JP5132045B2 - Composition and method for temporarily fixing member using the same - Google Patents

Description

The present invention is a temporary fixing method when processing various members, and also relates to a composition and an adhesive suitable for the method, and more specifically, a method of temporarily fixing the member when processing an optical member, It is related with the photocurable adhesive suitable for the said use.

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 a semiconductor mounting component, after fixing these components to a base material with a double-sided tape, a desired part is cut, and further, the double-sided tape is irradiated with ultraviolet rays to be peeled off from the part. 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 achieve thickness accuracy, the adhesive strength is weak, so chipping properties are inferior when parts are processed, and it cannot be peeled off unless heat of 100 ° C or higher is applied. In the case of peeling by the method, there is a problem that peeling is not possible if 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 drawbacks, a photo-curing or heating adhesive for temporary fixing containing a water-soluble compound such as a water-soluble vinyl monomer has been proposed. In these adhesive compositions, releasability in water is proposed. However, the adhesive strength at the time of component fixing is low, and there is a problem that the dimensional accuracy of the member after cutting is poor. We have also proposed temporary fixing adhesives that have improved adhesion by using specific highly hydrophilic (meth) acrylates and improved peelability by swelling and partial dissolution. In order to generate frictional heat with a cutting jig such as a blade or a diamond cutter, and by cooling with a large amount of water, the above highly hydrophilic composition swells and becomes soft when cured, Higher dimensional accuracy cannot be reached. In addition, since a partially dissolved cured product remains in the peeled member, 10 to 60 minutes are immersed in warm water for 2 minutes, which is a problem in appearance, and more than swollen (Patent Document 1) 2, 3).
JP-A-6-116534. Japanese Patent Application Laid-Open No. 11-71553. Japanese Patent Application Laid-Open No. 2001-226641.

In order to improve the dimensional accuracy of the parts after cutting, it is hydrophobic, has high adhesive strength, has excellent releasability in water, and has excellent workability even in the environment where there is no adhesive residue on the parts after peeling. A photocurable adhesive is desired.

As a result of various investigations in order to solve the problems of the prior art, the present invention uses specific hydrophobic (meth) acrylic monomers, combined with them, and does not impair the adhesion of one or more selected from the carbonate compound group. By adding about a certain amount, the inventors have found that an adhesive composition having high adhesive strength and good releasability in warm water achieves this object, and has completed the invention.

That is, the present invention provides (A) 1,2-polybutadiene-terminated urethane (meth) acrylate, polyfunctional (meth) acrylate that is one or more selected from dicyclopentanyl di (meth) acrylate, (B) phenol (ethylene Monofunctional (meth) acrylate which is at least one selected from oxide 2 mol modified) acrylate , dicyclopentenyloxyethyl (meth) acrylate , 2- (1,2-cyclohexacarboximido) ethyl acrylate, (C) ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, a composition characterized by containing methyl ethyl carbonate, carbonate compounds is one or more selected from methyl propylene carbonate Natick preparative and (D) a photopolymerization initiator, (A) is Is a 2-polybutadiene-terminated urethane meta acrylate, one or more selected from dicyclopentanyl diacrylate, (B) phenol (ethylene oxide 2 mol modified) acrylate, di cyclopentenylene b carboxyethyl meth acrylate, 2- (1 a composition which is characterized in that at least one selected from 2-cyclohexadiene dicarboximide) acrylate, containing (a) is 1,2-polybutadiene-terminated urethane methacrylate and dicyclopentanyl diacrylate , (B) comprising phenol (ethylene oxide 2 mol modified) acrylate and / or dicyclopentenyloxyethyl methacrylate and 2- (1,2-cyclohexacarboximido) ethyl acrylate a composition, (C) It is this composition characterized by being 1 or more types chosen from ethylene carbonate, propylene carbonate, and dimethyl carbonate, (A) is 1-50 mass parts, (B) is 5-95 mass parts, (C). 0.1 to 10 parts by mass, 0.1 to 20 parts by mass of (D), and the composition does not dissolve in the polymerization inhibitor, the polar organic solvent, and (A) to (D) A composition comprising a particulate material, and an adhesive comprising the composition, wherein the composition is used to bond and temporarily fix a member, and the temporarily fixed member After the processing, the processed member is immersed in warm water of 90 ° C. or less, 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. Furthermore, the cured body has a feature that the member can be easily recovered because the adhesive strength is lowered by contact with warm water of 90 ° C. or less, and the bonding force between the members or between the member and the jig is lowered. Compared to 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. Furthermore, in the resin composition having a specific preferable composition range, the cured body comes into contact with hot water of 90 ° C. or less 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 90 ° C. or less. Therefore, the member can be easily recovered only by contacting with warm water. Compared with the case of the conventional adhesive agent, there is a feature that can be obtained, and 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.

