JP2001226641A - Adhesive composition for temporary fixation and method of using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for temporary fixation which is excellent in penetrability and therefore can perform adhesion by infiltrating into a gap between/among stacked workpieces, excellent in dimensional accuracy in alignment, having sufficient adhesiveness to endure machining after temporary fixation and also rapidly peelable without causing a defect by being soaked in a releasing liquid composed of comparatively low temperature water or a mixed liquid of water with a water-soluble organic solvent, and to provide a method of using the composition. SOLUTION: This adhesive composition for temporary fixation features comprising the following ingredients: (1) at least one kind of hydrophilic vinyl monomers selected from the group consisting of N,N-dimethylacrylamide, N- vinylcaprolactam, acryloyl morpholine, 2-hydroxyethyl (meth)acrylate, 2- hydroxypropyl (meth)acrylate and glycerol (meth)acrylate; (2) at least one kind of polyalkylene oxide mono(meth)acrylates represented by structural formula (I) (wherein R1, R2 and R3 are each H or CH3; and n is an integer of 4 to 8); and (3) a radical polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-performance temporary fixing adhesive which is excellent in workability and processing accuracy and uses water or an aqueous solution obtained by mixing water and a water-soluble organic solvent as a peeling liquid in a peeling step after machining. The present invention relates to an agent composition and a method for processing a part using the temporary fixing adhesive composition. More specifically, the present invention significantly improves environmental protection and work safety by eliminating harmful substances accompanied by environmental pollution from a machining process involving temporary fixing of parts, and greatly improves operability.
The present invention relates to a temporary fixing adhesive composition for improving processing accuracy and productivity and the above-mentioned stripping solution, and a method for processing a part using the temporary fixing adhesive composition and a stripping solution. The present invention also provides the above-mentioned adhesive composition for temporary fixing, and at least one selected from the group consisting of water or an alcohol-based, ketone-based, polyhydric alcohol-based, nitrogen compound-based, and sulfur compound-based water-soluble organic solvent. The present invention relates to a temporary adhesive kit including a stripping solution containing an aqueous solution obtained by mixing one type of water-soluble organic solvent and water.

[0002]

2. Description of the Related Art Quartz crystal, quartz, optical glass, ceramics, stainless steel, ferrite, aluminum, etc., vibrators, lenses, prisms, capacitors, package parts,
Hot melt adhesives such as wax and pine tar have been used for temporary fixing of workpieces (workpieces) during cutting and polishing of various precision parts such as magnets. However, this type of hot melt adhesive requires work at a high temperature of about 150 ° C. at the time of bonding and desorption, and further requires further washing with an alkaline solvent or a halogen-based organic solvent. For this reason, the temporary fixing operation and the peeling operation require skill and are not only dangerous, but also lead to deterioration of the working environment and environmental pollution.

Various publications have been disclosed in order to solve the above-mentioned drawbacks. JP-A-61-287976 discloses that (A) has a polymerizable ethylenic double bond at the terminal, and the main chain has? (CH
₂ -CH ₂ -O) n- (where n is an integer of 9 to 25) a prepolymer containing polyethylene oxide; (B) a water-soluble polymer having at least one polymerizable ethylenic double bond. A composition comprising a monomer and (C) a polymerization initiator is disclosed. This (A) is a urethane prepolymer having a polymerizable ethylenic double bond at the terminal and containing polyethylene oxide in the main chain. The urethane prepolymer is specifically a prepolymer obtained by reacting a polyurethane polymer obtained by reacting an organic mono- or polyhydric alcohol having a polyethylene oxide bond and an isocyanate group with a (meth) acrylate monomer having an active hydrogen. It is a polymer.

JP-A-2-140279 discloses a temporary fixing adhesive composition comprising a water-absorbing monomer having an ethylenic double bond and a photopolymerization initiator. JP-A-2-142874
In the publication, (A) a water-absorbing monomer having at least one polymerizable ethylenic double bond in the molecule, (B) a water-absorbing or water-soluble polymer substance, (C) temporary fixing using a photopolymerization initiator An adhesive composition is disclosed.

Japanese Patent Application Laid-Open No. 2-147678 discloses an adhesive composition for temporary fixing using (A) a water-absorbing monomer having at least one polymerizable ethylenic double bond in a molecule, and (B) a redox initiator. Articles and methods of using the same are disclosed.

JP-A-6-116534 discloses a resin composition containing a (meth) acrylamide resin component having a water-soluble heterocyclic secondary amine residue, a photopolymerization initiator, and, if necessary, water. An ultraviolet-polymerizable adhesive composition for temporary fixing, in which the cured adhesive is soluble in water, is disclosed. JP-A-6-116535 discloses a methyl chloride salt of N, N-dimethylaminoethyl methacrylate. An adhesive composition using a quaternary ammonium salt is disclosed.

[0007] JP-A-10-245526 discloses (A) N-vinyl-
One or more compounds selected from 2-pyrrolidone, N, N-dimethylaminoethyl (meth) acrylate and the like, (B)
N-vinyl-2-pyrrolidone homopolymer, and N, N-dimethyl (meth) acrylamide homopolymer, N-vinyl-2-
One or more polymer substances having a water-soluble or water-swelling swelling property selected from copolymers of pyrrolidone and N, N-dimethyl (meth) acrylamide, (C) for temporary fixing comprising a polymerization initiator A method for processing a small article using the adhesive composition is disclosed.

[0008]

The adhesive composition for temporary fixing described in Japanese Patent Application Laid-Open No. 61-287976 has a large number of prepolymers containing a long chain polyethylene oxide having a degree of polymerization of 9 to 25. It is difficult to penetrate the work into the gaps of the laminated body and apply it, or the thickness of the applied adhesive increases and the work floats, making precise positioning difficult. There is a drawback that processing accuracy cannot be obtained. In addition, the prepolymer containing the long-chain polyethylene oxide has a high molecular weight and therefore has poor compatibility with other components, and precipitates in the adhesive,
In some cases, it may cause problems such as solidification in winter. Furthermore, the processing method disclosed in this publication has a problem that small articles having a small thickness are easily broken when peeled, for example, because small articles having a small thickness are detached and dipped in high-temperature boiling water when removing the small articles after machining. .

[0009] The temporary fixing adhesive composition disclosed in JP-A-2-140279, JP-A-2-47678 and JP-A-6-116534 is composed of only a monomer having strong hydrophilicity. It takes a very long time to peel off due to too strong adhesive force, or it becomes a sticky gel when absorbing water and adheres to the surface of the work, which requires a lot of cleaning work. There were difficulties. Further, as a method of reducing the adhesive strength of the temporary fixing adhesive composition, the light irradiation time when curing the adhesive is very short, or the polymerization of the hydrophilic monomer by reducing the irradiance of ultraviolet rays. There is a method of interrupting halfway, but the characteristics of the polymer interrupted in this way are very unstable, daily temperature fluctuations in the working environment, irradiance reduction of the ultraviolet lamp over time, adhesives Adhesive strength is likely to change due to various inevitable variables in the process such as differences in ingredient lots of components and moisture absorption,
For example, the adhesive strength is greatly reduced and falls off during processing,
Alternatively, as described above, a problem in the process occurs such that the adhesive strength becomes unnecessarily high and peeling becomes difficult, and a problem arises in that process management becomes difficult.

The temporary fixing adhesive composition disclosed in JP-A-2-142874 contains a large amount of a water-soluble polymer.
Since the viscosity of the adhesive composition becomes high and cannot be used for precise temporary fixing as in the case of the adhesive composition described in JP-A-61-287976, it becomes a gel having tackiness when immersed in water, When a small component having a small thickness is peeled off, it has a drawback that the component does not peel off for a long time due to its adhesive force.

