JP2007169560A - Composition and method for temporarily fixing member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for temporarily fixing optical members in their processing, and to provide a composition suitable for the method. <P>SOLUTION: The composition comprises (A) a polyfunctional (meth)acrylate (B) a monofunctional (meth)acrylate, (C) a compound coloring on being irradiated with rays and (D) a photopolymerization initiator. Preferably, the components (A) and (B) are hydrophobic and the component(C) is a leuco dye. The method for temporarily fixing a member comprises temporarily adhesively fixing the member using the composition, processing the member thus temporarily fixed followed by immersing this member in a hot water of 90°C or lower to detach the cured form of the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

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.

With respect to the mounted parts and the like, these parts are fixed to the base material with a double-sided tape, and then the 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 bonding the members, the adhesive is infiltrated into the gap between the member and the substrate by heating, and then the desired part is cut and the adhesive is bonded in an organic solvent. Remove.

However, in the case of double-sided tape, it is difficult to obtain thickness accuracy, the adhesive strength is weak, so chipping properties are inferior when parts are processed, and it cannot be peeled off unless it is heated to 100 ° C or higher. In the case of peeling by irradiation, there is a problem that peeling is not possible 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 members and substrates 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 temporary fixing photo-curing or heating adhesive 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 adhesives for temporary fixing that have improved adhesiveness by using specific (meth) acrylates with high hydrophilicity and improved releasability by swelling and partial dissolution. Since the frictional heat generated between the part and the cutting jig such as the blade or diamond cutter is generated and cooled with a large amount of water, the above-mentioned highly hydrophilic composition swells and becomes flexible when it is cut. Therefore, higher dimensional accuracy cannot be reached. Moreover, since the hardened | cured material partially melt | dissolved in the peeled member remains in adhesiveness, it becomes a problem on an external appearance. Furthermore, when the cured adhesive remains on the part after peeling, it is difficult to remove it because it is difficult to distinguish it from the part. References 1, 2, and 3).
Japanese Patent Laid-Open No. 06-116534. Japanese Patent Application Laid-Open No. 11-071553. Japanese Patent Application Laid-Open No. 2001-226641.

In order to improve the dimensional accuracy of the part after cutting, when it is hydrophobic, has high adhesive strength, has excellent peelability in water, and there is little glue residue on the part after peeling, In this case, there is a strong demand for a photo-curing adhesive that can easily remove the cured adhesive and can be easily distinguished from components, and is excellent in workability from an environmental point of view.

As a result of various investigations to solve the problems of the prior art, the present inventor has used a specific hydrophobic (meth) acrylic monomer, combined with this, and added with a compound that is colored by light irradiation. Not only has high adhesive strength and good releasability in warm water, but also allows the cured product remaining on the member to be colored, so that the cured product can be easily removed and the adhesive residue phenomenon is temporarily avoided. When it occurred, the inventors have found that it can be easily found and can be easily detected before the next process of the member, and the invention has been completed.

That is, the present invention is characterized by containing (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, (C) a compound colored by light irradiation, and (D) a photopolymerization initiator. It is a composition.

The present invention is the above composition, wherein (C) is a leuco dye.

Furthermore, the present invention, in its preferred embodiment, (A) is 1 to 50 parts by mass, (B) is 5 to 95 parts by mass, (C) is 0.0001 to 20 parts by mass, and (D) is 0.00. It is the said composition characterized by containing 1-20 mass parts, It is an adhesive agent which consists of the said composition.

In addition, according to the present invention, the member is temporarily bonded and fixed using the composition, and after the temporarily fixed member is processed, the processed member is immersed in warm water of 90 ° C. or less, A method for temporarily fixing a member, comprising removing a cured body.

The composition of the present invention has photocurability due to its composition, and is cured by visible light or ultraviolet light, and produces a colored cured product. For this reason, compared with the conventional hot melt adhesive, when fixing a part, 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. In addition, even if a glue residue phenomenon occurs, it can be easily found and can be easily detected before passing the next process of the member, which can contribute to the prevention of the occurrence of a process failure in the next process and the loss of defective products.

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. In addition, since the cured product is colored even when the cured product remains in the member, the composition of the present invention can be easily distinguished from the member and can therefore be easily removed. Obtainable.

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.

The compound colored by (C) light irradiation used in the present invention is a compound colored by the same visible light or active light such as ultraviolet light that the photopolymerization initiator (D) described later operates. Preferable specific examples of this compound include leuco dyes, which generally exhibit a behavior of being colorless or light-colored before irradiation with light but being colored brown upon irradiation with light.

As the leuco dye, conventional triphenylmethane, fluorane, phenothiazine, olamine, and spiropyran dyes are preferably used. Specifically, 3- [N- (p-tolylamino)]-7-anilinofluorane, 3- [N- (p-tolyl) -N-methylamino] -7-anilinofluorane, 3- [ N- (p-tolyl) -N-ethylamino] -7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, crystal violet lactone, 4,4 ', 4 "-trisdimethyl Aminotriphenylmethanol, 4,4 ′, 4 ″ -trisdimethylamino] triphenylmethane, and the like.