As (A) polyfunctional (meth) acrylate used in the present invention, two or more (meth) acryloylated polyfunctional (meth) acrylate oligomer / polymer or two 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 Co., Ltd.) 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 urethane (Meth) acrylate, polyester (meth) acrylate, bis-A type epoxy (meth) acrylate (for example, Biscoat # 540 manufactured by Osaka Organic Chemical Co., Ltd., Biscoat VR-77 manufactured by Showa High Polymer Co., Ltd.), and the like.

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, in the case of being water-soluble, the cured product of the resin composition swells at the time of cutting, which may cause a positional shift and deteriorate the processing accuracy. 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, 2- (1,2-cyclohexadiene dicarboximide ) Ethyl acrylate and the like.

(B) Monofunctional (meth) acrylate is more preferably hydrophobic as in (A), and in the case of water solubility, the cured product of the resin composition swells during cutting to cause displacement and processing. This is not preferable because the accuracy may be inferior. 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, (C) one or more selected from the carbonate compound group is used together with (A) and (B), whereby the composition after curing is easily swollen by contact with hot water. Or the like, the phenomenon that the adhesive strength is lowered can be surely expressed. Examples of the (C) carbonate compound include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propylene carbonate, vinylene carbonate, and the like, from the viewpoint of reducing adhesive strength, ethylene carbonate, One of propylene carbonate and dimethyl carbonate or a mixture thereof is preferably selected.

(C) As for the addition amount of 1 or more types chosen from a carbonate compound group, 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 resin composition by sensitizing with visible light and actinic light of an ultraviolet-ray, and various well-known photoinitiators can be used. is there. Specifically, benzophenone and derivatives thereof, benzyl and derivatives thereof, enthraquinone 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. By adding 3 parts by mass or more of the component (D) as a more preferable form, 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. It is more preferable at the point which a point and peelability improve.

The resin 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.

0.001-3 mass parts is preferable with respect to 100 mass parts of (meth) acrylic acid ester monomers, and, as for the usage-amount of these polymerization inhibitors, 0.01-2 mass parts is more preferable. 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.

In the present invention, a polar organic solvent may be used together. By using the polar organic solvent together, it is possible to surely develop a phenomenon in which the cured composition comes into contact with warm water and easily swells to lower the adhesive strength.

The polar organic solvent preferably has a boiling point of 50 ° C. or higher and 130 ° C. or lower. When a polar organic solvent having a boiling point within the above range is selected, it is preferable because a phenomenon that the cured composition comes into contact with warm water and the adhesive strength decreases can be more reliably exhibited. Examples of such a polar organic solvent include alcohols, ketones, esters, and the like. Of these, alcohols are preferably selected according to the results of investigations by the inventors.

Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, 2-ethylbutyl alcohol and the like. Further, among the alcohols, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol having a boiling point of 120 ° C. or less are preferred, and among these, methanol, ethanol More preferred are isopropanol and n-butanol.

As for the addition amount of a polar organic solvent, 0.5-10 mass parts is preferable with respect to 100 mass parts of total amounts of (A) and (B). If it is 0.5 parts by mass or more, releasability 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 peels into a film.

In the present invention, a particulate substance that does not dissolve in (A) to (D) may be used together with (A) and (B). As a result, the cured composition can maintain a certain thickness, so that the processing accuracy is improved and the phenomenon that the adhesive strength is reduced due to contact with hot water and swelling easily can be exhibited. .

