JP2007056066A - Composition and method for temporarily fixing member by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for temporarily fixing an optical member during its processing and to provide a composition desirable therefor. <P>SOLUTION: What is provided is: a composition comprising (A) a (meth)acrylate, (B) a temperature-response polymer and/or a copolymer derived therefrom, (C) a polar solvent, and (D) a photopolymerization initiator; a method for producing the same; and a method for temporarily fixing a member comprising temporarily fixing a member by bonding with the composition, processing the temporarily fixed member, and immersing the processed member in warm water at 90°C or lower to remove a cured body of the composition from the processed member. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a temporary fixing method for processing various members, and also relates to a resin composition and an adhesive suitable for the method, and more specifically, a method for temporarily fixing the member when processing an optical member; The present invention relates to 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 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. Moreover, since the hardened | cured material partially melt | dissolved in the peeled member remains in an adhesive, it is a problem on an external appearance (refer 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 to solve the problems of the prior art, the present invention uses specific hydrophobic (meth) acrylic monomers and combines them with a copolymer composed of a specific temperature-responsive polymer as a polar solvent. Acquired knowledge that an adhesive composition with high adhesive strength and good releasability in warm water achieves this purpose by adding hydrogel swollen with water to such an extent that adhesiveness is not impaired. The invention has been completed.

The present invention has the following gist.
1. A composition comprising (A) (meth) acrylate, (B) a temperature-responsive polymer and / or a copolymer of a temperature-responsive polymer, (C) a polar solvent, and (D) a photopolymerization initiator. object.
2. (B) is an N-alkyl (meth) acrylamide derivative, a nitrogen-containing cyclic monomer, a polymer selected from one or more selected from vinyl group-containing amino acids, and / or an N-alkyl (meth) acrylamide derivative, 2. The composition according to 1 above, which is a copolymer comprising a nitrogen-containing cyclic monomer, at least one selected from vinyl group-containing amino acids, and a vinyl monomer.
3. (B) is a copolymer comprising an N-alkyl (meth) acrylamide derivative, a vinyl monomer having a carboxylic acid group, and a vinyl monomer copolymerizable with the former two. The composition as described.
4). 4. The composition according to any one of 1 to 3, wherein the N-alkyl (meth) acrylamide derivative is N-isopropylacrylamide.
5. (B) is a copolymer composed of N-isopropylacrylamide, diacetone acrylamide and acrylic acid, and / or a copolymer composed of N-isopropylacrylamide, acrylamide and acrylic acid. The composition according to 1.
6). (C) is 1 or more types chosen from the group which consists of water, methanol, ethanol, isopropyl alcohol, and n-butanol, The composition of any one of said 1-5 characterized by the above-mentioned.
7). (A) is hydrophobic, The composition of any one of said 1-6 characterized by the above-mentioned.
8). 100 parts by weight of (A), 0.001 to 10 parts by weight of (B), 0.1 to 20 parts by weight of (C), and 0.1 to 20 parts by weight of (D) 8. The composition according to any one of 1 to 7 above.
9. (A) Any one of the above 1 to 8 comprising 100 parts by mass of (A1) 1 to 50 parts by mass of polyfunctional (methacrylate) and 5 to 95 parts by mass of (A2) monofunctional acrylate. 2. The composition according to item 1.
10. A mixture of (B) and (C) is obtained, and then (A) and (D) are mixed into the mixture, according to any one of items 1 to 9 above A method for producing the composition.
11. An adhesive comprising the composition according to any one of 1 to 9 above.
12 Using the composition according to any one of 1 to 9 above, a member is temporarily fixed, and after processing the temporarily fixed member, the processed member is immersed in hot water of 90 ° C. or less, A method for temporarily fixing a member, comprising removing a cured body of the composition.

The resin composition of the present invention has photocurability because of 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 composition having a specific preferable composition range, the cured product comes into contact with warm water of 90 ° C. or less to swell and can be recovered from the member in the form of a film.