The quaternary ammonium salts such as the methyl chloride salt of N, N-dimethylaminoethyl methacrylate disclosed in JP-A-6-116535 are fixed at room temperature, so that water or 2-hydroxyethyl (meth) ) Acrylate and 2-hydroxypropyl (meth) acrylate are used in combination, but those containing water have poor adhesion at the time of temporary fixing and have the problem that the workpiece may fall off or chip off due to the processing pressure in the mechanical processing step. The quaternary ammonium salt is precipitated as a solid, and the water is evaporated during the coating, which causes a problem. Also, 2-
Adhesive strength can be increased by further adding hydroxyethyl (meth) acrylate, etc., but application is not possible due to unavoidable disturbances in the production process, such as changes in the temperature and humidity of the workplace due to the season, and a rise in the temperature during UV irradiation. The content of moisture contained in the applied adhesive changes, and the adhesive properties become unstable, causing problems such as falling off or chipping of the part being processed and making peeling difficult. Easy to occur.

The N-vinylpyrrolidone used in the adhesive composition disclosed in JP-A-10-245526 is disclosed in JP-A-6-165165.
It is mutagenic and harmful as disclosed in No. 34.
Although N, N-dimethylacrylamide and the like disclosed in the same report are not harmful, the viscosity becomes very high because a large amount of a water-soluble polymer is used as an adhesive component.
As in -287976, it is difficult to apply the adhesive by penetrating into the gap between the laminates, and it is easy to cause a decrease in the accuracy of positioning in temporary fixing. Further, similarly to Japanese Patent Application Laid-Open No. 2-142874, there has been a problem that when water is absorbed in the peeling step, the adhesive becomes tacky, and a thin small part is difficult to peel.

In view of the above-mentioned problems in the prior art, the present invention has excellent permeability and can penetrate into the gaps of the laminated workpieces and bond them, has excellent dimensional accuracy of positioning, and is suitable for machining after temporary fixing. Adhesive for temporary fixing that has sufficient adhesive strength to withstand and can be quickly peeled without causing any damage by immersing it in a stripping solution composed of water at a relatively low temperature or a mixture of water and a water-soluble organic solvent. It has been made to provide compositions and methods of processing the same. Further, the present invention provides the temporary fixing adhesive composition and the stripping solution, a temporary adhesive kit containing the composition and the stripping solution, and a method for using the same, from a machining process involving temporary fixing, The aim was to eliminate harmful and environmentally polluting halogenated solvents, greatly improve environmental protection and work safety, and greatly improve workability and productivity in the processing process.

[0014]

That is, the present invention relates to a temporary fixing adhesive composition comprising the following 1), 2) and 3): 1) N, N-dimethyl At least one hydrophilic vinyl monomer selected from the group consisting of acrylamide, N-vinylcaprolactam, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerol (meth) acrylate; 2) at least one polyalkylene oxide mono (meth) acrylate represented by the following structural formula (I)

[0015]

Embedded image

However, R1, R2 and R3 are H or C
H ₃ , n is an integer of 4 to 8; and 3) a radical polymerization initiator.

The work temporarily fixed by the composition of the present invention is water or at least one selected from the group consisting of water-soluble organic solvents of alcohol, ketone, polyhydric alcohol, nitrogen compound and sulfur compound. By immersing in a stripping solution composed of an aqueous solution obtained by mixing various types of water-soluble organic solvents and water, it is possible to quickly strip without causing defects. Therefore, the present invention also relates to the temporary fixing adhesive composition, the stripping solution, and a temporary adhesive kit including the adhesive composition and the stripping solution.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The components of the temporary fixing adhesive composition used in the present invention will be described in detail below. The at least one hydrophilic vinyl monomer contained in the composition of the present invention includes N, N-dimethylacrylamide, N-vinylcaprolactam, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, And glycerol (meth) acrylate. These monomers impart good adhesiveness to the temporary fixing adhesive and exhibit an affinity for moisture, thereby imparting a property of allowing water to permeate in a short time when immersed in water or water and the above-mentioned stripping solution, thereby accelerating the stripping time. Help.

The at least one polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention exhibits a proper adhesion to the work when the work is temporarily fixed, and is immersed in the stripping solution. In this case, it has a property of being rapidly peeled off by hydration, and therefore has very excellent properties as a component of the temporary fixing adhesive.
In the structural formula (I) representing the degree of polymerization of the polyalkylene oxide chain, n is from 4 to 8, and when n is less than this, it is difficult to peel when immersed in the stripping solution of the present invention. Further, when n exceeds the range of the present invention, the adhesiveness to the work is reduced to cause a defect in fixing the work, or becomes a solid at normal temperature, and the adhesive composition for temporary fixing with the hydrophilic vinyl monomer of the present invention is used. In addition to the non-uniformity, which causes a decrease in performance, the crystal state in winter makes it difficult to use, and other defects occur.In addition, the viscosity of the temporary fixing adhesive composition increases, and the work requiring precise fixing accuracy is required. Problems such as difficulty in temporary fixing occur.

The amount of the compound of the formula (I) to be used can be appropriately selected by those skilled in the art according to the type of the compound, the type and size of the work, etc., but is usually from 5 to 70% by weight.
Is preferable, and 10 to 60% by weight is more preferable. When used in the above preferable composition range, an adhesive for temporary fixing having a suitable fixing strength and a suitable peeling time in the processing of a general article having a size of about 0.3 to 50 mm can be obtained. However, when the size of the work is large, it is possible to further increase the use amount. Conversely, when a long time processing is required, the use amount is reduced to 3 to 5% by weight and the peeling during the processing is performed. Adjustments such as reducing defects are possible. However, if the compound of the formula (I) of the present invention is not used, there is a practical problem that the stripping time is extremely long and the productivity is significantly reduced.

As the radical polymerization initiator used in the temporary fixing composition for temporary fixing of the present invention, known thermal polymerization initiators such as organic peracids and azobisisobutyronitrile, ultraviolet polymerization initiators and visible light A polymerization initiator is used. Thermal polymerization initiator is benzoyl peroxide, 1,1-bis (t-butylperoxy)
Cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperloylbenzoate, n-butyl
Organic peroxides such as -4,4-bis (t-butylperloyl) valerate, 2,5-dimethyl-2,5-di (t-butylperloyl) hexane, and 2,2′-azobisiso Butyronitrile, 2-
And azo compounds such as (carbamoylazo) -isobutyronitrile and 2,2′-azobis (2,4,4-trimethylpentane). Examples of ultraviolet polymerization initiators include benzoin, benzoin based benzoin methyl ether and the like, benzoyl benzoic acid, benzophenone based such as 4-phenylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, 1- [4
-(2-hydroxyethoxy) -phenyl] -2-hydroxy-2-
Examples include acetophenones such as methyl-1-propan-1-one.

As the visible light polymerization initiator, benzyl,
Quinones, acylphosphine oxides, α-aminoketones, bisacylphosphine oxides, metallocenes, thioxanthones, and the like, and a group consisting of camphorquinone, acylphosphine oxides, α-aminoketones, bisacylphosphine oxides, and metallocenes It is preferable to select from Specific examples of compounds belonging to this group include camphorquinone, 2,
4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, bis (2,6
-Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η ⁵ -2,
4-cyclopentadien-1-yl) -bis (2,6-difluoro-3
-(1H-pyrrol-1-yl) -phenyl) titanium and the like. In addition, even when the above-mentioned visible light polymerization initiator is used, it is possible to temporarily fix by ultraviolet polymerization by irradiation with ultraviolet light. In the present invention, two or more of the above-mentioned radical polymerization initiators may be used as a mixture, and the total amount thereof is appropriately adjusted usually in the range of 0.05 to 10% by weight.

Further, as long as the effects of the present invention are not impaired, the viscosity and mechanical properties of the adhesive composition for temporary fixing of the present invention may be adjusted by adding a hydrophobic monomer, polymer, inorganic filler or the like as an optional component. Alternatively, it is also possible to add a pigment or the like to color. The hydrophobic monomer can be adjusted so as to impart appropriate hydrophobicity to the adhesive composition, improve water resistance during machining, and withstand long-term processing. Specific examples of the hydrophobic monomer include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl Monofunctional (meth) acrylates such as (meth) acrylate and 1,6-hexanediol di (meth) acrylate, triethylene glycol dimethacrylate, polyethylene glycol # 400
Examples include polyfunctional (meth) acrylates such as dimethacrylate and polyethylene glycol # 600 dimethacrylate. The polymer can increase the viscosity of the adhesive composition, and can easily fill gaps generated when a work with poor flatness is fixed to the substrate. However, since the viscosity of the temporary fixing adhesive composition of the present invention can be increased by adding a small amount of a polymer, the adhesive composition does not become a sticky substance when peeled by immersion in water or the like, and productivity such as delay in peeling time is increased. Does not occur. Specific examples of the polymer suitably used in the present invention include polyvinylpyrrolidone and polymethyl methacrylate, and the amount of addition is usually in the range of 1 to 10% by weight.

