KR20110031347A - Method for provisional fixing/release of member and adhesive for provisional fixing suitable therefor - Google Patents

Abstract

Provided is a temporary fixing method capable of obtaining a special effect in terms of the dimensional accuracy of the machining member. The coating step of applying the adhesive for temporary fixing to the fixing member, the mounting step of mounting the workpiece to the temporary fixing adhesive, and irradiating at least one of visible or ultraviolet rays to the temporary fixing adhesive after the mounting step to increase the adhesive strength of the temporary fixing adhesive A temporary fixing method comprising a pressure step including a step, and a pressure step of applying pressure to one or both of the fixed member and the member to be processed, wherein the pressure step and the irradiation step are simultaneously performed for at least a predetermined time. The adhesive for temporarily fixing is a composition containing (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C) photoinitiator.

Description

METHOD FOR PROVISIONAL FIXING / RELEASE OF MEMBER AND ADHESIVE FOR PROVISIONAL FIXING SUITABLE THEREFOR}

This invention relates to the temporarily fixing and peeling method at the time of processing various members, and also relates to the temporarily fixing adhesive for temporarily fixing it. For example, when processing an optical member, it relates to the method of temporarily fixing this member, the peeling method, and the photocurable temporarily fixed adhesive suitable for the said use.

Double-sided tapes or hot melt adhesives are used as temporary fixing adhesives for optical lenses, prisms, arrays, silicon wafers, and semiconductor mounting parts. Manufacturing of the member is performed. 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 the peeling from a part is performed by irradiating an ultraviolet-ray to a double-sided tape further. In the case of a hot melt adhesive, after joining the members, the adhesive is allowed to penetrate into the gap by heating, and then the desired parts are cut and the adhesive is peeled off in the organic solvent.

However, in the case of double-sided tapes, it is difficult to achieve dimensional accuracy or weak adhesive strength, and thus, there is a problem that peeling is not possible without inferior chipping property or heat applied at 100 ° C. or higher during machining of parts. When peeling by ultraviolet irradiation, there existed a problem that peeling was impossible if the permeability of a to-be-adhered body was insufficient.

In the case of a hot melt adhesive, it is necessary to use an organic solvent at the time of peeling, and the washing | cleaning process process of an alkaline solution and a halogen-type organic solvent has become complicated, and it also became a problem in working environment.

In order to solve such a fault, the photocurable or heating type adhesive for temporarily fixing containing water-soluble compounds, such as a water-soluble vinyl monomer, was proposed. In the temporary fixation method using these adhesives, peelability in water was solved, but there was a problem that the adhesive strength at the time of fixing the component was low and the dimensional accuracy of the member after cutting was insufficient.

Moreover, the adhesive for temporary fixation which improved adhesiveness by the use of the specific hydrophilic (meth) acrylate, and improved peelability by swelling and some dissolution was proposed. Since the adhesive for temporary fixation generates frictional heat between components and cutting jigs such as blades and diamond cutters during cutting, it has to be carried out by cooling with a large amount of water. In the said high hydrophilic composition, since hardened | cured material swells and becomes flexible at the time of cutting, there existed a subject that higher dimensional precision could not be reached. Moreover, since the hardened | cured material melt | dissolved partly in the peeled member remains an adhesive agent, it became a visual problem (refer patent document 1, 2, 3).

Japanese Patent Laid-Open No. 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 member after cutting, it is hydrophobic, high adhesive strength, and excellent in peelability in water, and has excellent workability in the environment without adhesive residue on the member after peeling and suitable for Temporary adhesive was desired.

As a result of various studies to solve these problems of the prior art, the present invention includes applying pressure to one or both of the fixing member and the member to be processed, and simultaneously applying the pressure and irradiating the pressure at least simultaneously. By carrying out, it was found that excellent dimensional accuracy at the time of processing can be obtained and the present invention can be achieved.

That is, this invention has the following structure.

(1) Applying a temporary fixing adhesive to a fixing member (hereinafter referred to as a coating step), mounting a member to the temporary fixing adhesive (hereinafter referred to as a mounting step), and visible on the temporary fixing adhesive after the mounting Irradiating at least one of light rays or ultraviolet rays and increasing the adhesion of the fixing adhesive (hereinafter referred to as irradiation step), and applying pressure to one or both of the fixing member and the workpiece (hereinafter referred to as pressure step) A temporary fixation method comprising: a temporary fixation method comprising simultaneously applying the pressure and irradiating at least a predetermined time.

(2) Applying a temporary fixing adhesive to a member to be processed (hereinafter referred to as a coating step), mounting a fixing member to a temporary fixing adhesive (hereinafter referred to as a mounting step), and visible on the temporary fixing adhesive after the mounting A method of temporarily fixing comprising irradiating at least one of light rays or ultraviolet rays to increase the adhesive strength of the temporary fixing adhesive, and applying pressure to one or both of the fixing member and the member to be processed (hereinafter referred to as a pressure step). A temporary fixing method wherein the applying of pressure and the irradiation are carried out simultaneously for at least a certain time.

(3) The temporarily fixed method according to the above (1) or (2), wherein the pressure applied from one or both of the fixing member and the member to be processed is controlled to 1 g / cm 2 or more and 1000 kg / cm 2 or less.

(4) The temporarily fixing method according to the above (1) or (3), wherein any one or more of the fixing member, the adhesive for temporarily fixing, and the member to be processed are controlled to 0 ° C or more and 150 ° C or less.

(5) Any of the above (1) to (4), wherein the adhesive for temporary fixation is a composition containing (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C) photopolymerization initiator. The temporarily fixed method of Claim.

(6) The temporarily fixed method of the member as described in said (5) whose (A) and (B) are all hydrophobic.

(7) The temporarily fixed method as described in any one of said (1)-(6) whose glass transition temperature of the adhesive for temporarily fixed is -50 degreeC or more and 50 degrees C or less.

(8) The adhesive for temporary fixation is (A) 1-90 weight part, (B) 10-99 weight part, and total amount of (A) and (B) in 100 weight part of total amounts of (A) and (B). The temporarily fixed method in any one of said (5)-(7) containing 0.1-30 weight part of (C) with respect to 100 weight part.

(9) Said (5)-which contains 0.1-20 weight part of granular substances (D) which the adhesive for temporarily fixing does not melt | dissolve in (A)-(C) with respect to 100 weight part of total amounts of (A) and (B). The temporary fixation method in any one of (8).

The temporary fixation method as described in said (9) whose shape of the granular substance (D) which does not melt | dissolve in (10) (A)-(C) is spherical.

(11) The granular material (D) which does not dissolve in (A) to (C) is any one or a mixture of crosslinked polymethyl methacrylate particles, crosslinked polystyrene particles and crosslinked polymethacrylate methyl polystyrene copolymer particles. The temporarily fixed method as described in said (9) or (10).

(12) The temporarily fixed method in any one of said (9)-(11) whose average particle diameter of the particulate matter (D) which does not melt | dissolve in (A)-(C) is 5 micrometers-200 micrometers.

(13) The standard deviation of the particle volume distribution with respect to the particle size when the particle size (μm) according to the laser diffraction method of the particulate matter (D) that does not dissolve in (A) to (C) is displayed in logarithmic scale is 0.0001 to 0.25. The temporarily fixed method in any one of said (9)-(12) in range.