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.

Among the (A) methacrylates used in the present invention, (A1) polyfunctional (meth) acrylates are polyfunctional (meth) acrylates having two or more (meth) acroylated at the terminal or side chain of the oligomer / polymer. Oligomers / polymers and monomers having two or more (meth) acryloyl groups 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.

(A1) The polyfunctional (meth) acrylate is more preferably hydrophobic. However, in the case of being water-soluble, the cured product of the composition swells during 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.

(A1) As for the addition amount of polyfunctional (meth) acrylate, 1-50 mass parts is preferable in 100 mass parts of (A). If the amount is 1 part by mass or more, the property that the cured body is peeled off from the adherend when the cured body of the resin composition is immersed in warm water (hereinafter simply referred to as “peelability”) is sufficiently promoted, and the resin composition It can be ensured that the cured product of the product peels into a film. Moreover, if it is 50 mass parts or less, there is no possibility that initial adhesiveness may fall.

(A2) 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-hydro Cypropyl (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, Enol (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, monohydroxy phthalate Chill (meth) acrylate, (meth) acrylic acid dimer, beta-(meth) acryloyloxyethyl hydrogen succinate, n-(meth) acryloyloxy alkyl hexahydrophthalimide and the like.

(A2) Monofunctional (meth) acrylate is more preferably hydrophobic as in (A1), and in the case of water solubility, the resin composition is swollen during the cutting process, causing 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.

(A2) As for the addition amount of monofunctional (meth) acrylate, 5-95 mass parts is preferable in 100 mass parts of (A). 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, to the blended composition of (A), (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, dioctyl 2- (meth) acryloyloxyethyl phosphate, diphenyl 2- Adhesion to metal surfaces is further improved by using a phosphate ester having a vinyl group or (meth) acryl group such as (meth) acryloyloxyethyl phosphate and (meth) acryloyloxyethyl polyethylene glycol acid phosphate. Can be made.

In the present invention, (B) a temperature-responsive polymer and / or a copolymer of a temperature-responsive polymer is dispersed and swollen in (C) a polar solvent to form a mixture, and the mixture is used together with (A). Thus, it is possible to reliably develop a phenomenon in which the cured composition comes into contact with warm water and easily swells to lower the adhesive strength.

The (B) temperature-responsive polymer of the present invention is a polymer that shrinks above a certain temperature, discharges water, and absorbs water below this temperature, that is, a polymer having a lower critical eutectic temperature with respect to water. Point to. Utilizing these properties, these have been put into practical use as diaper water-absorbing agents, soil modifiers, drug release bases for drug delivery systems, and cell culture sheets.

(B) As the temperature-responsive polymer and / or copolymer of the temperature-responsive polymer, specifically, methylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, poly (meth) acrylic acid, polyethylene polyvinyl acetate partially saponified product, poly Temperature-responsive polymers such as ethylene oxide, polyvinyl methyl ether, poly (N-alkyl (meth) acrylamide), poly (N-vinylpyrrolidone), poly (ethyloxazoline), poly (hydroxypropyl acrylate) and / or their polyfunctional Examples thereof include a copolymer that is three-dimensionally crosslinked with a crosslinking agent such as a vinyl monomer. Among these, N-alkyl (meth) acrylamide derivatives, nitrogen-containing cyclic monomers, polymers composed of one or more selected from vinyl group-containing amino acids, and / or N-alkyl (meth) acrylamide derivatives, nitrogen-containing cyclic monomers, vinyl A copolymer comprising at least one selected from group-containing amino acids and a vinyl monomer is preferred. Here, the vinyl monomer refers to a vinyl monomer copolymerizable with each of an N-alkyl (meth) acrylamide derivative, a nitrogen-containing cyclic monomer, and a vinyl group-containing amino acid.

