JP4932300B2 - Temporary fixing composition and member temporary fixing method 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. Further, the cured product was partially dissolved in peeled member that has become to rest glue, appearance problems (see Patent Documents 1, 2 and 3).
Japanese Patent Laid-Open No. 06-116534 Japanese Patent Application Laid-Open No. 11-071553 Japanese Patent 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 these conventional techniques, the present invention uses specific hydrophobic (meth) acrylic monomers, and combines them and adds polyvinyl alcohol to such an extent that adhesion is not impaired. Obtaining knowledge that an adhesive composition having high adhesive strength and good peelability in warm water achieves this object, the present invention has been completed.

That is, the present invention is characterized in that after temporarily fixing a member, processing the temporarily fixed member, immersing the processed member in warm water of 90 ° C. or less, and removing the cured body of the composition. And (A) 1 to 95 parts by mass of a polyfunctional (meth) acrylate, (B) monofunctional with respect to 100 parts by mass of the total amount of (A) and (B). 5 to 99 parts by mass of (meth) acrylate, (C) one of the group consisting of an organosilicon compound represented by formula 1, n-hexyltrimethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane 0.1 to 20 parts by mass or more, Ri temporary fixing composition der characterized by containing the (D) photopolymerization initiator 0.1 to 20 parts by weight,
Formula _1; X 3 Si-Y
X: one or more hydrolyzable groups in the group consisting of CH ₃ O—, C ₃ H ₅ O—, CH ₃ OC ₂ H ₄ O—
Y: One or more organic functional groups in the group consisting of vinyl group, epoxy group, amino group, mercapto group, and methacryl group
(A) and (B) are both the composition for temporary fixation characterized by being hydrophobic, (A) is 1 with respect to 100 mass parts of total amounts of (A) and (B). ˜50 parts by mass, (C) 0.1-20 parts by mass, (D) 0.1-20 parts by mass, (A) and (B) ) With respect to 100 parts by mass in total, (B) 5 to 95 parts by mass, (C) 0.1 to 20 parts by mass, and (D) 0.1 to 20 parts by mass. The temporary fixing composition, wherein (C) is an organosilicon compound represented by Formula 1,
Formula _1; X 3 Si-Y
X: one or more hydrolyzable groups in the group consisting of CH ₃ O—, C ₃ H ₅ O—, CH ₃ OC ₂ H ₄ O—
Y: One or more organic functional groups in the group consisting of vinyl group, epoxy group, amino group, mercapto group, and methacryl group
The composition for temporary fixing characterized by containing a polymerization inhibitor, The composition for temporary fixing characterized by containing the granular substance which is not melt | dissolved in (A)-(D), A temporary fixing adhesive comprising a temporary fixing composition, and using the temporary fixing composition, a member is bonded temporarily fixed, and the temporarily fixed member is processed and then processed. members was immersed in the following hot water 90 ° C. and Ru temporary fixing method der members, characterized in that to remove the cured product of said composition.

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 (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) acryloxytetraethoxyphenyl) propane, etc., and trifunctional (meth) acrylate monomers include tomethylolpropane tri (meth) acrylate, tris [(meta ) Acryloylethyl] isocyanurate, etc., and the tetrafunctional or higher (meth) acrylate monomers include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate. , Dipentaerystol penta (meth) acrylate, dipentaerystol hexa (meth) acrylate, etc.

(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 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) a compound composed of an organic substance and silicon is an organic compound having two or more types of functional groups having different reactivity in the molecule, as represented by the schematic chemical structural formula of Formula 1. It is a silicon compound.
Formula _1; X 3 Si-Y
X: hydrolyzable group _{CH 3 O-, C 3 H 5} O-, CH 3 OC 2 H 4 O -
Y: Organic functional group Vinyl group, epoxy group, amino group, mercapto group, methacryl group, etc. The hydrolyzable group represented by X in Formula 1 is water in the aqueous solution, air in the air, or water adsorbed on the inorganic surface. To produce a silanol group (SiOH) rich in reactivity. This silanol group can be adsorbed or chemically bonded to an inorganic material such as glass, silica, or metal, thereby improving the initial adhesiveness of the composition of the present invention. In addition, (C) a compound composed of an organic substance and silicon is hydrolyzed by being immersed in warm water of 90 ° C. or less, and alcohols such as methanol and ethanol are liberated, so that the adherend and the resin composition of the present invention Adhesive strength with the cured body is reduced and peelability can be improved. The hydrolyzable group represented by X is preferably a methoxy group or an ethoxy group from the viewpoint of stability and ease of handling. Y in Formula 1 may be anything as long as it is an organic functional group capable of reacting and bonding with various organic synthetic resins, and representative examples include vinyl, epoxy, methacryl, amino, mercapto groups and the like.

(C) As for the addition amount of the compound comprised from organic substance and silicon, 0.1-20 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 secured, and if it is 20 parts by mass or less, the cured product of the composition is peeled into a film without fear of lowering the initial adhesiveness. From the viewpoint of peelability and initial adhesiveness, it is preferably 0.5 parts by mass or more and 15 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less.