(14) After processing this temporarily fixed member using the temporary fixation method according to any one of the above (1) to (13), the processed member is immersed in warm water of 100 ° C or lower to obtain a cured product of the composition. Temporary fixation, peeling method of a member including peeling off.

(15) After processing this temporarily fixed member using the temporary fixation method described in any one of (1) to (13) above, visible or ultraviolet rays are irradiated to the temporary fixing adhesive and the processed member is 100 ° C. The temporarily fixing and peeling method of the member containing immersing in the following warm water and removing the hardened | cured material of the said composition.

(16) The temporarily fixed method according to any one of (1) to (13), wherein the amount of visible or ultraviolet radiation is in the range of 1 mJ / cm 2 to 4000 mJ / cm 2 at a wavelength of 365 nm.

(17) The temporary fixation according to (15), wherein the irradiation amount of visible or ultraviolet rays irradiated after the temporarily fixed member is in the range of 1000 mJ / cm 2 to 40000 mJ / cm 2 at a wavelength of 365 nm. Peeling method.

(18) any one of the above (5) to (13) in which the (A) polyfunctional (meth) acrylate contains a polyfunctional (meth) acrylate oligomer / polymer and / or a bifunctional (meth) acrylate monomer. Temporary fixation method described in the above.

(19) (A) The polyfunctional (meth) acrylate according to any one of the above (5) to (13), wherein the polyfunctional (meth) acrylate contains a polyfunctional (meth) acrylate oligomer / polymer and a bifunctional (meth) acrylate monomer. Temporarily fixed way.

(20) The temporary fixation according to the above (18) or (19), wherein the polyfunctional (meth) acrylate oligomer / polymer contains a polyester urethane (meth) acrylate and / or a polyether urethane (meth) acrylate. Way.

(21) The go described in (18) or (19), wherein the bifunctional (meth) acrylate monomer contains 1,6-hexanediol di (meth) acrylate and / or dicyclopentanyl di (meth) acrylate. Chung way.

(22) Said monofunctional (meth) acrylate containing phenol ethylene oxide 2 mol modified (meth) acrylate and / or 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate The temporarily fixed method in any one of (5)-(13).

(23) Said (5) in which monofunctional (meth) acrylate contains 2 moles of phenol ethylene oxide modified (meth) acrylate and 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate. The temporary fixation method in any one of)-(13).

(24) (C) photopolymerization initiator was benzyl dimethyl ketal, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydric The temporarily fixed method as described in any one of said (5)-(13) containing 1 type (s) or 2 or more types selected from the group which consists of oxy-ethoxy] -ethyl ester.

In the temporary fixation method of the present invention, a particular effect can be obtained in terms of dimensional accuracy of the member to be processed by simultaneously performing the pressure step and the irradiation step at least for a predetermined time.

In the present invention, the coating step applies the temporary fixing adhesive to the fixed member or the member to be processed. In this application | coating process, if it is a well-known application | coating process, there is no restriction | limiting in using any method, but the process of apply | coating an appropriate amount of an adhesive agent to the adhesive surface of one fixing member or a to-be-processed member to fix is preferable. The coating amount of the adhesive is preferably 0.00000001 to 0.1 mg / mm 2, more preferably 0.000001 to 0.001 mg / mm 2. The method of applying an appropriate amount is not particularly limited as long as it is a known method. For example, a method of using an applicator is simple, accurate, and preferable in terms of productivity.

In this invention, a mounting process is a process of mounting a to-be-processed member or a fixing member on the fixed member which apply | coated the temporary fixing adhesive after a coating process, or on the temporary fixing adhesive on a to-be-processed member. There is no restriction | limiting in particular if it is a well-known method in this mounting process, For example, the process of using automatic mounting apparatuses, such as an industrial robot, is preferable at the point which is simple, accurate, and productivity improves.

In the temporarily fixing method of this invention, the fluidity | liquidity of the adhesive for temporarily fixing can be controlled by controlling and implementing any one or more of a fixing member, the adhesive for temporarily fixing, and a to-be-processed member to 0 degreeC or more and 150 degrees C or less. If the fixing member, the temporary fixing adhesive and the member to be processed are 0 ° C or higher, the fluidity is excellent, and if it is 150 ° C or lower, the temporary curing adhesive is not polymerized by thermosetting and excellent in dimensional accuracy. From a viewpoint of fluidity and dimensional accuracy, Preferably they are 10 degreeC or more and 100 degrees C or less, More preferably, they are 20 degreeC or more and 80 degrees C or less. Even more preferably, they are 20 degreeC or more and 60 degrees C or less.

The pressure step of the present invention is preferably a step of applying pressure on one or both of the stationary member and the workpiece, and more preferably a step of applying pressure on one or both sides so as to equalize the distance between the stationary member and the workpiece. Although there is no restriction | limiting in particular if it is a well-known method in this pressure process, For example, the method of pressurizing using a vacuum press machine or a pressure press machine is preferable.

Uniformity in this invention means that the difference which subtracted the smallest place from the largest space | interval of a fixing member and a to-be-processed member exists in the range of 40 micrometers or less. If it exists in this range, favorable dimensional accuracy can be acquired when processing a to-be-processed member. From the point of view of dimensional accuracy, it is preferable that the difference obtained by subtracting the smallest part from the largest gap between the fixing member and the workpiece is within the range of 20 µm or less, and more preferably within the range of 10 µm or less, further preferably 5 µm. It is still more preferable if it exists in the following ranges.

Moreover, in the pressure process of this invention, it is preferable to apply and apply the pressure of 1 g / cm <2> or more and 1000 kg / cm <2> or less in one or both of a fixing member and a to-be-processed member. If the distance between the fixed member and the workpiece is uniform, there is no problem even if the pressure is applied locally to the fixed member and the workpiece, but it is preferable to apply pressure across the entire surface in view of the distance between the fixed member and the workpiece. When the pressure to be applied is 1 g / cm 2 or more, the interval between the fixing member and the workpiece can be made uniform, and if it is 1000 kg / cm 2 or less, no damage is caused to the fixing member or the workpiece. 3 g / cm <2> or more and 800 kg / cm <2> or less are preferable from a viewpoint of the uniformity and damage of the space | interval of a fixed member and a to-be-processed member, More preferably, it is more preferable if it is 5 g / cm <2> or more and 500 kg / cm <2> or less, It is still more preferable if it is more than 300 kg / cm <2> or more.

Moreover, this invention requires the irradiation process which irradiates at least one of visible light or an ultraviolet-ray to the temporarily fixing adhesive agent and raises the adhesive force of the temporarily fixing adhesive agent. The lamp used in the irradiation step or the re-irradiation step to be described later is not particularly limited as long as it improves the adhesive strength of the temporary fixing adhesive. desirable. 10-430 nm is preferable, as for the wavelength of an ultraviolet-ray, 200-420 nm is more preferable, and 330-405 nm is the most preferable.