As a granular substance which does not dissolve in (A) to (D), any organic or inorganic particles generally used may be used as the material. Specifically, examples of the organic particles include polyethylene particles, polypolypropylene particles, crosslinked polymethyl methacrylate particles, and crosslinked polystyrene particles, and inorganic particles include ceramic particles such as glass, silica, alumina, and titanium.

The particulate material not dissolved in (A) to (D) is preferably spherical from the viewpoint of improving processing accuracy, that is, controlling the thickness of the adhesive. Specifically, as the organic particles, methyl methacrylate monomer, crosslinked polymethyl methacrylate particles obtained as monodisperse particles by a known emulsion polymerization method of a styrene monomer and a crosslinkable monomer, spherical particles as crosslinked polystyrene particles and inorganic particles Silica is preferable because the deformation of the particle is small and the film thickness of the composition after curing due to particle size variation is uniform, and among them, from the viewpoint of storage stability such as sedimentation of the particle and reactivity of the composition. Cross-linked polymethyl methacrylate particles and cross-linked polystyrene particles are even more preferable.

The amount of the particulate material not dissolved in (A) to (D) is preferably 0.1 to 20 parts by mass, particularly 0.1 to 10 parts per 100 parts by mass of the total amount of (A) and (B). Part by mass is preferred. If it is 0.1 mass part or more, the film thickness of the composition after hardening will be substantially constant, and if it is 20 mass parts or less, there is no possibility that initial adhesiveness will fall.

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 80 ° C. or less, and can be recovered from the member in a film shape. 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 Adhesive strength is reduced due to the release, and in addition, one or more members selected from (C) carbonate compound group are bred out to work as a peeling force between the member and the cured product of the resin composition. This is preferable because the cured adhesive can be removed in a shape. 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.

In the present invention, the material of the member used for temporary fixing is not particularly limited, and when used as an ultraviolet curable adhesive, a member made of a material that can transmit ultraviolet rays is preferable. 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.

(Example 1) (A) multi as functional (meth) acrylate, (abbreviated as 1,2-polybutadiene-terminated urethane methacrylate hereinafter "TE-2000") manufactured by Nippon Soda Co., Ltd. TE-2000 35 parts by weight, dicyclohexyl Bae Ntaniruji Acrylate (Nippon Kayaku KAYARAD
R-684, hereinafter abbreviated as “R-684”) 15 parts by mass, (B) as monofunctional (meth) acrylate, 2- (1,2-cyclohexacarboximide) ethyl acrylate (Aronix M-manufactured by Toagosei Co., Ltd.) 140, hereinafter referred to as “M-140”) 20 parts by mass, dicyclopentenyloxyethyl methacrylate QM-657 (manufactured by Rohm & Haas, hereinafter abbreviated as QM), 30 parts by mass, (C) a type selected from carbonate group As described above, 4 parts by mass of ethylene carbonate (manufactured by Sigma-Aldrich), (D) I-907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- as a photopolymerization initiator ON (IRGACURE907 manufactured by Ciba Specialty Chemicals, hereinafter abbreviated as IRGACURE907) 6 parts by mass 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (hereinafter abbreviated as “MDP”) as a polymerization inhibitor, isopropyl alcohol (hereinafter abbreviated as “IPA”) as a polar organic solvent 2 parts by mass, crosslinked polymethyl methacrylate particles having an average particle diameter of 50 μm as a particulate material not dissolved in (A) to (D) (Negami Kogyo Art Pearl GR-200 or less, abbreviated as “GR-200”) 0.6 A resin composition was prepared by adding parts by mass. 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 method)
Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, using heat-resistant Pyrex glass (25 mm × 25 mm × 2.0 mm) as an adherent, the bonded portion was 8 mm in diameter, and two heat-resistant Pyrex (registered trademark) glasses were formed using the resin composition thus created. Were cured under the condition of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm, and a tensile shear bond strength test piece was prepared. 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 14 and Comparative Examples 1 to 5 Resin compositions were prepared in the same manner as in Example 1 except that the raw materials of the types shown in Tables 1 and 2 were used in the compositions shown in Tables 1 and 2. did. About the obtained composition, the measurement of the tensile shear adhesive strength and the peeling test were performed similarly to Example 1. The results are shown in Tables 1 and 2.