Examples of N-alkyl (meth) acrylamide derivatives include Nn-propyl (meth) acrylamide, N-isopropylacrylamide, N-cyclopropylacrylamide, Nn-ethylacrylamide, and the like. N-Acroylpyrrolidiene, N-Acroylpiperazine, N-Acroylmorphophorin, 1,4-dimethylpiperazine and the like are mentioned, and the vinyl group-containing amino acid includes N-Acroyl including a vinyl group-containing amino ester derivative. -L-pyrroline, N-acryloyl-L-pyrroline methyl ester, N-methaacryloyl-L-leucine methyl ester, N-metaacroyl-L-isoleucine methyl ester, N-metaacroyl-L-glutamic acid methyl ester, N-metaacroyl- - include vanillin methyl ester.

Examples of copolymerizable vinyl monomers include vinyl monomers such as (meth) acrylamide, diacetone acrylamide, (meth) acrylate, (meth) acrylonitrile, styrene, vinyl acetate, N, N-methylenebis (meth) acrylamide, and ethylene. Crosslinkable monomers such as glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, monocarboxylic acids such as acrylic acid and methacrylic acid, maleic acid, phthalates Examples thereof include vinyl monomers having a carboxylic acid group such as dicarboxylic acid such as acid and itaconic acid.

N-alkyl (meth) acrylamide derivatives, nitrogen-containing cyclic monomers, polymers composed of one or more selected from vinyl group-containing amino acids, and / or N-alkyl (meth) acrylamide derivatives, nitrogen-containing cyclic monomers, vinyl group-containing Among copolymers composed of one or more amino acids selected from amino acids and vinyl monomers, a copolymer composed of a polymer composed of N-isopropylacrylamide and / or a vinyl monomer is preferred from the viewpoint of temperature responsiveness.

Furthermore, a copolymer of an N-alkyl (meth) acrylamide derivative, a vinyl monomer having a carboxylic acid group, and a vinyl monomer copolymerizable therewith is more preferable.

Among these, a copolymer composed of N-isopropylacrylamide, diacetone acrylamide, and acrylic acid, or a copolymer composed of N-isopropylacrylamide, acrylamide, and acrylic acid is more preferable.

As a method of obtaining a temperature-responsive polymer or a copolymer of temperature-responsive polymer, a method of copolymerizing with a crosslinkable monomer when polymerizing the monomer that exhibits the temperature responsiveness, or a temperature response obtained after polymerization The copolymer of the heat-sensitive polymer and the temperature-responsive polymer may be crosslinked by irradiating with an electron beam or the like, but the one used in the present invention is not limited to the above method.

(B) As for the addition amount of the copolymer of a temperature-responsive polymer and a temperature-responsive polymer, 0.001-10 mass parts is preferable with respect to 100 mass parts of total amounts of (A) and (B). If it is 0.001 part by mass or more, releasability can be ensured, and if it is 10 parts by mass or less, the cured product of the resin composition peels into a film without fear of lowering the initial adhesiveness.

(B) As a method for adding a temperature-responsive polymer or a copolymer of a temperature-responsive polymer, (C) a polar solvent is preliminarily dispersed and swollen at room temperature or lower, and the dispersion-swelled product is added to (A) and (D). It is more preferable to add to the composition containing. Specifically, the mixture ratio of (B) and (C) is adjusted at room temperature or lower so as to be 1: 0.1 to 1: 1000 to obtain a mixture, and (A) and (D) are added to the mixture. It is preferable to add a composition containing.

(C) The polar solvent preferably has a boiling point of 50 ° C or higher and 130 ° C or lower. When a polar solvent having a boiling point within the above range is selected, it is preferable because the cured composition can exhibit a phenomenon in which the adhesive strength is lowered due to contact with warm water. In addition, examples of such a polar solvent include water, alcohol, ketone, ester, and the like, and water and alcohol are preferably selected among them according to the results of studies 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.