In the irradiation process of this invention, it is preferable that irradiation amount of visible light or an ultraviolet-ray is 1 mJ / cm <2> -4000 mJ / cm <2> in wavelength 365nm. If it exists in this range, favorable dimensional accuracy can be acquired when processing a to-be-processed member. It is preferable to exist in the range of 10 mJ / cm <2> -3000 mJ / cm <2> from a viewpoint of dimensional accuracy, and it is still more preferable if it exists in the range of 100 mJ / cm <2> -2000 mJ / cm <2>, It is still more preferable if it exists in the range.

In this invention, it is preferable to perform an irradiation process at least simultaneously for a predetermined time during a pressure process. By carrying out the irradiation step simultaneously for at least a certain time during the pressure step, the interval between the fixed member and the member to be processed becomes uniform, and a special effect can be obtained in terms of dimensional accuracy during processing of the member. The processing here means, for example, cutting, grinding, polishing, drilling, etc., into a desired shape of the member to be processed. The fixed time herein is not particularly limited as long as the curing time is included. It is preferable to perform a pressure process and an irradiation process simultaneously after performing a pressure process previously, in the point which can make the space | interval of a fixed member and a to-be-processed member uniform.

Although there is no restriction | limiting in particular in the material of a to-be-processed member and a fixing member in this invention, The member which consists of a material which can permeate | transmit an ultraviolet-ray or a visible ray is preferable. As such a material, a correction member, a glass member, a plastic member, etc. are mentioned.

As the (A) polyfunctional (meth) acrylate used in the present invention, two or more (meth) acryloylated polyfunctional (meth) acrylate oligomers / polymers or two or more (meth) acrylonitrile / polymer terminal or side chains are used. ) A monomer having acryloyl group can be used.

As a polyfunctional (meth) acrylate oligomer / polymer, a 1, 2- polybutadiene terminal urethane (meth) acrylate (for example, "TE-2000" and "TEA-1000" by the Japan procurement company), the said hydrogenated substance (example For example, "TEAI-1000" manufactured by Nippon Procurement Co., Ltd., 1,4-polybutadiene-terminated urethane (meth) acrylate (for example, "BAC-45" by Osaka Organic Chemical Co., Ltd.), polyisoprene terminal (meth) acrylate, poly Ester-based urethane (meth) acrylate (for example, "UV-2000B", "UV-3000B", "UV-7000B" made by Nippon Synthetic Co., Ltd. "KHP-11", "KHP-17" by Negami Kogyo Co., Ltd.), Polyether urethane (meth) acrylate (For example, "UV-3700B", "UV-6100B" by the Japan synthesis company), bis-A type epoxy (meth) acrylate, etc. are mentioned. In these, polyester urethane (meth) acrylate and / or polyether urethane (meth) acrylate are preferable at the point which has a big effect, and polyester urethane (meth) acrylate is more preferable.

10000-60000 are preferable and, as for the weight average molecular weight of a polyfunctional (meth) acrylate oligomer / polymer, 13000-40000 are more preferable. The weight average molecular weight was created by using a GPC system (SC-8010 manufactured by Tosoh Corporation) and the like using a standard polystyrene commercially available.

As the bifunctional (meth) acrylate monomer, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, neopentylglycol 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) acryloxy diethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy propoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy tetraethoxyphenyl) propane, 2- (1,2-cyclohexacarboxyimide ) Ethyl acrylate, hexanediol diacrylate, etc. are mentioned. Among these, 1,6-hexanediol di (meth) acrylate and / or dicyclopentanyl di (meth) acrylate are preferable at these points, and dicyclopentanyl di (meth) acrylate is more preferable.

Trimethylolpropane tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, etc. are mentioned as a trifunctional (meth) acrylate monomer.

As a (meth) acrylate monomer more than tetrafunctional, dimethylol propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

(A) It is more preferable that polyfunctional (meth) acrylate is hydrophobic. The hydrophobic term herein refers to a property that is difficult to dissolve in water or a property that is difficult to mix with water. Hydrophobic polyfunctional (meth) acrylate is, for example, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylic Laterate, 1,9-nonanediol di (meth) acrylate, neopentylglycol 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) acryloxy diethoxyphenyl ) Propane, 2,2-bis (4- (meth) acryloxy propoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy tetraethoxyphenyl) propane, 2- (1,2-cyclo Hexacarboxyimide) ethyl acrylate, hexanediol diacrylate, etc. are mentioned. Trimethylolpropane tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, etc. are mentioned as a hydrophobic trifunctional (meth) acrylate monomer. As the hydrophobic tetrafunctional or higher (meth) acrylate monomer, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. In the case of water solubility, since the hardened | cured material of a resin composition swells at the time of cutting, it is unpreferable since there exists a possibility that a position shift may occur and the dimensional precision at the time of processing may be inferior. Even if it is hydrophilic, you may use as long as the hardened | cured material of the composition does not have a big swelling or partial dissolution by water.

Among polyfunctional (meth) acrylates, it is preferable to contain a polyfunctional (meth) acrylate oligomer / polymer and / or a bifunctional (meth) acrylate monomer from the point that the effect is large, and a polyfunctional (meth) acrylate oligomer It is more preferable to use a polymer together with a bifunctional (meth) acrylate monomer.

The content ratio when using a polyfunctional (meth) acrylate oligomer / polymer and a bifunctional (meth) acrylate monomer together is 100 weight in total of a polyfunctional (meth) acrylate oligomer / polymer and a bifunctional (meth) acrylate monomer. Polyfunctional (meth) acrylate oligomer / polymer: bifunctional (meth) acrylate monomer = 30-95: 5-70 are preferable at a weight ratio by weight, 40-90: 60-10 are more preferable, 60-80 : 40-20 are the most preferable.

(A) 1-90 weight part is preferable in 100 weight part of total amounts of (A) and (B), and, as for the usage-amount of polyfunctional (meth) acrylate, 30-85 weight part is more preferable. When it is 1 weight part or more, when the hardened | cured material of a composition is immersed in warm water, the property (henceforth simply referred to as "peelability") which the hardened | cured material peels from a to-be-adhered body is fully encouraged, and it can ensure that the hardened | cured material of a composition peels in a film form. Can be. Moreover, if it is 90 weight part or less, there is no possibility that initial stage adhesiveness may fall.

As the monofunctional (meth) acrylate (B), a monofunctional (meth) acrylate monomer can be used. Monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (Meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobonyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylic , 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl ( Meta) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth Acrylate, phenol ethylene oxide modified acrylate, phenol (ethylene oxide 2 mole modified) acrylate, phenol (ethylene oxide 4 mole modified) acrylate, paracumylphenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, Nonylphenol (4 moles of ethylene oxide) acrylate, nonylphenol (8 moles of ethylene oxide) acrylate, nonyl phenol (2.5 moles of propylene oxide) acrylate, 2- Ethylhexylcarbitol 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 monohydroxyethyl (meth) acrylate, (meth) acrylic acid dimer, β- (meth) acryloyloxy ethyl hydrogen succinate, n- (meth) Acryloyloxy alkyl hexahydrophthalimide, 2- (1, 2- cyclohexacarboxyimide) ethyl acrylate, etc. are mentioned.