(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 a 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 200 ° 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 material that does not dissolve in (A) to (D) may be used together with (A) to (D). 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 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 decreases because it is released, and (C) the compound composed of organic matter and silicon is hydrolyzed by being immersed in warm water of 90 ° C. or less, and alcohols such as methanol and ethanol are liberated. The adhesive strength between the adherend and the cured product of the resin composition of the present invention is reduced, and the peelability can be improved. Since the alcohols are liberated, the adhesive strength between the member and the cured product of the resin composition is further reduced, and the cured adhesive product can be removed in the form of an adherend film, which is preferable. 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) As polyfunctional (meth) acrylate, 35 parts by mass of TE-2000 manufactured by Nippon Soda Co., Ltd. (1,2-polybutadiene-terminated urethane methacrylate, hereinafter abbreviated as “TE-2000”), dicyclotentanyl diacrylate (KAYARAD R-684 manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as “R-684”) 15 parts by mass, (B) 2- (1,2-cyclohexacarboximide) ethyl acrylate (monofunctional (meth) acrylate) 20 parts by mass of Aronix M-140 manufactured by Toa Gosei Co., Ltd., hereinafter abbreviated as “M-140”, 30 parts by mass of dicyclopentenyloxyethyl methacrylate QM-657 (manufactured by Rohm & Haas, hereinafter abbreviated as QM) AY43-206M (2 parts by mass, manufactured by Toray Dow Corning Co., Ltd., (D) I-907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907 manufactured by Ciba Specialty Chemicals, hereinafter abbreviated as IRGACURE907) as a photopolymerization initiator 6 mass Parts, 2,2-methylene-bis (4-methyl-6-tert-butylphenol) (hereinafter abbreviated as “MDP”) 0.1 parts by mass as a polymerization inhibitor, and isopropyl alcohol (hereinafter “IPA” as a polar organic solvent) (Abbreviated) 2 parts by mass, crosslinked polymethyl methacrylate particles having an average particle diameter of 50 μm as a granular material not dissolved in (A) to (D) (Negami Kogyo Art Pearl GR-200 or less, abbreviated as “GR-200”) 0 A resin composition was prepared by adding 6 parts by mass, and the evaluation method shown below was used using the obtained resin composition. Was measured and peel test Zhang shear strength. 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 × 2.0 mm) is used as the adherend, and the bonded portion is 8 mm in diameter. (Trademark) glass was bonded together, and cured with a fusion device made by Fusion Corporation using an electrodeless discharge lamp under conditions of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm to prepare a tensile shear bond strength test piece. 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 16 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 Table 1. 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)
AY43-206M (manufactured by Toray Dow Corning)
Z6341 (manufactured by Toray Dow Corning)
AY43-210MC (manufactured by Toray Dow Corning)
A-172 (Nihon Unicar)
A-174 (Nihon Unicar)
2-HEMA: 2-hydroxyethyl methacrylate MTEGMA: methoxytetraethylene glycol monomethacrylate (NK Nakamura Chemical Co., Ltd. NK ester M-90G)

(Examples 17 and 18) 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. A test was conducted. The results are shown in Table 3. As a result, it has peelability at any temperature.

(Example 19) Using the resin composition of Example 2, 150 mm × 150 mm × 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 (9)

Temporarily fixing a member, wherein the member is temporarily fixed by bonding, and after the temporarily fixed member is processed, the processed member is immersed in warm water of 90 ° C. or less to remove the cured body of the composition. And (A) 1 to 95 parts by mass of a polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate 5 to 100 parts by mass of the total amount of (A) and (B). 99 parts by mass , (C) one or more of the group consisting of an organosilicon compound represented by formula 1, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane 0.1-20 parts by weight, the temporary fixing composition characterized in that it contains 0.1 to 20 parts by weight (D) a photopolymerization initiator.
Formula _1; X 3 Si-Y
X: one or more hydrolyzable groups in the group consisting of CH ₃ O—, C ₃ H ₅ O—, CH ₃ OC ₂ H ₄ O—
Y: One or more organic functional groups in the group consisting of vinyl group, epoxy group, amino group, mercapto group, and methacryl group The temporary fixing composition according to claim 1, wherein both (A) and (B) are hydrophobic. (A) is 1 to 50 parts by mass, (C) is 0.1 to 20 parts by mass, and (D) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). The composition for temporary fixing according to claim 1 , wherein the composition for temporary fixing is contained. (B) is 5 to 95 parts by mass, (C) is 0.1 to 20 parts by mass, and (D) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). The composition for temporary fixing according to claim 1 , wherein the composition for temporary fixing is contained. (C) is the organosilicon compound shown by Formula 1, The composition for temporary fixing as described in any one of Claims 1 thru | or 4 characterized by the above-mentioned.
Formula 1; X ₃ Si-Y
X: CH ₃ O-, C ₃ H ₅ O-, CH ₃ OC ₂ H ₄ One or more hydrolyzable groups of the group consisting of O-
Y: One or more organic functional groups in the group consisting of vinyl group, epoxy group, amino group, mercapto group, and methacryl group The composition for temporary fixing according to any one of claims 1 to 5, comprising a polymerization inhibitor. The composition for temporary fixing according to any one of claims 1 to 6, comprising a particulate substance that does not dissolve in (A) to (D). Temporary fixing adhesive agent characterized in that it consists of temporary fixing composition according to any one of claims 1 to 7. A member is bonded temporarily fixed using the composition for temporary fixing according to any one of claims 1 to 7 , and the temporarily fixed member is processed, and then the processed member is heated to 90 ° C or less. A method for temporarily fixing a member, wherein the cured product of the composition is removed by dipping in the substrate.