(C) As for the addition amount of a polar solvent, 0.5-20 mass parts is preferable with respect to 100 mass parts of (A). If it is 0.5 parts by mass or more, the peelability can be ensured, and if it is 20 parts by mass or less, the initial adhesiveness is not lowered, and the cured product of the composition peels into a film. Preferably, the addition of (B) as described above and the dispersion-swelled (C) may be added from the viewpoint of peelability.

(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 100 mass parts of (A). 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.

In the present invention, when a granular material that does not dissolve in (A) to (D) is used together with (A), the cured composition can maintain a constant thickness, improve processing accuracy, and contact with warm water. Thus, the phenomenon of easily swelling and reducing the adhesive strength can be surely expressed.

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 granular material that does not dissolve in (A) to (D) is preferably spherical from the viewpoint of improving the processing accuracy, that is, controlling the film thickness of the adhesive. Spherical ones in the range are preferred. Specifically, the organic particles include 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.

As the particle diameter of the particulate material not dissolved in (A) to (D), the cured product film thickness of the composition can be appropriately selected by those skilled in the art depending on the type, shape, size, etc. of the member. The particle diameter is preferably 1 to 300 μm, more preferably 10 to 200 μm. If it is 1 μm or more, peelability can be secured, and if it is 300 μm or less, the processing accuracy does not decrease. The particle size distribution is preferably as narrow as possible.

0.1-20 mass parts is preferable with respect to (A) 100 mass parts, and, especially the addition amount of the granular material which is not melt | dissolved in (A)-(D) is 0.1-10 mass parts. 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 can use a small amount of a polymerization inhibitor in order to improve its storage stability. For example, polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl. Hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole, and 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 (A). 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 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 warm water, when using warm 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, the vapor pressure of the (C) polar organic solvent works with the peeling force between the member and the cured resin composition, and the cured adhesive is removed in the form of an adherend. This 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
(Adjustment of temperature-sensitive water-absorbing polymer dispersion swelling)
(B) As a temperature-responsive polymer, 1 part by mass of Kojinsha Thermogel R-60 (N-isopropylacrylamide / acrylic acid copolymer, hereinafter abbreviated as “R-60”) is used as (C) a polar solvent. In 50 parts by mass of isopropyl alcohol (hereinafter abbreviated as “IPA”), the mixture is dissolved and mixed in an atmosphere at 23 ° C. for 24 hours to obtain a dispersion swollen product (1) having a concentration of 0.5% (g / g) of (B) It was.

(Adjustment of composition)
(A) As polyfunctional (meth) acrylate, Nippon Soda Co., Ltd. TE-2000 (1,2-polybutadiene terminal urethane methacrylate, hereinafter abbreviated as “TE-2000”) 20 parts by mass, dicyclotentanyl diacrylate (Nippon Kayaku Co., Ltd.) KAYARAD R-684 manufactured, 15 parts by mass, hereinafter abbreviated as “R-684”, 2- (1,2-cyclohexacarboximido) ethyl acrylate (TO-1429 manufactured by Toagosei Co., Ltd.) as monofunctional (meth) acrylate 40 parts by mass (abbreviated as “TO-1429”), phenol ethylene oxide 2 mol modified acrylate (Aronix M-101A manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “M-101A”) 25 parts by mass, 100 parts by mass in total (D) light 10 parts by mass of benzyldimethyl ketal (hereinafter abbreviated as “BDK”) as a polymerization initiator, polymerization As a stopper, 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (hereinafter abbreviated as “MDP”) was added, and 2 parts by mass of the dispersion swelled product (1) ( (B) 0.04 parts by mass as component and 1.94 parts by mass as component C) were added to prepare a composition. Using the obtained 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 × 2.0 mm) was used as the adherend, and the bonded portion was 8 mm in diameter. ) Glass was pasted and cured with a fusion device manufactured by Fusion Corporation using an electrodeless discharge lamp under the condition of an integrated light amount of 2000 mJ / cm ² at 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: A composition prepared under the same conditions as above except that the composition was applied to the heat-resistant Pyrex (registered trademark) glass and bonded to a blue plate glass (150 mm × 150 mm × 1.7 mm) as a support. Curing was performed to prepare a peel test body. 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 11) Compositions were made in the same manner as in Example 1 except that the dispersion swollen material (1) prepared in Example 1 was used and the raw materials of the type shown in Table 1 were used in the composition shown in Table 1. I made a thing. 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 Table 1.

