysaccharide and 100 photopolymerization initiator with respect to 100 mass parts.   The composition according to any one of claims 1 to 2, wherein (C) is potato starch.   The composition according to any one of claims 1 to 3, further comprising a polymerization inhibitor. (C) swells or melt | dissolves by contact with water at 30-90 degreeC, The composition of any one of Claims 1 thru | or 4 characterized by the above-mentioned. (A) is 1 to 50 parts by mass in 100 parts by mass of the total amount of (A) and (B), (B) is 5 to 95 parts by mass in 100 parts by mass of the total amount of (A) and (B) , (C 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B), and 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). It contains 20 mass parts, The composition of any one of Claims 1 thru | or 5 characterized by the above-mentioned. An adhesive comprising the composition according to any one of claims 1 to 6 . A member is temporarily fixed using the composition according to any one of claims 1 to 6 , and after the temporarily fixed member is processed, the processed member is immersed in warm water of 30 to 90 ° C. And removing the cured body of the composition.