Furthermore, the present invention provides a method for temporarily fixing a workpiece using the temporary fixing adhesive composition of the present invention, performing predetermined machining, and then using water or water and an alcohol-based, ketone-based, It is characterized by being immersed in a stripping solution consisting of an aqueous solution mixed with at least one kind of water-soluble organic solvent selected from the group consisting of a water-soluble organic solvent of a polyhydric alcohol system, a nitrogen compound system, and a sulfur compound system, and being peeled off. The method relates to a method of processing a component to be manufactured. In the processing method of the present invention, there is no particular limitation on the material of the workpiece to be temporarily fixed using the temporary fixing adhesive composition of the present invention. Preferred examples of the transparent material include transparent glass, color glass, optical glass, laser glass, YAG, crystal, ruby, sapphire, and quartz. Further, as the opaque material, for example, alumina, zirconia, ferrite, rare earth magnetic material, ferroelectric ceramics, silicon wafer, titanium, titanium alloy, stainless steel, aluminum,
Examples include iron and brass. Hereinafter, the processing method of the present invention will be specifically described.

First, in order to temporarily fix a part to be processed, an appropriate amount of the temporarily fixing adhesive composition of the present invention is applied to one of the workpieces or the supporting substrate to be bonded and fixed according to the bonding area, and then the other is fixed. Or a method in which a plurality of works to be temporarily fixed are laminated in advance, and the temporary fixing adhesive composition of the present invention is applied by penetrating into gaps. The adhesive composition for temporary fixing of the present invention does not need to perform an application operation under heating conditions accompanied by a change in viscosity unlike hot melt adhesives such as wax and pine tar, and the worker has a stable viscosity at room temperature. Can be operated in any time required, and even inexperienced workers can easily perform accurate positioning, and there is no danger such as burns accompanying the positioning. Further, since the adhesive composition for temporary fixing of the present invention has a low viscosity, the thickness of the adhesive after application is reduced, the inclination and thickness unevenness of the work are extremely small, high fixing accuracy is obtained, and a large number of works are obtained. Can be quickly penetrated into the gap between the workpieces. In the case where the surface of the work to be temporarily fixed is rough or the flatness is poor, and a gap is generated between the substrate and the work surface, a small amount of the above-described polymer is added to the temporary fixing adhesive composition of the present invention. It is also possible to fill without gaps by increasing the viscosity.

Next, conventionally known thermal polymerization, ultraviolet polymerization, and visible light polymerization are performed, and the applied temporary fixing adhesive composition of the present invention is cured to temporarily fix the workpiece.
For example, when temporarily fixing opaque workpieces such as ceramics and metals such as stainless steel, aluminum, and ferrite, use an adhesive composition with a thermal polymerization initiator added as a radical polymerization initiator, and heat the workpiece after the application process. Just do it. At that time, the thermal polymerization can be carried out usually by heating at a temperature range of 40 ° C to 150 ° C for 5 minutes to 5 hours, preferably at a temperature range of 50 ° C to 120 ° C for 10 minutes to 120 minutes. Incidentally, those skilled in the art can appropriately adjust the polymerization temperature and the polymerization time by adjusting the amount and type of the thermal polymerization initiator so as to be convenient for the production process.

On the other hand, when a transparent work such as optical glass or quartz is temporarily fixed, it can be temporarily fixed by ultraviolet polymerization or visible light polymerization. When performing ultraviolet polymerization, an ultraviolet ray polymerization initiator or an adhesive composition to which a visible light polymerization initiator is added is used as a radical polymerization initiator, and the work after the application process is irradiated with light to be fixed. Light sources for UV polymerization include high-pressure mercury lamps, mercury xenon lamps, metal halide lamps,
An ultraviolet fluorescent lamp or the like is used. UV irradiation conditions can be appropriately determined by those skilled in the art, but irradiance at 360 nm is preferably 0.5 mW / cm ² or more, and irradiation time is preferably in the range of about 10 seconds to 30 minutes depending on irradiance. .

In the case of performing visible light polymerization, an adhesive composition containing a visible light polymerization initiator as a radical polymerization initiator is prepared, and the work after the application step is irradiated with visible light. As a light source, a fluorescent lamp exclusively for visible light, a halogen lamp, or the like is used. The conditions for irradiating visible light can be appropriately determined by those skilled in the art, but it is preferable that the irradiance at 420 nm is ² mW / cm ² or more and the irradiation time is 10 seconds to 20 minutes. In particular, when a temporary fixing adhesive composition containing a visible light polymerization initiator is used, even when an ultraviolet light source such as a chemical lamp is used, a large curing is achieved by light irradiation in a shorter time than when an ultraviolet polymerization initiator is used. Depth is obtained. Further, by performing visible light irradiation using a visible light source, the effect is further increased several times, and a curing depth of several tens of mm can be easily obtained. For example, when a large number of works are laminated and cured at once. In this case, it is possible to surely cure to the deep part of the work, which brings about very excellent effects such as a secure fixing property and an effect of shortening the curing time. In addition, when a visible light curable adhesive composition is added by adding a visible light polymerization initiator, and visible light is polymerized by a visible light source, an optical element having an ultraviolet absorbing property, a colored filter, and the like are similar to those of quartz and glass. In this case, temporary fixation by light irradiation for about several minutes becomes possible, and productivity can be greatly increased as compared with the conventional method using thermal polymerization which requires several tens of minutes or more. Further, by performing the polymerization with visible light, there is no danger that the worker is exposed to harmful ultraviolet rays, and a very favorable working environment can be constructed in terms of the safety of the temporary fixing step. In addition, the adhesive composition for temporary fixing of the present invention has a polymerization temperature, a polymerization time, and a polymerization temperature caused by the action of the polyalkylene oxide (meth) acrylate represented by the structural formula (I) of the present invention.
Even if irradiance or the like is increased, there is no possibility that peeling will be difficult.Therefore, even if excessive light irradiation is performed by mistake or the heating time is prolonged, troubles in the processing step or peeling step may be caused. Since it is not available, it is also useful for stabilizing the production process.

Next, the temporarily fixed work is subjected to ordinary machining such as cutting, grinding, polishing, and drilling into a desired shape, and further, a short-time joining such as soldering or brazing. Machining is also included in the machining of the method of the present invention. At this time, since the work temporarily fixed with the temporary fixing adhesive composition of the present invention is bonded with high adhesive strength, the work hardly falls off or deforms during machining and exhibits good processing durability. The machined workpieces are separated from the support substrate and the workpieces. The stripping method can be performed by simply immersing the work in the stripping solution. At this time, since the temporary fixing adhesive composition of the present invention peels off naturally without directly touching the work, breakage during peeling can be prevented. Further, since a halogen-based solvent or a strong alkaline aqueous solution is not used, it is excellent in work safety and environmental protection. In the case of peeling with water, the temperature is usually from room temperature to 90 ° C. When stripping is performed with a stripping solution in which water and a water-soluble organic solvent are mixed, the stripping is performed at a temperature lower than the azeotropic temperature. The temperature at the time of peeling is appropriately set according to the heat resistance of the work, etc.
It is preferred to peel at a temperature of from about 80C to about 80C. As the water-soluble organic solvent used in the stripping solution of the present invention, methanol, ethanol, 2-propanol, methyl 2-hydroxyisobutyrate, N-methylpyrrolidone, or dimethyl sulfoxide is particularly preferable. Can be used.

