JP4916681B2 - Photocurable adhesive for temporary fixing method and temporary fixing method of member using the same - Google Patents

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 semiconductor mounting parts, these parts are fixed to the base material with double-sided tape, then the parts are cut into a desired shape, and further, the double-sided tape is irradiated with ultraviolet rays to peel from the parts. I do. In the case of a hot-melt adhesive, after contacting the members with each other or a jig, etc., the adhesive is infiltrated into the gap between the two by heating, and then the parts are cut to a desired shape. After that, the adhesive is peeled off in an organic solvent.

However, in the case of double-sided tape, it is difficult to obtain accuracy with respect to thickness, the chipping property at the time of component processing is inferior due to weak adhesive strength, and it cannot be peeled off unless heat is applied at 100 ° C or higher. Further, when peeling by ultraviolet irradiation, there is a problem that peeling is impossible 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 of the prior art, a temporary fixing photo-curing type or heating type adhesive containing a water-soluble compound such as a water-soluble vinyl monomer has been proposed. However, in these adhesive compositions, the peelability in water is solved, but the adhesive strength at the time of fixing the component is low, and there is a problem that the dimensional accuracy of the member after cutting is poor. In addition, adhesives for temporary fixing that have improved adhesion by using specific (meth) acrylates with high hydrophilicity and improved releasability by swelling and partial dissolution have also been proposed. 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, it is impossible reach higher dimensional accuracy, a cured product was partially dissolved in peeled member that has become to rest glue, appearance problems (see Patent documents 1, 2 and 3).
JP-A-6-116534 Japanese Patent Laid-Open No. 11-71553 Japanese Patent Laid-Open No. 2001-226641

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

As a result of various investigations to solve the problems of the prior art, the present inventor has used a specific (meth) acrylic monomer, combined this, and a specific polar organic solvent and a specific granular material, A composition having high adhesive strength and good releasability in warm water was obtained, and the inventors obtained the knowledge that this achieves the object and completed the invention.

1. The member is temporarily fixed, and after the temporarily fixed member is processed, the processed member is immersed in warm water of 90 ° C. or less, and the cured body of the photocurable adhesive for temporary fixing is removed. (A) a polyfunctional (meth) acrylate containing 1,2-polybutadiene-terminated urethane methacrylate and dicyclopentanyl diacrylate, (B) 2- (1 , 2-cyclohexacarboximide) ethyl acrylate and phenol (ethylene oxide 2 mol modified) acrylate, monofunctional (meth) acrylate, (C) photopolymerization initiator, (D) polar organic solvent, and (E) said (A)-(D) containing the granular substance which does not melt | dissolve, The photocurable adhesive for temporary fixing methods characterized by the above-mentioned.
2. (E) is spherical, The photocurable adhesive for temporary fixing methods according to 1 above.
3. (E) The photocurability for the temporary fixing method according to the above 1 or 2, wherein the particulate material is at least one selected from the group consisting of crosslinked polymethyl methacrylate particles, crosslinked polystyrene particles, and spherical silica particles. adhesive.
4). (D) is 1 or more types chosen from the group which consists of methanol, ethanol, isopropyl alcohol, and n-butanol, The photocurability for temporary fixing methods of any one of said 1-3 characterized by the above-mentioned. adhesive.
5. 5. The photocurable adhesive for temporary fixing method according to any one of 1 to 4 above, which comprises a polymerization inhibitor.
6). (A) is 1 to 50 parts by mass in 100 parts by mass of the total amount of (A) and (B), and (C) is 0.1 parts per 100 parts by mass of (A) and (B). Temporary fixing according to any one of 1 to 5 above, comprising from 20 to 20 parts by weight, 0.1 to 10 parts by mass of (D) and 0.5 to 10 parts by mass of (E) Method photocurable adhesive.
7 . The structure formed by temporarily fixing using the photocurable adhesive for temporary fixing methods of any one of said 1-6 .
8 . The member is temporarily fixed using the photocurable adhesive for temporarily fixing method according to any one of 1 to 7 above, and after the temporarily fixed member is processed, the processed member is 90 ° C or lower. A method for temporarily fixing a member, wherein the member is immersed in warm water and the cured product 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 maintain high adhesive strength even when it comes into contact with cutting water or the like used during processing, there is an effect that a member excellent in dimensional accuracy can be easily obtained without being easily displaced during processing of the member. Can be achieved. In addition, the cured body has a feature that the member can be easily collected because the adhesive strength is reduced by contacting with warm water of 30 ° C. or more and the bonding force between the members or between the member and the jig is reduced. In addition, 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, which is required in the case of a conventional adhesive. Furthermore, in the composition having a specific preferable composition range, the cured product comes into contact with warm water of 30 ° C. or more and swells and can be recovered from the member in the form of a film.

