JPH1171553A - Production of photocurable composition for temporary fixation and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in adhesivity and the releasability or solubility to a releasant liquid and free from variance in performance, by combined use of each a specific water-soluble compound and a water- soluble solvent. SOLUTION: This composition comprises (A) a water-soluble compound bearing one ethylenic unsaturated double bond [e.g. (meth)acryloylmorpholine], (B) a water-soluble organic solvent >200 deg.C in boiling point [for example, 1-100 pts.wt. of diethylene glycol or the like based on 100 pts.wt. of the component A], and (C) a photopolymerization initiator (for example, 0.01-10 wt.% of 2,4,6- trimethylbenzoyl diphenylphosphine oxide or the like based on the component A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the manufacture of various parts such as inorganic parts such as glass parts and ceramic parts, metal parts, and plastic parts, and is preferably used for manufacturing quartz oscillators, glass lenses, plastic lenses and optical disks. In production, after temporarily fixing a plurality of rough-shaped articles as their raw materials and subjecting them to processing, etc., the cured product is washed with water or a water-based cleaning agent to allow the article to be attached and detached. The present invention relates to a composition and a method for producing an article using the composition.

[0002]

2. Description of the Related Art In the production of quartz oscillators, glass lenses, plastic lenses, optical discs, etc., rough-shaped articles, which are the raw materials thereof, are temporarily fixed with an adhesive or the like, and then machined such as cutting or polishing. It is manufactured by applying and processing into a predetermined shape, and then removing the cured product of the adhesive.

Generally, in the processing of a quartz oscillator, about 100 quartz plates are laminated one by one with a hot-melt adhesive and temporarily fixed, and after the processing, the laminate is treated with a high-temperature alkaline aqueous solution to bond the laminate. The cured product of the agent is melted and the temporary fix is removed. However, when a hot-melt adhesive is used for temporary fixing, the bonding operation must be performed in a heating state of about 150 ° C. at the time of bonding. It is necessary to apply the adhesive carefully to each sheet, which has a problem in workability. As an adhesive for temporary fixing that solves these problems, there is a photocurable adhesive (Japanese Patent Publication No. 5-54878,
JP-A-2-88604, etc.). Since the photocurable adhesive is liquid in a light-shielded environment, it does not need to be heated and melted to form a liquid like a hot-melt adhesive, and is excellent in coatability. Further, the lamination of the quartz plates may be performed by impregnating with an adhesive after laminating the quartz plates, and since the impregnated adhesive can be instantaneously fixed by light irradiation, the workability is excellent.

[0004]

However, as in the adhesive disclosed in Japanese Patent Publication No. 5-54878, a (meth) acrylate prepolymer such as urethane (meth) acrylate or polyester (meth) acrylate is mixed with a water-soluble adhesive. A photocurable adhesive consisting of a monomer having an ethylenic double bond can be removed with warm water after processing the laminate, but the cured product of the adhesive is in a film form and is insoluble in water Therefore, when used for a small article such as a quartz oscillator, it is difficult to remove the cured product of the adhesive remaining on the quartz oscillator surface after the article is detached.

In the case of a photocurable adhesive disclosed in JP-A-2-88604, which contains a water-soluble vinyl compound as a main component and does not contain a prepolymer or the like, the adhesive is cured with water or hot water. The product can be dissolved, but the cured product does not have sufficient releasability or solubility with respect to the release liquid, and it may take time to desorb the article, which is satisfactory in terms of productivity. Was not.

As a composition for solving these problems, a composition comprising a water-soluble vinyl compound and water (Japanese Patent No. 25559)
No. 51) and a composition comprising a water-soluble vinyl compound, a foaming agent and a solvent (JP-A-2-140279). However, although the releasability of the cured product is improved according to these compositions, the bonding surface varies due to vaporization of water and solvent contained in the composition due to a temperature rise during light irradiation during bonding. As a result, the adhesiveness of the composition and the desorption property of the cured product thereof are also varied, and there is a problem that the yield particularly in precision processing is increased.