The mixing ratio of water and the water-soluble organic solvent in the stripping solution of the present invention can be appropriately selected by those skilled in the art according to the type of the temporary fixing adhesive composition of the present invention.
It is preferable to set the weight ratio of water: water-soluble organic solvent to 3:97 to 80:20. In particular, when stripping with a stripping solution containing water and a water-soluble organic solvent, stripping can be performed in a shorter time than stripping with water alone, and when the work is made of stainless steel or alumina or the surface is rough. In such a case, the residue of the swollen temporary fixing adhesive can be easily peeled off from the surface of the work. In addition, when peeling is attempted using only the above-mentioned water-soluble organic solvent, there arises a problem that the peeling time is significantly increased or peeling is not possible. However, when a small amount of water is mixed with the water-soluble organic solvent, the peeling time is remarkably reduced, and excellent peeling properties are exhibited. This is a phenomenon found for the first time in the present invention, and is a very useful property obtained by combining with the temporary fixing adhesive composition of the present invention.

When a work made of a material which is easily corroded, such as iron, ferrite, or a rare earth metal, temporarily fixed with the temporary fixing adhesive composition of the present invention is peeled off, the above-mentioned water-soluble organic solvent is used. If an aqueous solution mixed with a small amount of water is used as a stripping solution, the effect of suppressing the generation of rust can also be obtained.However, as a method of more actively preventing the generation of rust, an aliphatic amine, Water-soluble adsorptive corrosion inhibitors such as aromatic amines, urea condensates and derivatives thereof, thioureas and substituted products thereof, and aldehydes can be contained. Specific examples of the water-soluble adsorption-type corrosion inhibitor include octylamine, dodecylamine, aniline, thiourea, acetaldehyde, and the like, and are disclosed in JP-A-9-291381, JP-A-9-3667, and the like. A high-performance water-soluble rust inhibitor or the like can be applied. The amount of these water-soluble adsorption-type corrosion inhibitors used is usually in the range of 1 to 10% by weight with respect to water, and is used when stripping with water alone, and in a stripping solution containing water and a water-soluble organic solvent. May be used. In particular, when the material of the work is very susceptible to corrosion such as a rare-earth magnetic material, use the above water-soluble adsorption-type corrosion inhibitor in addition to the stripping solution in which the weight ratio of water is reduced to about 3 to 20%. And a very excellent rust prevention effect can be obtained. In the present invention, as long as the effects of the present invention are not impaired, such as not damaging the work, the work is given a physical stimulus such as rocking, water flow, ultrasonic wave or temperature change at the time of peeling, and the peeling time and cleaning are reduced. The time required can be further reduced.

There is no particular limitation on the size of the workpiece to be processed by the processing method of the present invention. Thus, for example, width 1
It is also possible to temporarily fix a plate glass having a length of about mx 2 m. However, after machining, from the viewpoint that peeling is completed within a time that is practical as a production process, the size of the workpiece after machining is temporarily fixed with the temporary fixing adhesive composition of the present invention. It is preferable that the size of the portion that is located is preferably in the range of 0.1 mm to 200 mm.
Furthermore, the size of the part to be machined after machining is 0.3 mm
When it is within the range of ~ 50 mm, the time balance between the machining process and the subsequent peeling process is well maintained, and mass production of several thousand to tens of thousands per day is possible without delay.
It is advantageous.

Among the machining methods in the processing method of the present invention, in particular, the one in which the effect of the temporary fixing by the temporary fixing adhesive composition of the present invention is effectively exhibited is, for example, the case where the thickness after the mechanical processing is 0. Precision grinding and polishing steps that require high dimensional accuracy, such as in the range of 0.1 μm to 10 μm. That is, even if the temporary fixing adhesive composition of the present invention is a part to be processed having a size of several tens of mm, it can be temporarily fixed with an average thickness of 10 μm or less after the temporary fixing, and the unevenness of the thickness is reduced. It can be reduced to 10 μm or less, and further has a feature that a dimensional change due to processing pressure, heat during processing, and the like is extremely small. Therefore,
Even when a large number of workpieces are temporarily fixed repeatedly using the temporary fixing adhesive composition of the present invention, the thickness of the workpiece after the temporary fixing can always be suppressed to a fixing accuracy of 10 μm or less. In addition, the inclination angle of the temporarily fixed workpiece can be extremely small (about 50 seconds or less). Such a feature of the present invention is, for example, a performance particularly suitable for processing a component requiring a high thickness accuracy of several μm or less, such as a quartz oscillator, an ultrasonic delay line glass, a precision resistor, and a precision capacitor. . The thickness of the temporary fixing adhesive composition of the present invention is several μm.
Even if it fluctuates in the range of m, since it is possible to process while measuring and managing the thickness in the processing step of the high precision part,
Substantial thickness accuracy is governed by the inclination angle of the temporarily fixed workpiece. Since the inclination of the workpiece to be temporarily fixed with the temporary fixing adhesive composition of the present invention can be made 0.2 μm or less per 1 mm in length and width, the method of the present invention can be applied to the processing requiring the same degree of thickness accuracy. .

Other specific examples of machining that can suitably use the temporary fixing adhesive composition of the present invention include, for example, temporary fixing with the temporary fixing adhesive composition of the present invention after processing. Cutting or polishing of quartz or ceramic vibrators with the dimensions of the part in the range of 0.3mm to 30mm,
An optical prism whose dimensions are in the range of 0.3 mm to 50 mm,
Cutting, polishing, grinding, drilling of optical lens, optical filter, ultrasonic delay line glass, etc., package parts such as stainless steel or aluminum with the same size in the range of 1mm to 50mm, same size Cutting, grinding and polishing of miniature magnets for micro motors or relays whose size is in the range of 2mm to 50mm, the same size is 0.2mm to 30mm
Cutting, polishing, cutting and polishing of ceramic capacitors or precision resistors in the range of mm, silicon, germanium, silicon oxide and other micromachines or microcapacitors with the same dimensions in the range of 0.1 mm to several mm, and Cutting, grinding, and precision polishing of the ultrasonic delay line glass having the same dimension in the range of 0.3 mm to 20 mm.

[0035]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. These are merely examples and do not limit the technical scope of the present invention in any way. Preparation method of adhesive composition for temporary fixing: At the composition ratios shown in Tables 1 and 2, each component was weighed, stirred and dissolved to obtain an adhesive composition for temporary fixing. When an ultraviolet polymerization initiator or a visible light polymerization initiator was used, a light-shielding container was used.
The numerical values indicating the compositions in Tables 1 and 2 indicate parts by weight. Ultraviolet light polymerization method: UV irradiation was performed using a chemical lamp (manufactured by Toshiba Lighting & Technology Corp.). Thermal polymerization method: Heating was carried out at a constant temperature of 80 ° C. for 30 minutes. Visible light polymerization method: Visible light lamp (FL manufactured by Adel Co., Ltd.)
-V) was used to irradiate visible light. Peeling time measuring method: The temporarily fixed work was immersed in a stripping solution at a predetermined temperature, and the time required for natural peeling without touching the work was measured.

[0036]

Example 1 30 g of N, N-dimethylacrylamide (DMAA)
Polyalkylene oxide mono represented by the structural formula (I)
(Meth) acrylate 70 g of hexapropylene glycol monoacrylate (HPGA) with n = 6 and 0.5 g of 2,2'-azobisisobutyronitrile (AIBN) are put into a screw-neck glass bottle, stirred, dissolved and temporarily fixed. An adhesive composition was prepared.
Prepare two slide glasses (length 76, width 26, thickness 1.3 mm), apply the prepared adhesive composition on one slide glass, and on the other slide glass, Was placed so as not to get caught. At this time, there was no change in the viscosity of the adhesive composition, and the slide glasses were easily overlapped, and the operability was good. When the thermal polymerization was performed, the two slide glasses were firmly fixed, and the glass itself was damaged when the slides were to be peeled off with fingers. Pyrex glass having a diameter of 6 mm, a height of 10 mm, and a diameter of 20 mm and a height of 25 mm was temporarily fixed with the same adhesive composition under the same conditions, and a crosshead speed of 1 mm /
When a compression shear test was carried out at a pressure of min, a good adhesive strength of 7.0 MPa was exhibited. Next, the thickness of the two slide glasses temporarily fixed by the method described above was measured with a micrometer, and when the unevenness of the thickness of the cured adhesive composition was measured, the thickness was 0.010 mm or less. It was confirmed that high fixing accuracy with small unevenness was obtained. When the slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or break during cutting, and had good cutting durability. 80 cut glass slides
When immersed in water at ℃, it peeled off in 2 to 5 hours. As described above, it was confirmed that the temporary fixing adhesive composition of this example has good operability, high fixing accuracy, good processing durability, and excellent productivity to be peeled off in a short time. Was done.