As for (B) monofunctional (meth) acrylate, it is more preferable that it is hydrophobic like (A). Hydrophobicity here means the property which is hard to melt | dissolve in water, or the property which is hard to mix with water. Hydrophobic monofunctional (meth) acrylate is 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, dicyclopentenyloxyethyl (meth) acrylate, isobonyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, 3-cle Rho-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate Ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified acrylate, phenol (ethylene oxide 2 mole modified) acrylate, phenol (ethylene oxide 4 mole modified) acrylate, paracumylphenol ethylene oxide modified acrylate, Nonylphenol ethylene oxide modified acrylate, nonylphenol (4 mol modified ethylene oxide) acrylate, nonylphenol (8 mol modified ethylene oxide) acrylate, nonylphenol (2.5 mol modified propylene oxide) acrylate, 2-ethylhexylcarbitol Acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, trifluoro Tyl (meth) acrylate, ω-carboxy polycaprolactone mono (meth) acrylate, phthalic acid monohydroxyethyl (meth) acrylate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate Nate, n- (meth) acryloyloxy alkyl hexahydrophthalimide, 2- (1, 2- cyclohexacarboxyimide) ethyl acrylate, etc. are mentioned. In the case of water solubility, since the hardened | cured material of a resin composition swells at the time of cutting, it may cause a position shift and inferior processing precision, and it is unpreferable. Moreover, even if it is hydrophilic, you may use as long as the hardened | cured material of this resin composition does not swell or partially melt | dissolve by water.

Among monofunctional (meth) acrylates, the one containing phenol ethylene oxide 2 mole modified (meth) acrylate and / or 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate in terms of high effect It is more preferable to use together 2 mole phenol ethylene oxide modified (meth) acrylate and 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate. When the phenol ethylene oxide 2-mol modified (meth) acrylate and 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate are used together, the content ratio is phenol ethylene oxide 2-mol modified (meth) acrylate and 2- (1,2-cyclohexacarboxyimide) 2- (1,2-cyclohexacarboxyimide) phenol ethylene oxide 2 mole modified (meth) acrylate in a weight ratio of 100 parts by weight of the total of 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate Ethyl (meth) acrylate = 30-90: 10-70 are preferable, 40-80: 20-60 are more preferable, 50-70: 30-50 are the most preferable.

(B) 10-99 weight part is preferable in the total amount of 100 weight part of (A) and (B), and, as for the usage-amount of monofunctional (meth) acrylate, 15-70 weight part is more preferable. If it is 10 weight part or more, there is no possibility that initial stage adhesiveness may fall, and if it is 99 weight part or less, peelability can be ensured and the hardened | cured material of a composition will peel in a film form.

Moreover, (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, and dioctyl 2- (meth) acryloyl are added to the compound composition of said (A) and (B). By using together phosphate ester which has vinyl group or (meth) acrylic group, such as oxyethyl phosphate, diphenyl 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl polyethyleneglycol acid phosphate, The adhesiveness can be further improved.

(C) A photoinitiator is mix | blended in order to increase and decrease with visible light or the active light of an ultraviolet-ray, and to promote photocuring of a resin composition, and various well-known photoinitiators can be used. Examples of the photopolymerization initiator include benzophenone and its derivatives, benzyl and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether and benzyl dimethyl ketal. Acetophenone derivatives such as benzoin derivatives, diethoxyacetophenone, 4-t-butyl trichloroacetophenone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and derivatives thereof , Camphorquinone, 7,7-dimethyl-2,3-dioxo bicyclo [2.2.1] heptan-1-carboxylic acid, 7,7-dimethyl-2,3-dioxo bicyclo [2.2.1] heptane- 1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxo bicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3 Camphorquinone derivatives such as dioxobicyclo [2.2.1] heptan-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinop Α-aminoalkylphenone derivatives such as ropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoyl diphenyl phosphine oxide, 2,4, Acyl phos such as 6-trimethyl benzoyl diphenyl phosphine oxide, benzoyl diethoxy phosphine oxide, 2,4,6-trimethylbenzoyl dimethoxy phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diethoxy phenyl phosphine oxide Fin oxide derivatives, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and / or oxy-phenyl acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester Etc. can be mentioned. A photoinitiator can be used 1 type or in combination of 2 or more types. Among these, 1 benzyl dimethyl ketal, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl acetic acid 2- [2-hydroxy in terms of the effect thereof are great. 1 or 2 or more types selected from the group consisting of -ethoxy] -ethyl ester are preferable.

As for the usage-amount of (C) photoinitiator, 0.1-30 weight part is preferable with respect to a total of 100 weight part of (A) and (B). 0.5-25 weight part is more preferable. If it is 0.1 weight part or more, hardening acceleration effect can be acquired reliably, and a sufficient hardening rate can be obtained at 25 weight part or less. By using 1 weight part or more of (C) component as a more preferable aspect, it becomes possible to harden | cure irrespective of the light irradiation amount, Furthermore, the crosslinking density of the hardened | cured material of a composition becomes high, and the position which does not produce a position shift etc. at the time of cutting processing, and peelability improves the surface More preferred.

In this invention, it is preferable that the glass transition temperature of the hardened | cured material obtained from the adhesive for temporarily fixing exists in the range of -50 degreeC-50 degreeC. When the glass transition temperature of the hardened | cured material obtained from the said temporarily fixing adhesive exists in this range, when the member is temporarily fixed and adhesively fixed, and this processed member is immersed in warm water below 100 degreeC after processing this temporarily fixed member, the hardened | cured material of the temporarily fixing adhesive itself Large thermal expansion. As a result, a reduction in the adhesive area is achieved and the adhesive strength is lowered, so that only the member can be easily recovered. When the glass transition temperature of the hardened | cured material obtained from the adhesive for temporarily fixing is -50 degreeC or more, a shift | offset | difference hardly arises at the time of the process of the temporarily fixed member, and it is excellent in the aspect of dimensional precision. If it is 50 degrees C or less, it is excellent in hot water peelability. The glass transition temperature of the hardened | cured body obtained from the said adhesive agent for temporarily fixing from the surface of peelability and dimensional precision becomes like this. More preferably, it is -25 degreeC-45 degreeC, More preferably, it is -20 degreeC-42 degreeC, More preferably, Is 0 degreeC-40 degreeC.

Moreover, there is no restriction | limiting in particular in the measuring method of the glass transition temperature of the hardened | cured material obtained from the adhesive agent for temporarily fixing used by this invention, It measures by well-known methods, such as DSC and a dynamic viscoelastic spectrum. The preferred method is by dynamic viscoelastic spectrum.

In this invention, it is preferable to use the granular substance which does not melt | dissolve in (D) (A)-(C) with (A) and (B). Thereby, it becomes easy for the composition after hardening to maintain a fixed thickness, and can improve the dimensional precision at the time of processing more easily. Moreover, since the linear expansion coefficient of the hardening body of the adhesive for temporarily fixing and the granular material which does not melt | dissolve in (A)-(C) differs, it adhesive-fixes and fixes a member using the said adhesive composition, and this process after processing this temporarily fixed member When the obtained member is immersed in warm water of 100 ° C. or less, wavy or three-dimensional deformation occurs at the interface between the member and the cured product of the temporary fixing adhesive, and as a result, a reduction in the adhesion area is achieved and the peelability is further improved.