The present inventors have found a photocurable composition for temporary fixing and a method for producing an article, in which the adhesiveness and the cured product thereof are excellent in the releasability or solubility in a release solution and the performance thereof is not varied. For this reason, they conducted intensive studies.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a water-soluble compound having one ethylenically unsaturated double bond and a water-soluble compound having a boiling point exceeding 200 ° C. A photocurable composition used in combination with an organic solvent,
Excellent in adhesiveness and exfoliation or dissolvability with respect to the exfoliation liquid, their performance does not vary, and when manufacturing an article,
The inventors have found that they have excellent workability and productivity, and have completed the present invention. Hereinafter, the present invention will be described in detail. In this specification, an acryloyl group and / or a methacryloyl group is referred to as a (meth) acryloyl group, and an acrylate and / or methacrylate is referred to as a (meth) acrylate.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The first invention of the present invention relates to a water-soluble compound having one ethylenically unsaturated double bond, having a boiling point of 20.
It is a photo-curable composition for temporary fixing comprising a water-soluble organic solvent exceeding 0 ° C. and a photopolymerization initiator. Hereinafter, each component will be described.

(A) Water-soluble compound having one ethylenically unsaturated double bond In the composition of the present invention, a water-soluble compound having one ethylenically unsaturated double bond is used. Thereby, the cured product of the obtained composition can be made to have excellent exfoliation or solubility in a stripping solution, particularly water or an aqueous cleaning agent. In the case of a compound having two or more ethylenically unsaturated double bonds, the cured product has a three-dimensional structure, and thus does not have sufficient release properties and solubility in a release solution.

As the water-soluble compound having one ethylenically unsaturated double bond, various compounds can be used, and a water-soluble (meth) acrylate having one (meth) acryloyl group is preferable. Among water-soluble (meth) acrylates having one (meth) acryloyl group, hydroxyl group-containing (meth) acrylate, nitrogen-containing (meth) acrylate, carboxyl group-containing (meth) acrylate and phosphate group-containing (meth) acrylate The cured product of the composition is preferable because it has excellent releasability or solubility with water or an aqueous cleaning agent.

As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2
Hydroxyalkyl (meth) acrylates such as -hydroxypropyl (meth) acrylate, 2-hydroxy-
Aryl-substituted hydroxyalkyl (meth) acrylates such as 3-phenoxypropyl (meth) acrylate;
Dihydroxyalkyl (meth) acrylates such as 1,2-dihydroxyethyl (meth) acrylate, and 3
And halogen-substituted hydroxyalkyl (meth) acrylates such as -chloro-2-hydroxypropyl (meth) acrylate.

As the nitrogen-containing (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acryloylmorpholine, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminopropylmethyl (meth) acrylamide, etc. (Meth) acrylamide and the like. Among these, (meth) acryloyl morpholine is preferred because the composition has a low odor, a high curing rate, and excellent adhesion to quartz and glass.

Examples of the (meth) acrylate containing a carboxyl group include 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid. Can be

In the phosphoric acid group-containing monomer, 2- (meth)
Acryloyloxyethyl acid phosphate, 1-
(Meth) acryloyloxypropyl-2-acid phosphate and 1-chloro-3- (meth) acryloyloxypropyl-2-acid phosphate are exemplified.

Among these water-soluble (meth) acrylates having one (meth) acryloyl group, the use of a nitrogen-containing (meth) acrylate can improve the adhesiveness of the composition and the releasability or solubility of the cured product. The use of (meth) acryloyl morpholine is preferred because of its excellent balance of primary skin irritation (PII).
Is [P. of acryloylmorpholine. I. I. Is 0.5]
It is more preferable because it is low.

The water-soluble compounds having one ethylenically unsaturated double bond other than (meth) acrylate include N-
And vinylformamide.

These compounds having one ethylenically unsaturated double bond may be used in combination of two or more.

(B) Water-soluble organic solvent having a boiling point exceeding 200 ° C. The water-soluble organic solvent used in the present invention has a boiling point exceeding 200 ° C., preferably 230 ° C. or higher. This makes the composition excellent in adhesiveness to the substrate. Further, since the organic solvent is water-soluble, the cured product thereof has excellent release properties or solubility with a release liquid, particularly water or an aqueous cleaning agent. When a water-soluble organic solvent having a boiling point of 200 ° C. or lower is used, the component in the composition is vaporized by heat generated at the time of light irradiation. Variations occur in the adhesiveness. The upper limit of the boiling point of the water-soluble organic solvent is preferably 500 ° C. In the present invention, the boiling point refers to a value at normal pressure, and in the case of a high boiling water-soluble organic solvent whose boiling point cannot be measured at normal pressure, refers to a value obtained by converting the boiling point measured under reduced pressure to normal pressure. .