The following Comparative Examples 1 to 5 are examples of the present invention.
This is a comparative example with respect to No. 1, and more clearly shows the excellent features of the present invention. Comparative Example 1 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, two slide glasses were laminated by the same operation as in Example 1 without using the polyalkylene oxide mono (meth) acrylate. At this time, there was no change in the viscosity of the adhesive composition, the slide glasses were easily superimposed, and the operability was good. The two slide glasses fixed by thermal polymerization were firmly fixed. When measuring the adhesive strength in the same manner as in Example 1,
The bonding strength provided a very high bonding strength of 17.2 MPa or more. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, the thickness was 0.010 mm or less, and good fixing accuracy with small thickness unevenness was obtained. When the slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or break during cutting, and the processing durability was good. However, when the cut slide glass is immersed in water at 80 ° C., the adhesive composition becomes a sticky substance, and the slide glass does not peel off even after immersion for 20 hours, and cannot be used as a temporary fixing adhesive composition. Occurred. That is, it was confirmed that even when the hydrophilic vinyl monomer N, N-dimethylacrylamide (DMAA) disclosed in the present invention was used alone, it could not be used as a temporary fixing adhesive composition.

Comparative Example 2 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, two slide glasses were temporarily fixed by thermal polymerization in the same manner as in Example 1 without using a hydrophilic vinyl monomer. When the adhesive strength was measured in the same manner as in Example 1, it was found to be very small at 1.9 MPa. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass was peeled off during cutting, and sufficient processing durability was not obtained.
That is, it has been clarified that even if only hexapropylene glycol monoacrylate which is the compound of the structural formula (I) disclosed in the present invention is used alone, it cannot be used as an adhesive composition for temporary fixing.

Comparative Example 3 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, methoxypolyethylene glycol monomethacrylate (MPEGMA) where n is 23 was used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I). MPEGMA is N,
Precipitates without dissolving in N-dimethylacrylamide and at 12 ° C
In the vicinity, the adhesive composition hardened and was difficult to apply. That is, when n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention exceeds the range of the present invention, a homogeneous adhesive composition cannot be obtained, and the coating operation is difficult. It was confirmed that.

Comparative Example 4 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, as in Comparative Example 3, methoxypolyethylene glycol monomethacrylate (MPEGMA) in which n is 23 was used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I). However, MPEGMA did not dissolve in acryloylmorpholine and precipitated, and at around 12 ° C., the adhesive composition solidified and could not be applied. That is, when the number n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is equal to or more than the range of the present invention, it is possible to prepare a homogeneous adhesive composition even if the kind of the hydrophilic monomer is changed. It was confirmed that coating was not possible and coating was not possible.

Comparative Example 5 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, the polyalkylene oxide mono represented by the structural formula (I) disclosed in the present invention
Using diethylene glycol monomethacrylate (DEGMA) in which n of (meth) acrylate is 2, two slide glasses were laminated in the same manner as in Example 1. At this time, as in Example 1, the operability was good. The two slide glasses were firmly fixed by thermal polymerization. When the unevenness of the thickness of the cured adhesive composition was measured in the same manner as in Example 1, the unevenness of the thickness was small at 0.010 mm or less, and high fixing accuracy was obtained. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not drop or break during cutting, and showed good processing durability. However, when the cut slide glass was immersed in water at 80 ° C., it did not peel even after 20 hours. That is,
Polyalkylene oxide mono represented by the structural formula (I)
It was found that when the n of the (meth) acrylate falls below the range of the present invention, the peeling time of the part becomes extremely long, and the productivity is significantly reduced.

[0042]

Example 2 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, the structural formula (I) disclosed in the present invention
The polyalkylene oxide mono (meth) acrylate represented by n is 8, using octaethylene glycol monomethacrylate (OEGMA), when two slide glasses were overlapped by the same operation as in Example 1, Example
Good operability was shown as in 1. As a result of the thermal polymerization, the two slide glasses were firmly fixed, and the glass was broken enough to be peeled off with fingers. When the unevenness of the thickness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less, and the fixed adhesive had high fixing accuracy with a small unevenness of the thickness. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or break during cutting, indicating good processing durability. When the cut slide glass was immersed in an aqueous solution in which water and ethanol were mixed at a weight ratio of 50 to 50 at 60 ° C., the slide glass was spontaneously peeled in a short time of 2 to 5 hours. From these results, in Example 1, the structural formula (I)
N of the polyalkylene oxide mono (meth) acrylate
When the composition ratio of the hydrophilic monomer is changed to 8, the same operation as in Example 1 has good operability, high fixing accuracy, good processing durability, and a short peeling time. It has been confirmed that a temporary fixing adhesive composition having the features of the present invention can be obtained.

[0043]

Example 3 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, the structural formula (I) disclosed in the present invention
Using tetraethylene glycol monomethacrylate (TEGMA) in which n of the polyalkylene oxide mono (meth) acrylate represented by is 4, two slide glasses were laminated in the same manner as in Example 1. At this time, there was no change in the viscosity of the adhesive composition, the slide glasses could be easily superposed, and the operability was good. The two slide glasses fixed by ultraviolet polymerization were firmly fixed, and the glass itself was damaged when it was attempted to peel off with fingers. When the unevenness of the thickness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less, and the fixed adhesive had high fixing accuracy with a small unevenness of the thickness. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or break during cutting, indicating good processing durability. It was confirmed that when the cut slide glass was immersed in an aqueous solution in which water and ethanol were mixed at a weight ratio of 50:50 at 60 ° C., the slide glass was separated in a short time of 2 to 5 hours. When n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention is 4, the operability is good, the fixing accuracy is high, the processing durability is good, It was confirmed that the peeling time was short and good results were obtained.

[0044]

Example 4 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, the structural formula (I) disclosed in the present invention
In the polyalkylene oxide mono (meth) acrylate represented by 4, n is 4, using methoxytetraethylene glycol monomethacrylate (MTEGMA), prepared 50 cover glass laminated (24x60x0.15mm), laminated The adhesive composition was permeated from the side of the cover glass. The adhesive composition quickly penetrated into the gaps between the cover glasses, and showed excellent permeability. Ultraviolet rays were irradiated from the side of the laminated cover glass to temporarily fix the cover glass. The cure time required for complete cure was 30 minutes. The temporarily fixed cover glass was cut to a width of 5 mm with a diamond cutter. The temporarily fixed cover glass did not fall off or break during cutting, and showed good processing durability. When the cut cover glass is immersed in an aqueous solution in which water and ethanol at 60 ° C. are mixed at a weight ratio of 50 to 50, 3 to 6
All peeled off spontaneously over time, and there was no adhesion between the cover glasses or breakage during peeling. From the above, the present adhesive composition exhibited excellent performance, such as good penetration into a laminate, sufficient curing depth, good processing durability, and a short peeling time of a part after processing. .

[0045]

Example 5 An adhesive composition for temporary fixing was prepared in the same composition ratio as in Example 4, 50 cover glasses were prepared, and the adhesive composition was permeated from the side of the laminated cover glass. Was. The adhesive composition penetrated quickly and exhibited excellent permeability. Visible light was irradiated from the side of the laminated cover glass and temporarily fixed. The curing time was 5 minutes, and it was confirmed that the inside was cured in a much shorter time than the ultraviolet polymerization. The temporarily fixed cover glass was cut to a width of 5 mm with a diamond cutter. During the cutting, the cover glass did not fall off or was broken, and the processing durability was good. When the cut cover glass was immersed in an aqueous solution in which water and ethanol were mixed at a weight ratio of 50 to 50 at 60 ° C., the cover glass was peeled in 3 to 6 hours. Compared to Example 4 in which ultraviolet polymerization was performed using a visible light polymerization initiator, in this example in which visible light polymerization was performed, the curing time was significantly reduced, and performance equivalent to that in ultraviolet polymerization was achieved. It was confirmed that the productivity was further improved.