(D) As a material of the granular material which does not melt | dissolve in (A)-(C), any of the organic and inorganic particles generally used may be sufficient. Examples of the organic particles include polyethylene particles, polypropylene particles, crosslinked polymethyl methacrylate particles and crosslinked polystyrene particles. Examples of the inorganic particles include ceramic particles such as glass, silica, alumina, and titanium.

(D) It is preferable that the granular material which does not melt | dissolve in (A)-(C) is spherical from the surface of the improvement of the dimensional precision at the time of processing, ie, the film thickness control of an adhesive agent. Examples of the organic particles include a methyl methacrylate monomer, a crosslinked polymethacrylate particle obtained as a monodisperse particle by a known emulsion polymerization method of a styrene monomer and a crosslinkable monomer, a crosslinked polystyrene particle or a crosslinked polymethacrylate methyl polystyrene copolymer. Particles are preferred. As an inorganic particle, spherical silica is preferable because it has little deformation | transformation of particle | grains, and the nonuniformity of the film thickness of the composition after hardening by the nonuniformity of a particle size becomes small. Among them, crosslinked polymethacrylate particles, crosslinked polystyrene particles, crosslinked polymethyl methacrylate polystyrene copolymer particles, crosslinked polymethacrylate methyl particles, and the like in terms of storage stability due to sedimentation of particles and the reactivity of the composition. The crosslinked polystyrene particles, the crosslinked polymethyl methacrylate polystyrene copolymer particles, or a mixture thereof are more preferable. More preferred is any one or a mixture of crosslinked polymethyl methacrylate particles, crosslinked polystyrene particles, and crosslinked polymethacrylate methyl polystyrene copolymer particles.

(D) It is preferable that the average particle diameter by the laser method of the granular material which does not melt | dissolve in (A)-(C) exists in the range of 5 micrometers-200 micrometers. If the average particle diameter of the said granular material is 5 micrometers or more, it is excellent in peelability, and when it is 200 micrometers or less, a shift | offset | difference is hard to produce at the time of processing of a temporarily fixed member, and it is excellent in dimensional accuracy. The more preferable average particle diameter is 8 micrometers-150 micrometers from a viewpoint of peelability and dimensional precision, More preferably, they are 9 micrometers-120 micrometers. In addition, the standard deviation of the particle diameter and particle diameter distribution in this invention was measured with "Laser diffraction type particle size distribution measuring apparatus SALD-2200" by Shimadzu Corporation. Particle diameters are by volume.

(D) The standard deviation of the particle volume distribution with respect to the particle size when the particle size (μm) according to the laser method of the particle size of the granular material that does not dissolve in (A) to (C) is displayed in a logarithm is 0.0001 to 0.25 It is preferable to be in a range. If there is a standard deviation of the particle size of the granular material in this range, the film thickness non-uniformity of the composition after curing is reduced due to the non-uniformity of the particle size, so that no deviation occurs during processing of the temporarily fixed member, not only excellent in terms of dimensional accuracy, but also remarkably peelable. Improve. From the viewpoint of dimensional accuracy and peelability, the standard deviation of the particle size of the particulate matter is more preferably 0.0001 to 0.15, still more preferably 0.0001 to 0.1, still more preferably 0.0001 to 0.08, and remarkably preferable if it is 0.0001 to 0.072. .

(D) As for the usage-amount of the granular material which does not melt | dissolve in (A)-(C), 0.1-20 weight part is preferable with respect to 100 weight part of total amounts of (A) and (B) from the surface of adhesive strength, processing precision, and peelability. More preferably, it is 0.2-10 weight part, More preferably, it is 0.2-6 weight part.

The temporary fixing adhesive of the present invention may use a small amount of polymerization inhibitor to improve its storage stability. Polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary-butylphenol), catechol, hydroquinone monomethyl ether, monotertiary-butyl hydroquinone, 2 , 5-di-butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, ter Sherry-butyl catechol, 2-butyl-4-hydroxy anisole, 2,6-di-butyl p-cresol and the like.

0.001-3 weight part is preferable with respect to 100 weight part of total amounts of (A) and (B), and, as for the usage-amount of these polymerization inhibitors, 0.01-2 weight part is more preferable. Storage stability is ensured at 0.001 part by weight or more, good adhesion can be obtained at 3 parts by weight or less, and there is no uncuring.

In the adhesive agent for temporarily fixing of this invention, you may use a polar organic solvent together.

The adhesive for temporary fixation of the present invention is a variety of elastomers, inorganic fillers, solvents, extenders, reinforcing materials, plasticizers such as acrylic rubbers, urethane rubbers, acrylonitrile-butadiene-styrene rubbers that are generally used within the scope of not impairing the object of the present invention. You may use additives, such as a thickener, dye, a pigment, a flame retardant, a silane coupling agent, and surfactant.

This invention is the temporarily fixing and peeling method of the member which processes the member temporarily fixed by the said method using the adhesive for temporarily fixing, and removes the temporarily fixed adhesive which hardened by immersing this processed member in 100 degreeC or less warm water. According to this invention, the processing precision of various members, such as an optical member, can be made high, without using an organic solvent.

According to a preferred embodiment of the present invention, when the member to be processed is removed from the cured body of the adhesive for temporary fixation, the temporarily fixed adhesive is irradiated with visible light or ultraviolet rays to immerse the cured body of the temporary fixative adhesive in warm water at 100 ° C. or lower for curing. The time to remove the adhesive can be shortened.

In the present invention, when the member to be processed is removed from the cured body of the temporary fixing adhesive, when the irradiation amount of visible or ultraviolet rays irradiating visible or ultraviolet rays to the temporary fixing adhesive is 1000 mJ / cm 2 or more and 40000 mJ / cm 2 or less at 365 nm, The effect which can shorten the time which removes the hardening | curing agent for temporarily fixed by immersing the hardened | cured material of an adhesive agent in 100 degreeC or less hot water, and is large is preferable (reinspection process). The irradiation dose is more preferably 2000 mJ / cm 2 or more and 38000 mJ / cm 2 or less, and still more preferably 4000 mJ / cm 2 or more and 36000 mJ / cm 2 or less.

In the present invention, when hot water moderately heated, for example, hot water at 100 ° C. or lower, peelability in water can be achieved in a short time, and productivity is preferable. Preferably, when using 30 degreeC-100 degreeC, More preferably, 40-99 degreeC warm water, the residual distortion stress which generate | occur | produces when the hardened | cured material of an adhesive heat-expands and hardens a composition for a short time is released. Furthermore, since the linear expansion coefficients of the hardened | cured material of a temporarily fixing adhesive agent and a granular material differ, the member is temporarily fixed by using the said adhesive composition, and after processing this temporarily fixed member, this processed member is immersed in 100 degreeC or less warm water. When it does, wavy or three-dimensional deformation occurs at the interface between the member and the cured product of the temporary adhesive. As a result, the reduction of the adhesion area is achieved, the adhesive strength is lowered, and the cured product of the adhesive for temporary fixation can be peeled off on the film. Moreover, about the contact method of the hardened | cured material of a temporarily fixing adhesive agent, and water, the method of immersing for every joined body in water is recommended from the simple thing.

An Example and a comparative example are given to the following, and this invention is demonstrated in more detail. The present invention is not limited to these examples.