As described above, the method for temporarily fixing a member of the present invention uses a composition that reduces the adhesive strength by contacting with warm water of 30 ° C. or higher, so that 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.

The (A) polyfunctional (meth) acrylate used in the present invention is a polyfunctional (meth) acrylate oligomer / polymer having 2 or more (meth) acroylated terminals or side chains of the oligomer / polymer, or 2 or more A monomer having a (meth) acryloyl group can be used. For example, as the polyfunctional (meth) acrylate oligomer / polymer, 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, TE-2000, TEA-1000 manufactured by Nippon Soda Co., Ltd.), the hydrogenated product (for example, Nippon Soda 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, and the like .

(A) 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.

(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), and 5-30 mass parts is especially preferable. 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 composition swells at the time of cutting, causing displacement and processing accuracy. Is not preferable because it may be inferior. Even if it is hydrophilic, it can be used if the cured product of the 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), and 10-80 mass parts is still more preferable. 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.

(C) 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 (C) as a more preferable form, the composition can be cured without depending on the amount of light irradiation, the cross-linking degree of the cured product of the composition is increased, and 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, by using the polar organic solvent (D) together with (A) and (B), the phenomenon that the cured composition comes into contact with warm water and easily swells to reduce the adhesive strength is ensured. Can be expressed.

(D) 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.

(D) 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, (E) a granular material that does not dissolve in (A) to (D) is used together with (A) to (D), whereby the composition after curing is constant. Since the thickness can be maintained, the processing accuracy is improved, and the phenomenon that the adhesive strength is lowered due to being easily swollen by contact with hot water can be surely exhibited.

(E) The particulate material that does not dissolve in (A) to (D) may be either organic or inorganic particles generally 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.

(E) The granular material that does not dissolve in (A) to (D) is preferably spherical from the viewpoint of improving processing accuracy, that is, controlling the film thickness of the adhesive. A spherical one in the range of 8 to 1 is preferred. Specifically, as the organic particles, methyl methacrylate monomer, cross-linked polymethyl methacrylate particles, cross-linked polystyrene particles and inorganic particles are spherical silica, and the composition of the composition after curing due to particle size variation is small. Among these, crosslinked polymethyl methacrylate particles and crosslinked polystyrene particles are more preferable from the viewpoint of storage stability such as sedimentation of particles and reactivity of the composition.

(E) 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 average particle diameter of the particles 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.

(E) The addition amount of the particulate material that does not dissolve in (A) to (D) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). 1-10 mass parts is preferable. 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 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.

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 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 processed. This is a method for temporarily fixing a member that removes the cured adhesive by immersing the processed member in warm water, thereby processing various members such as optical members with high processing accuracy without using an organic solvent. can do.

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

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

In the temporary fixing method of the present invention, the structure in which the member is temporarily fixed with the composition of the present invention can reliably obtain the effects of the present invention.