The following Comparative Examples 6 and 7 are Comparative Examples with respect to Examples 4 and 5 of the present invention, and clearly show the excellent features of the present invention. Comparative Example 6 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, the structural formula (I) disclosed in the present invention
Using a methoxy nona ethylene glycol monomethacrylate (MNPGMA), wherein n of the polyalkylene oxide mono (meth) acrylate represented by The adhesive composition was permeated from the lamination surface. The adhesive composition penetrated quickly and exhibited excellent permeability. Ultraviolet rays were irradiated from the side of the laminated cover glass to temporarily fix the cover glass. The curing time required 30 minutes. When the cover glass temporarily fixed was cut to a width of 5 mm with a diamond cutter, the cover glass fell off during cutting, and sufficient processing durability was not obtained. Thus, when n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) exceeds the range of the present invention, it is apparent that the adhesion to the work is reduced and the processing durability cannot be obtained. It became. Comparative Example 7 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, 50 sheets of cover glass were prepared in the same manner as in Example 4 without containing the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I), and the adhesive composition was permeated from the laminated surface. I let it. The adhesive composition permeated quickly, and the permeability was excellent. Ultraviolet rays were irradiated from the lamination side. The curing distance when irradiated for 30 minutes is
3 mm and the center remained uncured. Thus, compared to Examples 4 and 5, an adhesive composed of only a hydrophilic monomer and an ultraviolet polymerization initiator without containing the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) The adhesive composition was found to be unsuitable as an adhesive composition because the laminated product could not be temporarily attached.

[0047]

Example 6 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (BTP) was used as a radical polymerization initiator instead of (AIBN) used in Example 1.
Using O), two slide glasses were overlaid in the same operation as in Example 1. At this time, there was no change in the viscosity of the adhesive composition, the slide glasses could be easily superposed, and the operability was good. The two slide glasses were firmly fixed by visible light polymerization. When the unevenness of the thickness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less, and high fixing accuracy with small unevenness of the thickness was obtained. When this slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or break during cutting, and showed good processing durability. When the cut slide glass was immersed in water at 80 ° C., it was peeled off in 2 to 5 hours.

[0048]

Example 7 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, the amount of HPGA used as the polyalkylene oxide mono (meth) acrylate in Example 6 was reduced from 70 parts by weight to 60 parts by weight, and two slide glasses were overlapped by the same operation as in Example 1. Was. At this time, there was no change in the viscosity of the adhesive composition, the slide glasses could be easily superposed, and the operability was good. The two slide glasses fixed by visible light polymerization were firmly fixed as in Example 1. The thickness unevenness of the cured adhesive composition was measured to be 0.010 mm or less in the same manner as in Example 1, and the thickness unevenness was small and high fixing accuracy was obtained. Temporarily fixed slide glass with diamond cutter, width 10
When cut into mm, the slide glass did not fall off or break during cutting, indicating good processing durability. When the cut slide glass was immersed in water at 80 ° C., it was peeled in 2 hours and peeled in a shorter time than in Example 6. From these results, the amount of HPGA used as the polyalkylene oxide mono (meth) acrylate was lower than that in Example 6.
It was confirmed that by adjusting the amount from 70 parts by weight to 60 parts by weight, the peeling time was further shortened, and the productivity was further improved.

[0049]

Example 8 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, the amount of MTEGMA used as the polyalkylene oxide mono (meth) acrylate in Example 4 was reduced from 70 parts by weight to 50 parts by weight, and a cover glass was prepared by stacking 50 sheets in the same manner as in Example 4. Then, the adhesive composition was permeated from the side surface of the laminated cover glass.
The adhesive composition quickly penetrated and exhibited excellent permeability.
Ultraviolet rays were irradiated from the side of the laminated cover glass to temporarily fix the cover glass. The curing time required 30 minutes, and the inside was cured. This cover glass is 5m wide with a diamond cutter
Cut to m. In the cutting step, the cover glass did not fall off or was broken, showing good processing durability. When the cut cover glass was immersed in an aqueous solution in which water and ethanol were mixed at a weight ratio of 50 to 50 at 60 ° C., the cover glass was peeled in 2 to 4 hours, and peeled in a shorter time than in Example 4. From these results, the amount of MTEGMA used as the polyalkylene oxide mono (meth) acrylate was 70 parts by weight in Example 4, whereas the amount of MTEGMA was 50 parts by weight in this example. And increased productivity.

[0050]

Example 9 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, the amount of MTEGMA used was reduced to 50 parts by weight in the same manner as in Example 8, 50 cover glasses were prepared, and the adhesive composition was permeated from the side surfaces of the laminated cover glasses. The adhesive composition quickly penetrated and exhibited excellent permeability. Visible light was irradiated from the side of the laminated cover glass and temporarily fixed. The curing time required 5 minutes, and the inside was cured in a short time. This cover glass was cut to a width of 5 mm with a diamond cutter. The workpiece did not fall off or break during the cutting process and showed good processing durability. When the cut cover glass is immersed in an aqueous solution in which water and ethanol at 60 ° C. are mixed at a weight ratio of 50 to 50, 2 to 4
Peeled in time. From these results, it was found that, in Example 8 in which ultraviolet polymerization was performed using an ultraviolet initiator, when visible light polymerization was performed using a visible light polymerization initiator, the curing time was further reduced. .

[0051]

Example 10 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, two slide glasses were overlapped by the same operation as in Example 1, except that the amount of OEGMA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention was 7 parts by weight. At this time, there was no change in the viscosity of the adhesive composition, the slide glasses could be easily superposed, and the operability was good. The two slide glasses fixed by ultraviolet polymerization were firmly fixed as in Example 1. When the adhesive strength was measured in the same manner as in Example 1, the adhesive strength was 11.0 MPa, showing excellent adhesive strength. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, the thickness was 0.010 mm or less, and the thickness unevenness was small and high fixing accuracy was obtained. When this slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or break during cutting, and showed good processing durability. Cut glass slides
When immersed in water at 80 ° C., it peeled in 6 hours. From these results, even if the amount of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention is 10 parts by weight or less, the polyalkylene oxide has good permeability to the laminated work, It has been found that an excellent temporary fixing adhesive composition exhibiting good operability and high fixing accuracy, having good processing durability and having no trouble even at the time of peeling can be obtained.

[0052]

Example 11 Using the adhesive composition prepared at the same composition ratio as in Example 10, 50 slide glasses were temporarily fixed and cut in the same manner as in Example 10. When the cut slide glass having a width of 10 mm was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 80:20, the slide glass was peeled in 3 hours, and the peel time was shorter than that in Example 10.
It was confirmed that the peeling time was further shortened when peeling was performed using an aqueous solution in which water and ethanol disclosed in the present invention were mixed at a weight ratio of 80:20 instead of water.

[0053]

Example 12 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, the amount of HPGA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention was 7 parts by weight, and
A laminated cover glass was prepared, and the adhesive composition was permeated from the side surface of the laminated cover glass. The adhesive composition quickly penetrated and exhibited excellent permeability. Ultraviolet light was irradiated from the side of the laminated cover glass. The curing time required 30 minutes. This cover glass was cut into a width of 2 mm with a diamond cutter. In the cutting step, the cover glass did not fall off or was broken, showing good processing durability. When the cut cover glass was immersed in an aqueous solution in which water and ethanol were mixed at a weight ratio of 50:50 at 60 ° C., the cover glass was peeled in 3 hours. From these results, even when the amount of polyalkylene oxide mono (meth) acrylate used is small, it shows excellent permeability, has a short curing time, shows good processing durability, and has a short processed part. Peeled in time.