Example

(Example 1)

( Temporarily fixed  Making of glue)

The adhesive for temporary fixation was produced by the following procedure. (A) "UV-3000B" made from Japan Synthetic Co., Ltd. as polyfunctional (meth) acrylate (we abbreviate as polyester-based urethane acrylate "UV-3000B", it is hydrophobic (meth) acrylate, weight average molecular weight 15000) 30 parts by weight, dicyclopentanyl diacrylate (hereinafter referred to as "KAYARAD R-684" manufactured by Nippon Chemical Co., Ltd., hereinafter abbreviated as "R-684", hydrophobic (meth) acrylate) 15 parts by weight, (B) monofunctional ( 2- (1,2-cyclohexacarboxyimide) ethyl acrylate as a meta) acrylate ("Aronix M-140" by Toa Synthetic Co., Ltd., hereafter abbreviated as "M-140") is a hydrophobic (meth) acrylate. ) 20 parts by weight, 2 moles of phenol ethylene oxide (modified acrylate `` Aronix M-101A '', hydrophobic (meth) acrylate) 35 parts by weight, (C) benzyl dimethyl ketal (Ciba. Specialty chemicals company made `` IRGACURE 651 (Hereinafter abbreviated as "BDK") 10 parts by weight, (D) for the particle size when the average particle diameter 100 μm, particle size (μm) is displayed in logarithm as a particulate matter that does not dissolve in (A) to (C) 1 part by weight of spherical crosslinked polystyrene particles (&quot; GS-100S &quot; manufactured by Gantz Chemical Co., Ltd.) having a standard deviation of particle volume distribution of 0.063, and 2,2-methylene-bis (4-methyl-6-tert-butylphenol) as a polymerization inhibitor. ("Sumiiser MDP-S" by Sumitomo Chemical Co., Ltd., abbreviated as "MDP" hereafter.) The resin composition was produced using 0.1 weight part.

Using the obtained resin composition, the glass transition temperature, the tensile shear bond strength, and the peeling test were implemented by the evaluation method shown below. Such results are shown in Table 1. Moreover, the standard deviation of the particle volume distribution with respect to the particle size at the time of displaying the average particle diameter and particle diameter (micrometer) of the particulate matter which does not melt | dissolve in (D) (A)-(C) was also measured.

(Assessment Methods)

Glass transition temperature: The resin composition was inserted into PET film using the 1 mm-thick silicone sheet as a template. The resin composition was cured from an upper surface under a condition of an integrated light quantity of 2000 mJ / cm 2 at 365 nm wavelength by a curing apparatus made by a fusion company using an electrodeless discharge lamp, and then accumulated light quantity of 2000 mJ / cm 2 at 365 nm wavelength from below. It hardened | cured further on conditions, and the hardened | cured material of the resin composition of thickness 1mm was produced. The produced hardened | cured material was cut into length 50mm width 5mm with the cutter, and it was set as the hardened | cured material for glass transition temperature measurement. The resulting hardened body was subjected to stress and distortion in the tensile direction of 1 Hz to the hardened body in a nitrogen atmosphere by Seiko Electronics Co., Ltd., a dynamic viscoelasticity measuring device "DMS210", and the tan δ was measured while increasing in temperature at a rate of 2 ° C per minute. The temperature of the peak top of this tan-delta was made into glass transition temperature.

Tensile shear adhesive strength ("adhesive strength" in the table): Measured according to JIS K 6850. Specifically, heat-resistant glass (25 mm x 2 5 mm x thickness 2.0 mm) made of a to-be-adhered material was used, and two heat-resistant glass were pasted together with a resin composition produced by bonding an adhesive site with a diameter of 8 mm to use an electrodeless discharge lamp. It was hardened on the conditions of the integrated light quantity of 2000 mJ / cm <2> of 365 nm wavelength by the fusion apparatus by a fusion company, and the tensile shear bond strength test piece was produced. The produced test piece measured the tensile shear bond strength at the tensile speed of 10 mm / min in the environment of the temperature of 23 degreeC, and 50% of humidity using the universal testing machine.

Peeling test ("80 degreeC hot water peeling time" "peeled state" of a table): On the same conditions as the above except apply | coating a composition to the said heat-resistant glass, and sticking it to the blue plate glass (150 mm x 150 mm x thickness 1.7 mm) as a support body. The produced resin composition was hardened and the peeling test body was produced. The obtained test body was immersed in warm water (80 degreeC), the time which heat-resistant glass peeled was measured, and the peeling state was also observed.

Standard deviation of the particle volume distribution with respect to the particle size when the average particle diameter and the particle diameter (μm) of the granular material are displayed in logarithms (the standard of the particle size of the granular material which does not dissolve in "(A), (B), (C) in the table) Deviation "): It measured by the laser diffraction type particle size distribution measuring apparatus (" SALD-2200 "by Shimadzu Corporation).

( Temporarily fixed Peeling method)

The blue plate glass (150 mm x 150 mm x thickness 1.7 mm) which is a fixing member was heated at 80 degreeC on the hotplate, and 1g of the produced temporarily fixing adhesives were apply | coated (coating process). Then, the blue plate glass (80 mm x 80 mm x thickness 1.1 mm) which is a to-be-processed member was mounted from the upper side (mounting process). Next, a 50 mm-thick quartz glass (80 mm x 80 mm x thickness 5 mm) was mounted on the blue plate glass, which is the member to be processed, from above, and a load was applied from above the quartz glass to add 12.5 g of the total weight and weight of the quartz glass. The pressure of / cm <2> was added and it left to stand for 5 minutes (pressure process). The distance between the stationary member and the member to be processed was 5 µm or less in the difference minus the smallest.

Subsequently, 300 mJ / cm <2> of UV light of 365 nm wavelength was irradiated using black light from the blue plate glass which is a fixed member, applying the pressure of 12.5 g / cm <2> (irradiation process was performed simultaneously with a pressure process (30 second)). . Only the blue plate glass which is a to-be-processed member of the obtained adhesive test body was cut | disconnected in 10 mm square using the dicing apparatus. Dropping of the blue plate glass which is a member to be processed during cutting did not occur, and showed good workability. The adhesive test piece cut only the blue plate glass, which is a member, was irradiated with 16000 mJ / cm2 of UV light having a wavelength of 365 nm using a metal halide lamp (re-irradiation step (for 40 seconds)) and then immersed in warm water at 80 ° C. Peeling (hot water peeling time). Moreover, ten peeled cutting specimens were arbitrarily taken out, and each side of the back surface (surface temporarily fixed with the adhesive for temporary fixation) of the said cutting specimen was observed using the optical microscope, and the maximum width of the glass defect is measured and the The mean and standard deviation were obtained. Moreover, since the hardened | cured material film of the temporarily fixing adhesive agent can be obtained from the cut test piece of the temporarily fixing adhesive agent peeled off, ten peeled cutting test pieces which peeled off arbitrarily are taken out, and the film thickness of the said hardened | cured material is measured by a micro gauge, and the average value and standard Deviation was obtained. In Table 1, the average value and standard deviation of the maximum width of the location where the glass of each side was flawed, and the average value of the film thickness of the hardened | cured material of the adhesive agent for temporarily fixing, and the measurement result of the standard deviation were shown in Table 1.