(Materials used)
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO manufactured by BASF)
I-907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907 manufactured by Ciba Specialty Chemicals)
QM: Dicyclopentenyloxyethyl methacrylate (Rohm & Haas QM-657)
BZ: benzyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester BZ)
IBX: Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester IB-X)

(Comparative Examples 1-5)
A resin 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 peeling test were performed in the same manner as in Example 1. The results are shown in Table 2.

(Materials used)
2-HEMA: 2-hydroxyethyl methacrylate MTEGMA: methoxytetraethylene glycol monomethacrylate (Shinnaka

(Examples 12 and 13) Using the resin compositions of Examples 1 and 4, 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 14 Using the composition of Example 1, 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. Further, 10 pieces of the peeled test specimens were taken out arbitrarily, and each piece on the back surface (the surface temporarily fixed with the resin composition) of the test specimen was observed using an optical microscope. 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-methylpidrirone solution for 1 day, the cut test piece was collected, and 10 pieces of the cut test piece peeled off in the same manner as in Example 14 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 from which the cut test pieces were peeled off in the same manner as in Example 25 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 above-described characteristic composition, so that it is not necessary to use an organic solvent that has been necessary in the prior art, and it can be recovered from the member in the form of a film, thus improving workability. Since it has the feature of being excellent, it is very useful in industry.

Claims (12)

A composition comprising (A) (meth) acrylate, (B) a temperature-responsive polymer and / or a copolymer of a temperature-responsive polymer, (C) a polar solvent, and (D) a photopolymerization initiator. (B) is an N-alkyl (meth) acrylamide derivative, a nitrogen-containing cyclic monomer, a polymer selected from one or more selected from vinyl group-containing amino acids, and / or an N-alkyl (meth) acrylamide derivative, The composition according to claim 1, which is a copolymer comprising a nitrogen-containing cyclic monomer, at least one selected from vinyl group-containing amino acids and a vinyl monomer. (B) is a copolymer comprising an N-alkyl (meth) acrylamide derivative, a vinyl monomer having a carboxylic acid group, and a vinyl monomer copolymerizable with the former two. The composition according to 1. The composition according to any one of claims 1 to 3, wherein the N-alkyl (meth) acrylamide derivative is N-isopropylacrylamide. (B) is a copolymer composed of N-isopropylacrylamide, diacetone acrylamide and acrylic acid, and / or a copolymer composed of N-isopropylacrylamide, acrylamide and acrylic acid. Item 2. The composition according to Item 1. The composition according to any one of claims 1 to 5, wherein (C) is at least one selected from the group consisting of water, methanol, ethanol, isopropyl alcohol, and n-butanol. The composition according to any one of claims 1 to 6, wherein (A) is hydrophobic. 100 parts by weight of (A), 0.001 to 10 parts by weight of (B), 0.1 to 20 parts by weight of (C), and 0.1 to 20 parts by weight of (D) The composition according to any one of claims 1 to 7. (A) Of 100 parts by mass, 1 to 50 parts by mass of (A1) polyfunctional (methacrylate) and 5 to 95 parts by mass of (A2) monofunctional acrylate are contained. The composition according to claim 1. The composition according to any one of claims 1 to 9, wherein a mixture of (B) and (C) is obtained, and then (A) and (D) are mixed with the mixture. Manufacturing method. An adhesive comprising the composition according to any one of claims 1 to 9. A member is temporarily fixed using the composition according to any one of claims 1 to 9, and after the temporarily fixed member is processed, the processed member is immersed in warm water of 90 ° C or lower. A method for temporarily fixing a member, comprising removing a cured body of the composition.