[0054]

Example 13 Using the adhesive composition prepared in the same composition ratio as in Example 12, 50 cover glasses were prepared in the same manner as in Example 12, and from the side of the laminated cover glass. The adhesive composition was infiltrated. The adhesive composition quickly penetrated and exhibited excellent permeability. Visible light was irradiated from the side of the laminated cover glass. Its curing time is
It took 5 minutes. This cover glass was cut into a width of 2 mm with a diamond cutter. The workpiece did not fall off or break during the cutting process and showed good processing durability. Cut the cut cover glass with water and ethanol at 60 ° C in a weight ratio of 50:50.
When immersed in an aqueous solution mixed with the above, it was peeled off in 3 hours. Example 12 in which UV polymerization was performed using a visible light initiator
On the other hand, the curing time was further shortened by further performing visible light polymerization after using the visible light polymerization initiator.

[0055]

Example 14 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, two alumina test pieces (length 25, width 25, thickness 2 mm) with 25 parts by weight of TEGMA as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention. Was prepared, the adhesive composition was applied onto one of the alumina test pieces, and another alumina test piece was placed thereon. At this time, there was no change in the viscosity of the adhesive composition, the superposition of the alumina test pieces was easy, and the operability was good. The two alumina test pieces were firmly fixed by thermal polymerization. This alumina test piece was cut into a width of 5 mm with a diamond cutter.
During the cutting step, the alumina test piece did not fall off or was broken, and the processing durability was good. When the cut alumina test piece was immersed in water at 80 ° C., it was peeled off in 4 hours. Some residue of the adhesive composition was adhered on the peeled alumina test piece. This additional deposit was removed by an additional 1 hour immersion. 50% instead of additional immersion
It was found that when ultrasonic cleaning was performed in an aqueous alcohol solution, the water was removed in 10 minutes. Further, a diameter of 6 mm, a height of 10 mm, a diameter of 20 mm and a height of 20 m separately prepared according to Example 1.
The m test pieces made of alumina were bonded by thermal polymerization using the adhesive composition of the present invention under the same conditions as in this example. When the compressive shear adhesive strength of this test piece was measured at a crosshead speed of 1 mm / min using a material testing machine, 10MP
a exhibited excellent adhesive strength.

[0056]

Example 15 Using an adhesive composition prepared in the same composition ratio as in Example 14, an alumina test piece was temporarily fixed and cut under the same conditions as in Example 14. Cut the cut alumina specimen into water at 80 ° C and methyl 2-hydroxyisobutyrate.
When (HBM) was immersed in an aqueous solution mixed at a weight ratio of 50:50, the exfoliation occurred in 3 hours, and the exfoliation was shorter than in Example 13. In this example, no residue of the adhesive composition adhered to the peeled alumina test piece. That is, when peeling with an aqueous solution in which water and methyl 2-hydroxyisobutyrate (HBM) are mixed at a weight ratio of 50:50 instead of water, the peeling time is shortened, and the peeled adhesive composition adheres to the parts. By not doing so, it was found that the washing process of the parts could be simplified and the productivity improved.

[0057]

Example 16 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, using 25 parts by weight of HPGA as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention, two stainless steel test pieces (length 8, width 5, thickness 5 mm) ) Was prepared, the adhesive composition was applied on one of the stainless steel test pieces, and another stainless steel test piece was placed thereon. Two stainless steel test pieces were temporarily fixed by thermal polymerization. At this time, there was no change in the viscosity of the adhesive composition, the stainless steel test pieces could be easily overlapped, and the operability was good. The two stainless steel specimens were firmly fixed by thermal polymerization. In the same manner as in Example 14, a stainless steel test piece for an adhesion test was prepared, temporarily fixed under the polymerization conditions of this example, and the adhesive strength was measured. As a result, an excellent adhesive strength of 11.0 MPa was shown. Next, the stainless steel test piece temporarily fixed and cut in this example was heated to 60 ° C.
When immersed in an aqueous solution in which water and ethanol were mixed at a weight ratio of 50:50, the adhesive was peeled off in 2 hours, but some residue of the adhesive composition adhered to the surface. Thereafter, when additional immersion was performed for 1 hour, the deposits were completely removed. When ultrasonic cleaning was performed in a 50% aqueous ethanol solution instead of performing the additional immersion, it was found that it was removed in 10 minutes.

[0058]

Example 17 Using the adhesive composition prepared in the same composition ratio as in Example 16, a stainless steel test piece temporarily fixed in Example 16 was subjected to water / HBM at 80 ° C. = 50/50 wt / When immersed in an aqueous solution of wt, it peeled in 2 hours. In this example, the adhesive composition did not adhere to the peeled stainless steel test piece. That is, when the stripping solution is stripped as an aqueous solution in which water and methyl 2-hydroxyisobutyrate (HBM) are mixed in a weight ratio of 50:50 instead of the aqueous solution in which water and ethanol are mixed in a weight ratio of 50:50. It was found that the peeling time was shortened, and the peeled adhesive composition did not adhere to the parts, thereby simplifying the washing process of small articles and improving the productivity.

[0059]

Example 18 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, with the use amount of HPGA as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention being 15 parts by weight, two rare earth magnetic material test pieces having a length and width of about 50 mm were prepared. The adhesive composition was applied on one of the rare earth magnetic test pieces, and another rare earth magnetic test piece was placed thereon. At this time,
There was no change in the viscosity of the adhesive composition, the test piece made of a rare earth magnetic material was easily superimposed, and the operability was good.
The two rare earth magnetic specimens were firmly fixed by thermal polymerization. The test piece made of the rare earth magnetic material was cut into a width of 2 mm with a diamond cutter. No cutting-off or chipping occurred in the cutting process, indicating excellent processing durability. Cut the cut test piece made of rare earth magnetic material into water at 80 ° C and methyl 2-hydroxyisobutyrate.
(HBM) was immersed in an aqueous solution having a weight ratio of 3:97, and peeled off in 4 hours. This test piece did not show any rust during peeling. However, when it was taken out of the stripping solution and left in a room where the stripping solution was wiped off and dried for 3 days, signs of slight rusting were observed.

Comparative Example 8 A test piece made of a rare-earth magnetic material cut to a width of 2 mm in Example 18 was immersed in a 100% HBM solvent at 80 ° C., and did not peel off even after 20 hours. Compared with Example 18, when the HBM is 100% and does not contain water, it does not peel off. However, the effect of the present invention that the peeling time can be significantly reduced by using the aqueous solution of the present invention to which 3% water is added is used. Briefly shown.

[0061]

Example 19 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, as in Example 4, 50 cover glass sheets were prepared by using HPGA as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention in an amount of 15 parts by weight, The adhesive composition was permeated from the side of the laminated cover glass. The adhesive composition penetrated quickly and exhibited excellent permeability.
When visible light was irradiated from the side of the laminated cover glass, the whole was completely polymerized in 5 minutes. When the adhesive strength was measured in the same manner as in Example 1, excellent adhesive strength of 11.0 MPa or more was shown. The temporarily fixed cover glass was cut to a width of 2 mm with a diamond cutter. During the cutting, the cover glass did not fall off or was broken, and the processing durability was good. When the cut cover glass was immersed in an aqueous solution in which water and ethanol were mixed at a weight ratio of 50 to 50 at 60 ° C., the cover glass was peeled off in 2 hours. Example 13 was a polyalkylene oxide mono
When the amount of (meth) acrylate used increased, the peeling time was shortened. The test piece made of the rare earth magnetic material did not rust during immersion in the stripping solution. However, when it was taken out of the stripping solution, the stripping solution was wiped off and left in a dry room, it was found that rust was generated the next day.

[0062]

Example 20 An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, two test pieces made of a rare earth magnetic material similar to those of Example 18 were prepared, with the amount of OEGMA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention being 60 parts by weight. Then, the adhesive composition was applied on one of the rare earth magnetic test pieces, and another rare earth magnetic test piece was placed thereon. At this time, there was no change in the viscosity of the adhesive composition, the test pieces made of the rare earth magnetic material could be easily superposed, and the operability was good. When two rare earth magnetic test pieces were temporarily fixed by thermal polymerization, the rare earth magnetic test piece was firmly fixed.
The test piece made of the rare earth magnetic material was cut into a width of 5 mm with a diamond cutter. No cutting-off or chipping occurred in the cutting process, indicating excellent processing durability. Cut the cut test piece made of rare earth magnetic material into water at 80 ° C and methyl 2-hydroxyisobutyrate (HBM).
When immersed in an aqueous solution in which 10 and 90 are mixed by weight,
Peeled in time. No rust was observed during the peeling of the test piece made of the rare earth magnetic material. However, the test piece was taken out of the stripping solution, wiped off the stripping solution, and left in a dry room.
On the day, slight rust occurred.