(Examples 2-7, Comparative Examples 1 and 2)

Except having performed the temporarily fixing and peeling method on the conditions shown to Tables 1-2, and 4, the hardened | cured material film of the average value and standard deviation of the maximum width of the location where the glass of each edge | side is defective, and the adhesive for temporarily fixing The average value and standard deviation of the film thicknesses were measured. The measurement result was shown to Tables 1-2 and 4.

(Examples 8-11)

Except having used the raw material of the kind shown in Tables 2 and 3 by the composition shown in Tables 2 and 3, it carried out similarly to Example 1, the average value of the width | variety of the location where the glass of each side is flawed, the standard deviation, and the diameter of the adhesive for temporarily fixing The average value and standard deviation of the cargo film film thickness were measured. The measurement results are shown in Tables 2 and 3.

(Example 12)

(D) Spherical crosslinked polymethyl meta with a standard deviation of 0.086 in the particle volume distribution with respect to the particle size when the average particle diameter and the particle size (μm) are displayed in logarithm as a granular material which does not dissolve in (A) to (C). Except using the raw material of the kind shown in Table 3 using the acrylate particle | grains ("GM-5003 by Gantz Chemical Co., Ltd. was sifted using the sieve of 150 micrometers of graduation | interval and 125 micrometers) using the composition shown in Table 3 In the same manner as in Example 1, an adhesive for temporarily fixing was produced. About the obtained adhesive for temporarily fixing, glass transition temperature, the tensile shear bond strength, and the peeling test were implemented similarly to Example 1. Moreover, the standard deviation of the particle volume distribution with respect to the particle size at the time of displaying the average particle diameter and particle diameter (micrometer) of the particulate matter which does not melt | dissolve in (D) (A)-(C) was also measured. Such results are shown in Table 3.

Except having performed the temporarily fixing and peeling method using the adhesive agent for temporarily fixing on the conditions shown in Table 3, it carried out similarly to Example 1, and the average value and standard deviation of the maximum width of the location where the glass of each edge | side is defective, and the adhesive agent for temporarily fixing The average value and standard deviation of the cured film thickness of the film were measured. The measurement results are shown in Table 3.

(Example 13)

(D) Spherical crosslinked polystyrene particles having a standard deviation of 0.062 of the particle volume distribution with respect to the particle size when the average particle diameter is 40 μm and the particle size (μm) is displayed in logarithm as a granular material that does not dissolve in (A) to (C) ( Using the Sekisui Chemical Co., Ltd. "GS-240"), the adhesive for temporary fixation was produced like Example 1 except having used the raw material of the kind shown in Table 3 by the composition shown in Table 3. About the obtained adhesive for temporarily fixing, glass transition temperature, the tensile shear bond strength, and the peeling test were implemented similarly to Example 1. Moreover, the standard deviation of the particle volume distribution with respect to the particle size at the time of displaying the average particle diameter and particle diameter (micrometer) of the particulate matter which does not melt | dissolve in (D) (A)-(C) was also measured. Such results are shown in Table 3.

Except having performed the temporary fixation and peeling method using the adhesive agent for temporarily fixing on the conditions shown in Table 3, it carried out similarly to Example 1, and the average value and the standard deviation of the maximum width of the location where the glass of each edge | side is defective, and the adhesive for temporarily fixing adhesive The average value and standard deviation of the cured product film thickness were measured. The measurement results are shown in Table 3.

(Example 14)

(D) Spherical crosslinked polystyrene particles having a standard deviation of 0.061 in the particle volume distribution with respect to the particle size when the average particle diameter is 20 μm and the particle size (μm) is displayed in logarithm as a granular material that does not dissolve in (A) to (C) ( Using the Sekisui Chemical Co., Ltd. "GS-220"), the adhesive for temporarily fixing was produced like Example 1 except having used the raw material of the kind shown in Table 3 by the composition shown in Table 3. About the obtained adhesive for temporarily fixing, glass transition temperature, the tensile shear bond strength, and the peeling test were implemented similarly to Example 1. Moreover, the standard deviation of the particle volume distribution with respect to the particle size at the time of displaying the average particle diameter and particle diameter (micrometer) of the particulate matter which does not melt | dissolve in (D) (A)-(C) was also measured. Such results are shown in Table 3.

Except having performed the temporary fixation and peeling method using the adhesive agent for temporarily fixing on the conditions shown in Table 3, it carried out similarly to Example 1, and the average value and the standard deviation of the maximum width of the location where the glass of each edge | side is defective, and the adhesive for temporarily fixing adhesive The average value and standard deviation of the cured product film thickness were measured. The measurement results are shown in Table 3.

(Example 15)

(D) Spherical crosslinked polystyrene particles having a standard deviation of 0.058 of the particle volume distribution with respect to the particle size when the average particle diameter and the particle size (μm) are expressed in logarithm as a particulate material that does not dissolve in (A) to (C) ( Using the Sekisui Chemical Co., Ltd. "SP-210"), the adhesive for temporary fixation was produced like Example 1 except having used the raw material of the kind shown in Table 3 by the composition shown in Table 3. About the obtained adhesive for temporarily fixing, glass transition temperature, the tensile shear bond strength, and the peeling test were implemented similarly to Example 1. Moreover, the standard deviation of the particle volume distribution with respect to the particle size at the time of displaying the average particle diameter and particle diameter (micrometer) of the particulate matter which does not melt | dissolve in (D) (A)-(C) was also measured. Such results are shown in Table 3.

Except having performed the temporary fixation and peeling method using the adhesive agent for temporarily fixing on the conditions shown in Table 3, it carried out similarly to Example 1, and the average value and the standard deviation of the maximum width of the location where the glass of each edge | side is defective, and the adhesive for temporarily fixing adhesive The average value and standard deviation of the cured product film thickness were measured. The measurement results are shown in Table 3.

(Material used)

UV-3700B: Polyether urethane acrylate ("UV-3700B" by the Japan synthesis chemical company), hydrophobic (meth) acrylate, weight average molecular weight 38000

1.6-X-A: Hexanediol diacrylate ("light acrylate 1.6-HX-A" by Kyoisha Chemical Co., Ltd.), hydrophobic (meth) acrylate

I-754: Oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester Mixture ("IRGACURE 754" made by Chiba Japan)

The present invention includes a pressure step of applying a pressure of 1 g / cm 2 or more and 1000 kg / cm 2 or less on one or both sides so as to equalize the distance between the fixing member and the work piece, and processing by simultaneously performing the pressure step and the irradiation step. Excellent dimensional accuracy can be obtained at the time.

In the present invention, by using a specific hydrophobic (meth) acrylic monomer and by using an adhesive for temporary fixation of a specific composition in combination thereof, the cured product can exhibit high adhesive strength without being affected by cutting water, etc. This difficult to occur and more excellent workpiece in terms of dimensional accuracy is easily obtained. The present invention reduces the adhesive strength by immersing the fixing member and the work member in hot water after processing, thereby lowering the adhesive strength between the fixing member and the work member, thereby easily recovering the work member.

The present invention has photocurability due to the composition of the temporary fixing adhesive and cures with visible or ultraviolet rays. For this reason, compared with the conventional hot melt adhesive, the remarkable effect can be acquired in terms of energy saving, energy saving, and work shortening.