Specific examples of the water-soluble organic solvent include diethylene glycol (boiling point (hereinafter abbreviated to 244 ° C.)), dipropylene glycol (231 ° C.), triethylene glycol (270 ° C.), tetraethylene glycol (32 ° C.).
7 ° C.) and alkylene glycols such as polyethylene glycol, diethylene glycol monoethyl ether (2
Alkylene glycol monoalkyl ether such as diethylene glycol monobutyl ether (230 ° C.) and triethylene glycol dimethyl ether (2
Alkylene glycol dialkyl ethers such as 16 ° C); carbonates such as ethylene carbonate (238 ° C); ethanolamines such as diethanolamine (269 ° C) and triethanolamine (360 ° C); lactams such as N-methylpyrrolidone (204 ° C); And alkanolamines such as N-methyl-N, N-diethanolamine (246 ° C.). Among these, alkylene glycols having a boiling point of 230 or more are preferred, and more preferred are diethylene glycol and triethylene glycol which are inexpensive as well as less in odor.

The mixing ratio of the water-soluble organic solvent used in the present invention is preferably 1 to 100 parts by weight based on 100 parts by weight of the water-soluble compound having one ethylenically unsaturated double bond. Preferably it is 5 to 50 parts by weight.
If this ratio is less than 1 part by weight, the cured product of the composition may not be difficult to be sufficiently dissolved or peeled off by water or an aqueous detergent, while if it exceeds 100 parts by weight, the adhesive strength to the substrate May decrease.

(C) Photopolymerization Initiator The photopolymerization initiator used in the present invention may be any compound that generates a radical upon irradiation with ultraviolet light or visible light. Examples of the ultraviolet polymerization initiator include acetophenone-based initiators such as diethoxyacetophenone and benzyldimethyl ketal, benzoin-ether-based initiators such as benzoin and benzoin-ethyl ether, benzophenone-based initiators such as benzophenone and methyl o-benzoylbenzoate, and butanedione. , Benzyl and acetonaphthophenone, etc., and thio compounds such as methylthioxanthone. Examples of the visible light polymerization initiator include camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxylic acid, and 7,7-dimethyl-2,3-dioxo. Bicyclo [2.2.1] heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,
3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester and 7,7-dimethyl-
2,3-dioxobicyclo [2.2.1] heptane-1
-Camphorquinone compounds such as carboxylic acid chloride, and benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6 -Trimethylbenzoyldimethoxyphenylphosphine oxide and 2,4,
Examples include acylphosphine oxide compounds such as 6-trimethylbenzoyldiethoxyphenylphosphine oxide. Some of these have an absorption region in the ultraviolet region. When used for temporary fixing of the laminate, it is preferable to use a visible light polymerization initiator because light is easily transmitted. Further, an acylphosphine oxide compound having a good curing depth is more preferable, and among them, it is particularly preferable to use 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

The compounding ratio of the photopolymerization initiator in the composition is based on the water-soluble compound having one ethylenically unsaturated double bond or the photocurable non-water-soluble monofunctional monomer described below in the composition. When a polyfunctional monomer or oligomer is blended, the amount is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of these. When the amount is less than 0.01% by weight, the photocurability becomes insufficient, and when it exceeds 10% by weight, the cost increases without improving the photocurability.

(D) Other Components Various plasticizers and photocurable oligomers can be added to the composition of the present invention for the purpose of improving the solubility and adhesion of the obtained cured product. Further, for the purpose of improving the adhesiveness, etc., a photocurable water-insoluble monofunctional monomer, polyfunctional monomer and oligomer can be blended in such a ratio that there is no problem in desorption of the cured product.

The photocurable, water-insoluble monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate and cetyl (meth) acrylate. Alkyl (meth) acrylates such as acrylates, cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, aryl (meth) acrylates such as phenyl (meth) acrylate and nonylphenyl (meth) acrylate, benzyl Examples include aryl-substituted alkyl (meth) acrylates such as (meth) acrylate, heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, and cyclic alkenyl (meth) acrylates. That. As the cyclic alkenyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth)
Examples include acrylate and dicyclopentenyloxyalkyl (meth) acrylate such as dicyclopentenyloxypropyl (meth) acrylate.

Examples of the photocurable polyfunctional monomer include ethylene glycol di (meth) acrylate,
Glycol di (meth) acrylates such as tetraethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate, alkylene oxides such as bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct or propylene oxide adduct Di (meth) acrylates of adducts, and polyols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate and alkylene oxide (meth) A) acrylate and the like.

Examples of the photocurable oligomer include urethane (meth) acrylate, epoxy (meth) acrylate and polyester (meth) acrylate.