[0063]

EXAMPLE 21 The rare earth magnetic material having a width of 5 mm cut in Example 20 was added as a water-soluble adsorption-type corrosion inhibitor to Yushiloken SC25A manufactured by Yushiro Chemical Industry Co., Ltd. in an amount of 4% by weight in water. When immersed in an aqueous solution (60 ° C) mixed with 10-90 by weight ratio of methyl-hydroxyisobutyrate (HBM) and peeled, the peeling time was as short as 4 hours, showing good peelability. Furthermore, the exfoliated rare-earth magnetic test piece does not rust during the exfoliation, and does not rust even after being taken out of the exfoliation solution, wiped off water drops, and left in a dry room for 3 days. showed that.

[0064]

The adhesive composition for temporary fixing of the present invention does not need to be applied under heating conditions involving a change in viscosity, unlike hot melt adhesives such as wax and pine tar, and is stable at room temperature. Can be operated at any time required by the worker with the adjusted viscosity, so even inexperienced workers can easily perform accurate positioning and high operability, and there is no danger of burns due to positioning because high temperature operation is not performed No safety. Since the temporary fixing adhesive composition has excellent permeability, the laminated work can be temporarily fixed, so that a large number of parts can be collectively processed by one temporary fixing operation, and high productivity is obtained. Can be Further, since the thickness unevenness of the temporarily fixed adhesive composition is small, the processing accuracy at the time of machining is high. Further, since the adhesive strength at the time of the temporary fixing is excellent, sufficient machining durability is exhibited in machining of the object to be machined, falling off or breakage of the part during machining is prevented, and the production yield is improved. Furthermore, by immersing the processed part in water or an aqueous solution of a mixture of water and an organic solvent, it can be peeled off quickly without any defects, thereby contributing to shortening of the process time and improvement of the yield, and good production. Shows sex. In addition, when a visible light polymerization initiator is used as the radical polymerization initiator of the temporary fixing adhesive composition of the present invention, it is simple and short-time, especially for a multi-layered work or an ultraviolet absorbing work object. Can be temporarily fixed by light irradiation, and the productivity can be further improved. Furthermore, if the amount of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) in the adhesive composition for temporary fixing of the present invention is limited, the peeling time can be further shortened, and the productivity is further improved. Can also be improved.

When the temporary fixing adhesive composition of the present invention is peeled off by using the method disclosed in the present invention for immersion in an aqueous solution in which water and a specific water-soluble organic solvent are mixed, the peeling time can be further shortened. It is also possible. Further, by adding the water-soluble adsorption-type corrosion inhibitor disclosed in the present invention to water used as a stripping solution, rust is generated even on parts made of a material such as a metal or a rare earth magnetic material, which is likely to generate rust. The temporary fixing adhesive composition of the present invention can also be applied without causing the problem of the present invention, and the practical problem that often occurred when conventionally using water or an aqueous solution as a stripping solution for these materials is also solved. You. Furthermore, the processing method of the present invention is a method characterized in that after temporarily fixing using the temporary fixing adhesive of the present invention, the mixture is peeled off with water or an aqueous solution of a mixture of water and a specific water-soluble organic solvent. Because there is no need to use harmful or dangerous hydrocarbon solvents or halogen solvents, environmental pollutants are eliminated from the processing of parts, greatly improving environmental protection and work safety. I can do it. Such excellent effects of the present invention are specific effects of the temporary fixing adhesive composition of the present invention obtained when water or water and a specific water-soluble organic solvent are used as a stripping solution, and are disclosed in the present invention. The method for processing the parts described above is achieved by fully exhibiting the features of the temporary fixing adhesive of the present invention.

Tables 1 and 2 are shown below. Further, Table 3 and Table 4 summarize the meanings of the abbreviations of the substances used in the specification and these tables.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

[Table 5]

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J027 AC02 AC03 AC04 AC06 AJ02 AJ08 BA02 BA07 BA08 BA11 BA13 BA14 BA19 CB03 CB09 CB10 CC04 CC05 CD09 4J040 FA011 FA012 FA101 FA102 FA141 FA142 FA171 FA172 FA281 FA282 JB07 KA12 KA13 MA05 MA02 MA06 PA42

Claims (12)

[Claims] 1. An adhesive composition for temporary fixing comprising the following 1), 2) and 3): 1) N, N-dimethylacrylamide, N-vinylcaprolactam, acryloylmorpholine, 2- At least one hydrophilic vinyl monomer selected from the group consisting of hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerol (meth) acrylate; 2) at least one represented by the following structural formula (I) One kind of polyalkylene oxide mono (meth) acrylate However, R1, R2, R3 is H or _CH 3, n is 4-8
And 3) a radical polymerization initiator. 2. The radical polymerization initiator is at least one visible light polymerization initiator selected from the group consisting of camphorquinone, acylphosphine oxide, α-aminoketone, bisacylphosphine oxide, and metallocene. The adhesive composition for temporary fixing according to claim 1, characterized in that: 3. The method according to claim 1, wherein the amount of the at least one polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is 10 to 60% by weight. Adhesive composition for temporary fixing. 4. The radical polymerization initiator is at least one visible light polymerization initiator selected from the group consisting of camphorquinone, acylphosphine oxide, α-aminoketone, bisacylphosphine oxide, and metallocene. The temporary fixing according to claim 1, wherein the amount of the at least one polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is 10 to 60% by weight by weight. Adhesive composition. 5. A part to be processed is temporarily fixed using the adhesive composition for temporary fixing according to claim 1, and after predetermined machining, water or an alcohol, a ketone, or a polyhydric alcohol. The workpiece is immersed in a stripping solution consisting of an aqueous solution of at least one water-soluble organic solvent selected from the group consisting of water-soluble organic solvents selected from the group consisting of water-soluble organic solvents, nitrogen compounds, and sulfur compounds. A method for processing a part, characterized by that: 6. A method for processing a component according to claim 5, wherein the temporary fixing is performed by irradiating the adhesive composition for temporary fixing according to claim 2 with visible light. 7. A method for processing a part according to claim 5, wherein the adhesive composition for temporary fixing according to claim 3 is used. 8. The method according to claim 5, wherein the temporary fixing adhesive composition is temporarily fixed by irradiating visible light. 9. The water-soluble organic solvent is at least one organic solvent selected from the group consisting of methanol, ethanol, 2-propanol, methyl 2-hydroxyisobutyrate, N-methylpyrrolidone, and dimethyl sulfoxide. The mixing ratio is water: water-soluble organic solvent = 3:
The method for processing a part according to any one of claims 5 to 8, wherein the ratio is 97 to 80:20. 10. The stripping solution further comprises at least one water-soluble adsorption-type corrosion inhibitor selected from the group consisting of aliphatic amines, aromatic amines, thiourea and its substituted products, and aldehydes. The component processing method according to any one of claims 5 to 9, wherein the component is contained. 11. An aqueous solution in which at least one water-soluble organic solvent selected from the group consisting of alcohol-based, ketone-based, polyhydric alcohol-based, nitrogen compound-based, and sulfur compound-based water-soluble organic solvents is mixed with water. The stripping solution for an adhesive composition for temporary fixing according to any one of claims 1 to 4, comprising: 12. The adhesive composition for temporary fixing according to claim 1, wherein the adhesive composition is water, or an alcohol, a ketone, a polyhydric alcohol, a nitrogen compound, and a sulfur compound. A temporary adhesive kit comprising a stripping solution composed of an aqueous solution obtained by mixing water with at least one water-soluble organic solvent selected from the group consisting of water-soluble organic solvents.