The present invention can obtain a particular effect in terms of dimensional accuracy of a member to be processed by performing an irradiation step during the pressure step. That is, it becomes easy to control the thickness of the adhesive for temporarily fixing by performing an irradiation process during a pressure process.

According to the present invention, more preferable dimensional accuracy can be obtained by using an adhesive for temporary fixation containing particulate matter having a small standard deviation of the particle volume distribution.

In particular, the cured product temporarily fixed by the present invention lowers the adhesive strength by contacting hot water at 100 ° C. or lower to lower the adhesive strength between the members or between the members and the jig, and thus the member can be easily recovered. For this reason, compared with the case of the conventional temporarily fixed adhesive for temporary fixation, the special effect that it does not need to use the organic solvent which is expensive, has a strong ignition, or produces the gas which is harmful to a human body can be acquired.

In the adhesive agent for temporarily fixing of the specific preferable composition range of this invention, since hardened | cured material contacts with 100 degreeC or less hot water, and can collect | recover from a member in film form, the effect that it is excellent in workability can be acquired.

Although this invention was demonstrated in detail or with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (Japanese Patent Application No. 2008-188295) of an application on July 22, 2008, The content is taken in here as a reference.

Industrial availability

The temporary fixation method of the present invention is industrially useful as an adhesive for temporary fixation of optical lenses, prisms, arrays, silicon wafers, semiconductor mounting components and the like.

Claims (24)

Applying the adhesive for temporary fixing to the fixing member, mounting the workpiece to the temporary fixing adhesive, and irradiating at least one of visible or ultraviolet rays to the temporary fixing adhesive after the mounting to increase the adhesive strength of the temporary fixing adhesive, A temporary fixation method comprising applying pressure to one or both of a stationary member and a workpiece, wherein the temporary fixation method simultaneously performs the application of the pressure and the irradiation at least for a predetermined time. Applying the adhesive for temporarily fixing to the member to be processed, mounting the fixing member to the adhesive for temporarily fixing, irradiating at least one of visible light or ultraviolet rays to the temporarily fixing adhesive after the mounting, and increasing the adhesive strength of the temporarily fixing adhesive, A temporary fixation method comprising applying pressure to one or both of a stationary member and a workpiece, wherein the temporary fixation method simultaneously performs the application of the pressure and the irradiation at least for a predetermined time. The method according to claim 1 or 2,
The temporarily fixed method of controlling the pressure exerted from one or both of a fixing member and a to-be-processed member to 1 g / cm <2> or more and 1000 kg / cm <2> or less. The method according to any one of claims 1 to 3,
The temporary fixing method of controlling any one or more of a fixing member, the adhesive for temporarily fixing, and a to-be-processed member to 0 degreeC or more and 150 degrees C or less. The method according to any one of claims 1 to 4,
The temporary fixing method in which the adhesive agent for temporarily fixing is a composition containing (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C) photoinitiator. The method according to claim 5,
The method of temporarily fixing in the absence of which both (A) and (B) are hydrophobic. The method according to any one of claims 1 to 6,
The glass transition temperature of the adhesive for temporarily fixing is -50 degreeC or more and 50 degrees C or less. The method according to any one of claims 5 to 7,
The adhesive for temporary fixation is 1 to 90 parts by weight of (A), 10 to 99 parts by weight of (B) and 100 parts by weight of the total amount of (A) and (B) in 100 parts by weight of the total amount of (A) and (B). The temporary fixing method containing 0.1-30 weight part of (C) with respect to. The method according to any one of claims 5 to 8,
The temporary fixation method which contains 0.1-20 weight part of granular substances (D) which an adhesive for temporarily fixing does not melt | dissolve in (A)-(C) with respect to 100 weight part of total amounts of (A) and (B). The method according to claim 9,
The temporarily fixed method in which the shape of the granular substance (D) which does not melt | dissolve in (A)-(C) is spherical. The method according to claim 9 or 10,
The granular material (D) which does not melt | dissolve in (A)-(C) is any one or a mixture of crosslinked polymethyl methacrylate particle, crosslinked polystyrene particle, and crosslinked polymethacrylate methyl polystyrene copolymer particle, or a mixture thereof. . The method according to any one of claims 9 to 11,
The temporary fixation method of 5 micrometers-200 micrometers in average particle diameter of the particulate matter (D) which does not melt | dissolve in (A)-(C). The method according to any one of claims 9 to 12,
The standard deviation of the particle volume distribution with respect to the particle size when the particle size (μm) according to the laser diffraction method of the particulate matter (D) which does not dissolve in (A) to (C) is displayed in logarithmic range is in the range of 0.0001 to 0.25. Temporarily fixed way. After processing this temporarily fixed member using the temporarily fixing method of any one of Claims 1-13, the member which includes immersing this processed member in 100 degreeC or less hot water, and removing the hardened | cured material of the said composition. Temporary fixation, peeling method. After processing this temporarily fixed member using the temporarily fixed method of any one of Claims 1-13, visible light or an ultraviolet-ray is irradiated to the adhesive for temporarily fixing, and this processed member is immersed in warm water of 100 degrees C or less, The temporarily fixing and peeling method of the member containing removing the hardened | cured material of the said composition. The method according to any one of claims 1 to 13,
A temporary fixation method in which the amount of visible or ultraviolet radiation is in the range of 1 mJ / cm 2 to 4000 mJ / cm 2 at a wavelength of 365 nm. The method according to claim 15,
The irradiation amount of visible or ultraviolet-ray which irradiates the said temporarily fixed member after a process is 1000 mJ / cm <2> -40000 mJ / cm <2> in wavelength 365nm, The temporarily fixing and peeling method characterized by the above-mentioned. The method according to any one of claims 5 to 13,
(A) The temporarily fixed method in which a polyfunctional (meth) acrylate contains a polyfunctional (meth) acrylate oligomer / polymer and / or a bifunctional (meth) acrylate monomer. The method according to any one of claims 5 to 13,
(A) The temporary fixing method in which a polyfunctional (meth) acrylate contains a polyfunctional (meth) acrylate oligomer / polymer and a bifunctional (meth) acrylate monomer. The method according to claim 18 or 19,
The temporary fixing method in which a polyfunctional (meth) acrylate oligomer / polymer contains polyester urethane (meth) acrylate and / or polyether urethane (meth) acrylate. The method according to claim 18 or 19,
The temporary fixation method in which a bifunctional (meth) acrylate monomer contains 1, 6- hexanediol di (meth) acrylate and / or dicyclopentanyl di (meth) acrylate. The method according to any one of claims 5 to 13,
(B) The temporary fixation method in which a monofunctional (meth) acrylate contains 2 mol of phenol ethylene oxide modified (meth) acrylates and / or 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate. The method according to any one of claims 5 to 13,
(B) The temporary fixation method in which a monofunctional (meth) acrylate contains 2 moles of phenol ethylene oxide modified (meth) acrylate and 2- (1,2-cyclohexacarboxyimide) ethyl (meth) acrylate. The method according to any one of claims 5 to 13,
(C) the photopolymerization initiator was added to benzyl dimethyl ketal, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy- A methoxy] -ethyl ester containing one or two or more selected from the group consisting of.