In the present invention, when warm water heated moderately, specifically, hot water of 30 ° C. or higher is used, releasability in water can be achieved in a short time, which is preferable from the viewpoint of productivity. Regarding the temperature of the hot water, when using hot water of 30 ° C. to 90 ° C., preferably 40 to 90 ° C., the cured product of the adhesive swells in a short time and the residual strain stress generated when the composition is cured is Since it is released, the adhesive strength is reduced. In addition, the vapor pressure of the (E) 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 a film on the 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) as (A) a polyfunctional (meth) acrylate, manufactured by Nippon Soda Co., Ltd. TE-2000 (1,2-polybutadiene-terminated urethane methacrylate, hereinafter abbreviated as "TE-2000") 20 parts by weight, dicyclohexyl Bae Ntaniru 15 parts by mass of diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R-684, hereinafter abbreviated as “R-684”), (B) 2- (1,2-cyclohexacarboximide) ethyl acrylate as monofunctional (meth) acrylate 40 parts by mass (Aronix M-140 manufactured by Toa Gosei Co., Ltd., hereinafter abbreviated as “M-140”), 2 mol of phenol ethylene oxide modified acrylate (Aronix M-101A produced by Toa Gosei Co., Ltd., hereinafter abbreviated as “M-101A”) 25 100 parts by weight in total, (C) benzyl dimethyl ketal (hereinafter “BDK”) as a photopolymerization initiator (Abbreviated) 10 parts by mass, (D) 2 parts by mass of isopropyl alcohol (hereinafter abbreviated as “IPA”) as a polar organic solvent, and (E) (A) to (D) as a particulate substance that does not dissolve in crosslinked polymer having an average particle size of 50 μm 0.2 parts by mass of methyl methacrylate particles (Negami Kogyo Art Pearl GR-200, hereinafter abbreviated as “GR-200”), 2,2-methylene-bis (4-methyl-6-tertiary) as a polymerization inhibitor Butylphenol) (hereinafter abbreviated as “MDP”) 0.1 part by mass was added to prepare a composition. Table 1 shows the results obtained by the following evaluation method for the ratio of the major axis to the minor axis of the granular material not dissolved in (E), (A) to (D). 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 2.

(Evaluation methods)
Long and short diameter ratio: (E) As an index representing the sphericity of a granular material that does not dissolve in (A) to (D), close-up was performed 20,000 times with a scanning electron microscope (“JSM-T200” manufactured by JEOL Ltd.) The particle image was taken into an image analyzer (manufactured by Nippon Avionics Co., Ltd.), and the average of the ratio of the major axis to the minor axis of 100 arbitrarily selected particles was determined.

Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, heat-resistant Pyrex (registered trademark) glass (25 mm × 25 mm × thickness 2.0 mm) was used as the adherend, and the bonded portion was 8 mm in diameter. (Registered Trademark) glass was laminated and cured by a fusion device made 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: Composition prepared under the same conditions as above except that the resin composition was applied to the above heat-resistant Pyrex (registered trademark) glass and bonded to blue plate glass (150 mm × 150 mm × 1.7 mm thick) 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 Compositions were prepared in the same manner as in Example 1 except that raw materials of the types shown in Tables 2 and 3 were used in the compositions shown in Tables 2 and 3. 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 2 and 3.

(Materials used)
GR-600: Cross-linked polymethyl methacrylate particles having an average particle size of 25 μm (Art Pearl GR-600 manufactured by Negami Industrial Co., Ltd.)
GM-1005-10: Cross-linked polymethyl methacrylate particles having an average particle diameter of 10 μm (Gantz Pearl GM-1005-10 manufactured by Ganz Kasei Co., Ltd.)
GM-5047: average particle diameter 10 μm cross-linked polybutyl methacrylate particles (Ganz Pearl GM-1005-10 manufactured by Ganz Kasei Co., Ltd.)
SGP-150C: Crosslinked polystyrene particles having an average particle diameter of 55 μm (Chemisnow SGP-150C manufactured by Soken Chemical Co., Ltd.)
SGP-140C: average particle diameter 42 μm cross-linked polystyrene particles (Chemisnow SGP-140C manufactured by Soken Chemical Co., Ltd.)
SGP-100C: Cross-linked polystyrene particles having an average particle size of 25 μm (Chemisnow SGP-100C manufactured by Soken Chemical Co., Ltd.)
2100JPD: average particle size 147 μm polyethylene particles (Hi-Zex2100JPD manufactured by Mitsui Chemicals)
PE-130: Average particle diameter of 12.5 μm polyethylene particles (CAERIDUST PE-130 manufactured by Clariant Japan)
PP-6071: Polypropylene particles having an average particle diameter of 20 μm (CAERIDUST PP-6071 manufactured by Clariant Japan)
LS-L100: spherical silica particles having an average particle size of 10 μm (LS-L100 manufactured by Tokuyama Corporation)

(Comparative Examples 1-5)
A composition was prepared in the same manner as in Example 1 except that the raw materials of the type shown in Table 4 were used in the composition shown in Table 3. 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 4.