(Materials used)
BDK: benzyl dimethyl ketal (IRGACURE651 manufactured by Ciba Specialty Chemicals)
M101A: Phenolethylene oxide 2 mol modified acrylate (Aronix M-101A manufactured by Toa Gosei Co., Ltd.)
BZ: benzyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester BZ)
IBX: Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester IB-X)
Propylene carbonate (manufactured by Sigma-Aldrich)
Dimethyl carbonate (Sigma-Aldrich)
2-HEMA: 2-hydroxyethyl methacrylate MTEGMA: methoxytetraethylene glycol monomethacrylate (NK Nakamura Chemical Co., Ltd. NK ester M-90G)

(Examples 15 and 16) Using the resin compositions of Examples 2 and 6, peel test specimens were prepared in the same manner as in Example 1, and the temperature was changed to 40 ° C, 50 ° C, 60, and 70 ° C, and then peeled off. A test was conducted. The results are shown in Table 3. As a result, it has peelability at any temperature.

(Example 17) Using the resin composition of Example 2, 150 mm x 150 mm x 2 mm heat-resistant Pyrex (registered trademark) glass and the blue plate glass used in Example 1 were bonded and cured in the same manner as in Example 1 It was. 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. Also, 10 pieces of the peeled test specimens were taken out at random, and each piece on the back surface (the surface temporarily fixed with the resin composition) of the test piece was observed using an optical microscope, and the glass was missing. The maximum width was measured, and the average value and standard deviation were obtained. The results are shown in Table 4.

(Comparative Example 6) 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 17 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 4.

(Comparative Example 7) 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 that were peeled off in the same manner as in Example 17 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 4.

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 (meth) acrylate, polyfunctional (meth) acrylate that is at least one selected from dicyclopentanyl di (meth) acrylate, (B) phenol (ethylene oxide 2 mol modified) acrylate , Dicyclopentenyloxyethyl (meth) acrylate , monofunctional (meth) acrylate that is one or more selected from 2- (1,2-cyclohexacarboximido) ethyl acrylate, (C) ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, composition characterized by containing a carbonate compound is one or more selected from methyl propylene carbonate Natick preparative and (D) a photopolymerization initiator. (A) is 1,2-polybutadiene-terminated urethane meta acrylate, and at least one selected from dicyclopentanyl diacrylate, (B) phenol (ethylene oxide 2 mol modified) acrylate, di cyclopentenylene b carboxyethyl meth acrylate , 2- (1,2-cyclohexadiene dicarboximide) composition of claim 1, characterized in that at least one selected from ethyl acrylate. (A) contains 1,2-polybutadiene terminated urethane methacrylate and dicyclopentanyl diacrylate, (B) is phenol (ethylene oxide 2 mol modified) acrylate and / or dicyclopentenyloxyethyl methacrylate, 2- The composition according to claim 1, comprising (1,2-cyclohexacarboximide) ethyl acrylate. The composition according to any one of claims 1 to 3, wherein (C) is one or more selected from ethylene carbonate, propylene carbonate, and dimethyl carbonate. 1 to 50 parts by mass of (A), 5 to 95 parts by mass of (B), 0.1 to 10 parts by mass of (C), and 0.1 to 20 parts by mass of (D). The composition according to any one of claims 1 to 4. 6. The composition according to any one of claims 1 to 5, comprising a polymerization inhibitor, a polar organic solvent, and a particulate material that does not dissolve in (A) to (D). An adhesive comprising the composition according to any one of claims 1 to 6. Using the composition according to any one of claims 1 to 7, a member is temporarily bonded and fixed, and after the temporarily fixed member is processed, the processed member is immersed in warm water of 90 ° C or lower. And removing the cured body of the composition.