Developers preferably used with these leuco dyes include initial polymers of phenol formalin resins, aromatic carboxylic acid derivatives, electron acceptors such as activated clay, and various other known color developments when changing the color tone. Combinations of agents can also be used.

(C) As for the compound colored by light irradiation, 0.0001-20 mass parts is preferable with respect to 100 mass parts of total amounts of (A) and (B). If it is 0.0001 part by mass or more, the cured product can be clearly colored, and if it is 20 part by mass or less, the initial adhesiveness is not inferior and the film is surely peeled off. From the viewpoints of colorability and initial adhesiveness and peelability, 0.0005 to 15 parts by mass is preferable, and 0.001 to 10 parts by mass is even more preferable.

(D) As a photoinitiator, it mix | blends in order to accelerate | stimulate photocuring of a composition by sensitizing with active rays, such as visible light and an ultraviolet-ray, Various well-known photoinitiators can be used. is there.

Specifically, benzophenone and derivatives thereof, benzyl and derivatives thereof, entraquinone and derivatives thereof, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, 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-dioxo Bicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy- -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- Α-aminoalkylphenone derivatives such as dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2 , 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, , Etc. acylphosphine oxide derivatives such as 4,6-trimethylbenzoyl dichloride ethoxyphenyl phosphine oxide. A photoinitiator can be used 1 type or in combination of 2 or more types.

As for the addition amount of a photoinitiator, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of (A) and (B). More preferably, 3-20 mass parts is preferable. If it is 0.1 mass part or more, the effect of hardening acceleration | stimulation will be acquired reliably, and sufficient curing rate can be obtained if it is 20 mass parts or less. As a more preferable form, by adding 3 parts by mass or more of the component (D), it is possible to cure without depending on the amount of light irradiation, and further the degree of cross-linking of the cured product of the composition is increased, resulting in misalignment during cutting. It is more preferable at the point which loses and the peelability improves.

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 in total of (A) and (B). Storage stability is ensured at 0.001 part by mass or more, good adhesiveness is obtained at 3 parts by mass or less, and it does not become uncured.

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, particulate materials that do not dissolve in (A) to (D) may be used together. 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 the particulate material that does not dissolve in (A) to (D), either organic or inorganic particles that are generally used may be used. 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, 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.

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

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

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

Further, according to a preferred embodiment of the present invention, when removing the cured body of the composition, the cured body swells in contact with hot water of 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.

Further, since the cured adhesive material remaining on the member is colored and can be easily distinguished from the member, an effect that the cured adhesive material can be easily removed is obtained.

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

In the present invention, when warm water heated moderately, specifically, hot water of 90 ° C. or less is used, the releasability in water can be achieved in a short time, which is preferable from the viewpoint of productivity. Regarding the temperature of the hot water, when using hot water of 30 ° C. to 90 ° C., preferably 40 to 90 ° C., the cured product of the adhesive swells in a short time and the residual strain stress generated when the composition is cured is Since it is released, the adhesive strength is lowered, and it works with the peeling force between the member and the cured product of the resin composition, so that the cured adhesive product can be removed in the form of a film on the adherend, 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 used for temporary fixing and the material of the substrate are not particularly limited, and when used as an ultraviolet curable adhesive, a member and a substrate made of a material capable of transmitting ultraviolet rays are 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. In addition, since the cured adhesive material remaining on the member is colored and easily distinguished from the member, the cured adhesive material can be easily removed.

Example 1
(A) As polyfunctional (meth) acrylate, Nippon Soda Co., Ltd. TE-2000 (1,2-polybutadiene terminal urethane methacrylate, hereinafter abbreviated as “TE-2000”) 35 parts by mass, dicyclotentanyl diacrylate (Nipponization) KAYARAD R-684 manufactured by Yakuhin Co., Ltd., hereinafter abbreviated as “R-684”.) 15 parts by mass, (B) As monofunctional (meth) acrylate, 2- (1,2-cyclohexacarboximide) ethyl acrylate (Toagosei) Aronix M-140, abbreviated as “M-140” hereinafter) 20 parts by mass, dicyclopentenyloxyethyl methacrylate QM-657 (Rohm & Haas, abbreviated as “QM” hereinafter) 30 parts by mass, C) As a compound colored by light irradiation, 4,4 ′, 4 ″ -trisdimethylamino] triphenylmethane (Hodoga) A-DMA manufactured by Tani Chemical Industry Co., Ltd., hereinafter abbreviated as “A-DMA”.) 0.0002 parts by mass, (D) As a photopolymerization initiator, I-907: 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one (IRGACURE907 manufactured by Ciba Specialty Chemicals, hereinafter abbreviated as “IRGACURE907”), 6 parts by mass, 2,2-methylene-bis (4-methyl) as a polymerization inhibitor -6 (tertiary butylphenol) (hereinafter abbreviated as “MDP”) 0.1 part by mass, 2 parts by mass of isopropyl alcohol (hereinafter abbreviated as “IPA”) as a polar organic solvent, dissolved in (A) to (D) As a granular material, a crosslinked polymethyl methacrylate particle having an average particle diameter of 50 μm (Negami Kogyo Art Pearl GR-200, hereinafter abbreviated as “GR-200”) .) Have created to compositions blended 0.6 parts by weight. Using the obtained composition, measurement of tensile shear bond strength, peel test, and color difference measurement were performed by the following evaluation methods. 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 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: It was 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 × 1.7 mm thick) as a support. The composition 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.