(Materials used)
2-HEMA: 2-hydroxyethyl methacrylate IBX: isobornyl methacrylate (Light Ester IBX manufactured by Kyoeisha Chemical Co., Ltd.)
BZ: benzyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester BZ)
MTEGMA: methoxytetraethylene glycol monomethacrylate (NK ester M-90G manufactured by Shin-Nakamura Chemical Co., Ltd.)

Example 17 The composition of Example 1 was applied to a 200 mm square polyethylene terephthalate (hereinafter abbreviated as PET) film, 150 mm × 150 mm × 2 mm heat-resistant Pyrex (registered trademark) glass was laminated, and the pressure was 32 kg / A constant load was applied to the glass with a weight so as to be cm ² for 10 minutes, and then the adhesive was cured in the same manner as in Example 1. Thereafter, the PET film was peeled off, and the film thicknesses at 16 arbitrary locations divided into 16 parts of the composition cured on 150 mm square glass were measured with a micrometer. The result is shown in FIG. As a result, it was found that a substantially constant film thickness was obtained.

(Example 18) Using the composition of Example 1, 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 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 5.

(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 25 were taken out, and the back side of the cut test piece (hot melt adhesive) Each piece of the surface temporarily fixed with the agent was observed using an optical microscope, the maximum width of the portion where the glass was missing was measured, and the average value and the standard deviation were obtained. The results are shown in Table 5.

(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 5.

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 maintain high adhesive strength even when it comes into contact with cutting water. In addition, it is possible to easily obtain a member that is excellent in terms of dimensional accuracy, and further, the adhesive strength is reduced by contacting with hot water, and the bonding force between the members or between the member and the jig is reduced. Since it is reduced, the member can be easily collected, and thus 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.

The figure which shows the measurement result of the film thickness distribution of the composition which concerns on Example 17. FIG.

Claims (8)

The member is temporarily fixed, and after the temporarily fixed member is processed, the processed member is immersed in warm water of 90 ° C. or less, and the cured body of the photocurable adhesive for temporary fixing is removed. (A) a polyfunctional (meth) acrylate containing 1,2-polybutadiene-terminated urethane methacrylate and dicyclopentanyl diacrylate, (B) 2- (1 , 2-cyclohexacarboximide) ethyl acrylate and phenol (ethylene oxide 2 mol modified) acrylate, monofunctional (meth) acrylate, (C) photopolymerization initiator, (D) polar organic solvent, and (E) said (A)-(D) containing the granular substance which does not melt | dissolve, The photocurable adhesive for temporary fixing methods characterized by the above-mentioned. The photocurable adhesive for temporary fixing according to claim 1, wherein (E) is spherical. (E) The particulate material is at least one selected from the group consisting of crosslinked polymethyl methacrylate particles, crosslinked polystyrene particles, and spherical silica particles. Photo-curable adhesive. 4. The photo-curing property for a temporary fixing method according to claim 1, wherein (D) is at least one selected from the group consisting of methanol, ethanol, isopropyl alcohol, and n-butanol. adhesive. The photocurable adhesive for a temporary fixing method according to any one of claims 1 to 4, further comprising a polymerization inhibitor. (A) is 1 to 50 parts by mass in 100 parts by mass of the total amount of (A) and (B), and (C) is 0.1 parts per 100 parts by mass of (A) and (B). 6 to 20 parts by weight, 0.1 to 10 parts by weight of (D), 0.5 to 10 parts by weight of (E), and the provisional of any one of claims 1 to 5 Photocurable adhesive for fixing method. The structure formed by temporarily fixing using the photocurable adhesive for temporary fixing methods of any one of Claims 1 thru | or 6 . A member is temporarily fixed using the photocurable adhesive for temporarily fixing method according to any one of claims 1 to 7 , and after the temporarily fixed member is processed, the processed member is heated to 90 ° C. A method for temporarily fixing a member, wherein the member is immersed in the following warm water to remove the cured body of the composition.

Images