Urethane (meth) acrylates include:
Reactants of alcohols, organic polyisocyanates and hydroxyl group-containing (meth) acrylates. In this case, examples of the alcohol include lower alcohols such as ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexane dimethanol and 3-methyl-1,5-pentanediol, and polyether polyols such as polyethylene glycol and polypropylene glycol. And polyester polyols obtained from dihydric acids such as adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof. Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

As the epoxy (meth) acrylate,
For example, a reaction product of bisphenol A type epoxy resin or its halogen nucleus-substituted product, or bisphenol F type epoxy resin or its halogen nucleus-substituted product and (meth) acrylic acid can be used.

Examples of the polyester acrylate include ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, trimethylolpropane, and alkylenes thereof. A polyester polyol obtained from an alcohol such as an oxide adduct, and an acid such as an adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid or an anhydride thereof; ) Dehydration condensate with acrylic acid.

In the composition of the present invention, sensitizers such as amine compounds (Michler's ketone), organic peroxides and dyes (specifically, oil-soluble substances such as oil red and Sudan-I) may be used as desired components. Dyes, azo dyes such as Orange II and Seriton Fast Yellow G, quinone imine dyes such as rhodamine B, indigo dye dyes such as indathrene brilliant pink R, anthranquinone dyes such as Sun Red No. 1 and Sun Red LN, White Flow B Fluorescent dyes such as Red No. 2, Red No. 3, Red No. 106, Yellow No. 5
No. 1, Blue No. 1, edible dyes such as Akamin FR-100 and Vermilion No. 101), and a redox-based polymerization initiator and a radical polymerization stabilizer.

(E) Method of Use The composition of the present invention can be preferably used for temporary fixing in the production of various articles such as inorganic parts such as glass parts and ceramic parts, metal parts and plastic parts, and more preferably visible light. Or, it can be used for temporary fixing in the manufacture of crystal parts, glass parts, plastic parts, etc. manufactured from a material that can transmit ultraviolet rays, and more preferably used for temporary fixing in the manufacture of quartz oscillators, glass lenses, plastic lenses, and optical disks. it can.

The second invention of the present invention is a method for processing an article comprising the following steps (1) to (4) using the composition of the first invention. (1) Laminate a plurality of roughly shaped articles via the composition of the first invention. (2) Visible light or ultraviolet light is applied to the laminated rough-shaped articles to cure the composition and temporarily fix the articles together. (3) The temporarily fixed laminate is subjected to mechanical processing to have a predetermined shape. (4) The machined laminate is immersed in water or a water-based cleaning agent to remove or dissolve the cured product of the composition and to remove each article.

In the step (1), as a method of laminating a plurality of coarse articles through the composition of the first invention, various methods are adopted. For example, after a plurality of coarse articles are bundled, (1) A method of impregnating the composition of the present invention. As a method for impregnating the composition of the first invention between the plates of the roughly shaped article, there are an ultrasonic impregnation method and a vacuum impregnation method.

Next, in the step (2), the laminated rough-shaped article obtained in the step (1) is irradiated with visible light or ultraviolet light to cure the composition and temporarily fix the articles together. Irradiation conditions with visible light or ultraviolet light may be appropriately set according to the curing conditions of the composition to be used.

Further, in the step (3), the temporarily fixed laminate is subjected to mechanical processing such as cutting, polishing, and the like to be formed into a predetermined shape.
The method of mechanical processing may be in accordance with the processing method of the target article.

In the step (4), the machined laminate obtained in the step (3) is immersed in a stripping solution capable of peeling or dissolving the cured product of the composition to peel or cure the cured product of the composition. Dissolve and remove each article. Examples of the stripping solution for dissolving or stripping the cured product of the temporarily fixed composition include water, an aqueous cleaning agent, and an organic solvent. The second invention uses water or an aqueous cleaning agent as the stripping solution.
According to the water or water-based cleaning agent, the cured product of the composition of the present invention can be easily dissolved or peeled off, and the water or water-based cleaning agent has no flammability and is inexpensive. Can be manufactured.

As an aqueous cleaning agent, for example, 0.01
Examples thereof include those in which caustic soda of about 20% by weight is dissolved, those in which a household or industrial cleaning agent is blended, and those in which a hydrophilic organic solvent such as ethanol is blended.

Examples of the organic solvent include aliphatic solvents such as nonane, decane and tridecane, cycloaliphatic naphthenic solvents, alkylbenzene solvents such as toluene and xylene, diethylene glycol monoethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether. Glycol ethers, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl isobutyl ketone, and chlorinated solvents such as methylene chloride and trichloroethylene. Thinners obtained by mixing these at any mixing ratio Organic solvents.