Color difference: White plate glass (750 mm × 250 mm × thickness 1.0 mm) is coated with a 100 μm tape (3 mm width) on two opposite sides, the composition is applied to the white plate glass, and white plate glass (750 mm × 250 mm × thickness) 1.0 mm) and cured with a fusion device using a non-electrode discharge lamp under the conditions of an integrated light quantity of 2000 mJ / cm ² with a wavelength of 365 nm, a test piece was prepared, and a color difference meter (Nippon Denshoku) The color difference ΔE was measured by a model ZEL1001DP manufactured by Kogyo Co.

(Examples 2-14, Comparative Examples 1-9)
Various compositions were prepared in the same manner as in Example 1 except that the raw materials of the types shown in Tables 1 and 2 were used in the compositions shown in Tables 1 and 2. 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 Tables 1 and 2.

(Materials used)
BDK: benzyl dimethyl ketal (IRGACURE651 manufactured by Ciba Specialty Chemicals)
M101A: phenol ethylene oxide 2 mol modified acrylate (Aronix M-101A manufactured by Toa Gosei Co., Ltd.)
BZ: benzyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester BZ)
IBX: Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester IB-X)
Propylene carbonate (manufactured by Sigma-Aldrich)
Dimethyl carbonate (Sigma-Aldrich)
2-HEMA: 2-hydroxyethyl methacrylate MTEGMA: methoxytetraethylene glycol monomethacrylate (NK Nakamura Chemical Co., Ltd. NK ester M-90G)
MCB: Macrolex Blue (Colorant for plastics manufactured by Bayer Japan)
R-5B: Macrolex Red 5B (A plastic colorant manufactured by Bayer Japan)
GG: Macrolex Green G (Colorant for plastics manufactured by Bayer Japan)

(Examples 15 and 16)
Using the compositions of Examples 2 and 6, peel test specimens were prepared in the same manner as in Example 1, and peel tests were performed while changing the temperature of hot water at 40 ° C, 50 ° C, 60, and 70 ° C. The results are shown in Table 3. As a result, it has peelability at any temperature.

(Example 17)
Using the resin composition of Example 2, 150 mm × 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. 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 10)
A hot-melt adhesive (Adfix A manufactured by Nikka Seiko Co., Ltd.) is heated to 90 ° C. and dissolved to bond the 150 mm × 150 mm × 2 mm heat-resistant Pyrex (registered trademark) glass and the blue plate glass used 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. 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 11)
A 150 mm × 150 mm × 2 mm heat-resistant Pyrex (registered trademark) glass 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 and is cured by actinic rays such as visible light and ultraviolet rays, and since the cured product can express high adhesive strength without being affected by cutting water or the like, There is an effect that a member that hardly causes a shift when the member is processed and that is excellent in terms of dimensional accuracy can be easily obtained. Furthermore, the adhesive strength is reduced by contact with hot water, and the bonding force between the members or between the member and the jig is reduced, so that there is a feature that the member can be easily recovered, so that the optical lens, prism, array, It is industrially useful as an adhesive for temporarily fixing silicon wafers, semiconductor mounting parts and the like.

The method for temporarily fixing the member of the present invention uses the characteristic resin composition, so it is not necessary to use an organic solvent required in the prior art, and not only can be recovered from the member in the form of a film, Even if the cured adhesive remains in the member, the cured adhesive is colored and easily distinguishable from the member. is there.

Claims (6)

A composition comprising (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, (C) a compound colored by light irradiation, and (D) a photopolymerization initiator. The composition according to claim 1, wherein (C) is a leuco dye. The composition according to claim 1 or 2, wherein both (A) and (B) are hydrophobic. 1 to 50 parts by mass of (A), 5 to 95 parts by mass of (B), 100 parts by mass of (A) and (B), and (C) to 0.0001 to 20 parts by mass, ( D) 0.1-20 mass parts is contained, The composition as described in any one of Claim 1 thru | or 3 characterized by the above-mentioned. An adhesive comprising the composition according to any one of claims 1 to 4. Using the composition according to any one of claims 1 to 5, a member is temporarily bonded and fixed, and after the temporarily fixed member is processed, the processed member is immersed in warm water of 90 ° C or lower. And removing the cured body of the composition.