As a method for detaching the temporarily fixed material, a method generally used industrially can be employed. For example, the temporarily fixed laminate is immersed in water or an aqueous cleaning agent as it is, and preferably heated to dissolve or peel off the cured product. In this case, operations such as immersion rocking, ultrasonic waves, and bubbling can be added mechanically.

[0041]

The present invention will now be described more specifically with reference to examples and comparative examples. In each example, parts means parts by weight. Example 1 100 parts of acryloylmorpholine, 20 parts of diethylene glycol and 2,4,6-trimethylbenzoyldiphenylphosphine oxide [Lucillin T manufactured by BASF
PO] was mixed to prepare a composition. Using the obtained composition, the following adhesion test and desorption test were performed. Table 1 shows the results.

Adhesion test 25 × 2 of glass test piece (30 × 25 × 8 mm)
The composition was applied to a 5 mm portion, and another same glass test piece was wrapped around the 5 mm portion. After irradiating the test piece with light using a spot-type light irradiation device SPOTCURE (manufactured by Ushio Inc.) and performing temporary bonding,
Furthermore, 4000m by the conveyor type high pressure mercury lamp
The main curing was performed by irradiating light under the condition of J / cm ² . Using the obtained test specimen, the compression shear adhesive strength was measured according to JIS K 6852.

Desorption test 5 × 76 of slide glass (26 × 76 × 1.5 mm)
The composition was applied to the mm portion, and the composition was cured under the same conditions as described above except that another same slide glass was wrapped around the same. The obtained test body is heated with hot water (60 ° C.)
And the time required for desorption was measured.

Examples 2 to 5 Compositions were produced in the same manner as in Example 1 except that the raw materials of the types shown in Table 1 were used in the compositions shown in Table 1. The obtained composition was subjected to an adhesion test and a desorption test in the same manner as in Example 1. Table 1 shows the results.

[0045]

[Table 1] * The numbers in each composition indicate parts. * DEAB: diethylaminobenzophenone

Comparative Examples 1 to 5 Compositions were produced in the same manner as in Example 1 except that the raw materials of the types shown in Table 2 were used in the compositions shown in Table 2. The obtained composition was subjected to an adhesion test and a desorption test in the same manner as in Example 1. Table 2 shows the results.

[0047]

[Table 2] * The numbers in each composition indicate parts. ** DEAB: Diethylaminobenzophenone

The compositions of Comparative Examples 4 and 5 had a boiling point of 200 ° C.
Since less than a water-soluble solvent was added, the adhesive strength and the desorption time varied, and a constant value could not be obtained.

Example 4 100 quartz plates having the same dimensions of 5 mm long × 40 mm wide × 0.4 mm thick were bundled with rubber bands. This was placed in a Petri dish and placed in the Petri dish until the composition of Example 1 was completely submerged. The petri dish containing the bundled quartz plates was placed in a vacuum dryer, the pressure in the vacuum dryer was reduced, and the vessel was degassed under vacuum. Then, the petri dish was taken out of the vacuum dryer.
The bundled quartz plates were taken out of the petri dish, and the laminated surface was irradiated with visible light from above and below to cure and temporarily fix the composition in the gap between the quartz plates. The temporarily fixed quartz plate laminate was machined into the shape of a quartz oscillator, and then the cured product of the composition was dissolved under the same conditions as in Example 1. The children could be removed without any problems, and they had no cured product of the composition. When a test was performed in the same manner using the compositions of Examples 2 to 5 and all compositions were used, a quartz oscillator could be manufactured without any problem.

[0050]

The photo-curable composition for temporary fixing of the present invention has excellent adhesiveness and its cured product has excellent releasability or solubility in a release solution, and furthermore, there is no variation in the performance thereof. When used to produce an article, it is excellent in workability and productivity.

Claims (2)

[Claims] 1. A photocurable composition for temporary fixing comprising a water-soluble compound having one ethylenically unsaturated double bond, a water-soluble organic solvent having a boiling point exceeding 200 ° C., and a photopolymerization initiator. 2. A method for producing an article comprising the following steps (1) to (4). (1) A plurality of roughly shaped articles are laminated via the photo-curable composition for temporary fixing according to claim 1. (2) Visible light or ultraviolet light is applied to the laminated rough-shaped articles to cure the composition and temporarily fix the articles together. (3) The temporarily fixed laminate is subjected to mechanical processing to have a predetermined shape. (4) The machined laminate is immersed in water or a water-based cleaning agent to remove or dissolve the cured product of the composition and to remove each article.