JP2001293731A - Method for manufacturing resin substrate having coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To apply a coating film good in adhesion on a three-dimensionally crosslinked resin substrate. SOLUTION: In a method for manufacturing a resin substrate having the coating film, the three-dimenhsionally crosslinked resin substrate is taken out of a mold before the completion of the curing of the substrate and the coating film is applied to the substrate and, thereafter, the curing of the substrate is completed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a resin substrate having a coating film, and more particularly, to a method for manufacturing a transparent resin substrate useful in the field of electronic materials and the like.

[0002]

2. Description of the Related Art In recent years, in the field of spectacle lenses and electronic materials, glass products have been converted to plastics because they are light and do not break. Above all, as a substrate for a liquid crystal display, glass having excellent heat resistance, dimensional stability, gas barrier properties and the like is generally used, but various attempts have been made to replace it with plastic. For example, JP-polymethylmethacrylate as No. 59-204545, polycarbonate, polyethersulfone, or on general thermoplastic resins such as polyethylene terephthalate, in turn SiO _x undercoat film, ITO (I
An electrode substrate having an ndium tin oxide) film has been proposed. Further, as in JP-A-5-323303, an example using a three-dimensional crosslinked resin excellent in optical isotropy and surface accuracy has been proposed. As described above, an electrode film such as a SiO ₂ film, a tin oxide film, an ITO film, or the like as a gas barrier film is generally formed on a plastic substrate by vacuum evaporation, sputtering, ion plating, or the like. However, the adhesion of the inorganic film to the organic substrate becomes a problem, and requires a treatment such as providing a primer layer.
In particular, the three-dimensional cross-linked resin has poor adhesion, there is a method such as applying an alkali treatment to the substrate, a plasma treatment, or using an inner mold method in which a monomer is poured into a mold coated with a coating agent in advance and cured. Those which can sufficiently satisfy required characteristics such as productivity and adhesion have not yet been known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a coating film having better adhesion on a three-dimensional crosslinked resin substrate.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the curing of the three-dimensionally cross-linked resin substrate is temporarily stopped, taken out of the mold, applied with a coating liquid, and then cured. Was found to obtain a coating film having excellent adhesion, thereby completing the present invention. That is, the present invention provides a method of manufacturing a three-dimensional crosslinked resin substrate, wherein the substrate is removed from a mold before curing of the substrate is completed, a coating film is applied on the substrate, and then the curing is completed. A method for producing a resin substrate, comprising: curing the substrate by light irradiation, removing the substrate from the mold, applying a coating liquid, and then completing the curing by heat; A method for producing a resin substrate having a coating film, wherein the resin substrate is transparent, or the coating film is generally an organosilicon compound represented by the following general formula (1), and hydrolysis thereof: _{things, R n Si (OR ')} 4-n (1) (R, R' is an organic group having 1 to 10 carbon atoms, n represents an integer of 1 to 4) applying a solution composed mainly of, curing The method for producing a resin substrate having a coating film according to any one of-, wherein the three-dimensionally crosslinked resin substrate is represented by the following general formula (2) in one molecule: 3) a functional group represented by the following general formula (3)
Or (4) a resin (resin-a) obtained by polymerizing a monomer (A) having a functional group represented by the chemical formula (4),

[0005]

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(In the above formula, R ₁ represents a hydrogen atom or a methyl group, and X represents an oxygen atom or a sulfur atom.) Alternatively, the monomer (A) and the following formulas (5), (6) and (7) By copolymerizing a monomer (B) having m (m is an integer of 1 to 6) at least one kind of functional group selected from the group of functional groups represented by (Chem. 2) Resin (resin-b)
A method for producing a resin substrate having a coating film according to any one of the above.

[0007]

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[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a resin substrate having a coating film according to the present invention, the curing of the substrate is temporarily stopped in the middle,
It is characterized in that after being removed from the mold, the coating liquid is applied and curing is completed.

Although any resin can be used as the three-dimensionally crosslinked resin substrate in the present invention, the above-mentioned (resin-a) or (resin-b) is more preferable. (Resin-
a) is a monomer (A) having both a functional group represented by the general formula (1) and a functional group represented by the general formula (2) or (3) in one molecule. A monomer (B) having m (m is an integer of 1 to 6) at least one kind of functional group selected from the functional group group represented by the formulas (4), (5) and (6); ) Is a resin obtained by copolymerizing These (Resin-a) and (Resin-b) are described in JP-A-2-844.
06, JP-A-3-14804, JP-A-3-14804
No. 47817, JP-A-3-72513, JP-A-3-179015, and JP-A-4-2669.
It can be produced by the method described in JP-A-27-27, etc. A functional group represented by the general formula (1) in one molecule;
Examples of the monomer (A) having a functional group represented by the general formula (2) or (3) include, for example, isopropenyl-
α, α-dimethylbenzyl isocyanate and a compound (compound P) having at least either a hydroxyl group or a mercapto group in one molecule and a functional group represented by formula (2) or (3) Is obtained by the reaction of

The compounds P include: 1. Compounds obtained by ring-opening an epoxy group or a thiirane group with acrylic acid or methacrylic acid, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, , 4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, glycerol-1,2-diacrylate,
Glycerol-1,2 dimethacrylate, glycerol-1,3-diacrylate, glycerol-1,3-dimethacrylate, glycerol-1-acrylate-3
-Methacrylates, 2. Ring-opening reactants of acrylic acid or methacrylic acid of phenylglycidyl ethers, for example, 3-phenoxy-2
-Hydroxypropyl acrylate, 3-phenoxy-
2-hydroxypropyl methacrylate, 2,4-dibromophenoxy-2-hydroxypropyl acrylate, 2,4-dibromophenoxy-2-hydroxypropyl methacrylate, 3. Ring opening reaction of acrylic acid or methacrylic acid of bisphenol A-diglycidyl ether Pentaerythritol triacrylate, pentaerythritol trimethacrylate, 5. vinylbenzyl alcohol, vinylthiobenzyl alcohol, 6. bis (acryloyloxyethyl) isocyanurate, bis (methacryloyloxyethyl) isocyanurate, and the like.

That is, the monomer A is a carbamate or a thiocarbamate, for example, by reacting an isocyanate group of isopropenyl-α, α-dimethylbenzyl isocyanate with a hydroxyl group or a mercapto group of the compound P. can get. In this reaction, a tin compound such as dibutyltin dilaurate or dimethyltin dichloride, or an amine such as morpholine or dimethylaminobenzene may be added so that the synthesis reaction proceeds easily. Note that it is preferable to select a tin compound in order to prevent coloring due to a radical reaction at the time of subsequent polymerization. When a solvent is used during the reaction, the solvent is distilled off after the synthesis reaction, and the monomer (A) is obtained without purification or without purification.

As the monomer (A), specifically, N-
(3-isopropenyl-α, α-dimethylbenzyl)-
2-acryloyloxyethyl carbamate, N- (3
-Isopropenyl-α, α-dimethylbenzyl) -2-
Methacryloyloxyethyl carbamate, N- (4-
Isopropenyl-α, α-dimethylbenzyl) -2-acryloyloxyethyl carbamate, N- (4-isopropenyl-α, α-dimethylbenzyl) -2-methacryloyloxyethyl carbamate, N- (3-isopropenyl-α , Α-dimethylbenzyl) -1-acryloyloxypropan-2-ylcarbamate, N- (3
-Isopropenyl-α, α-dimethylbenzyl) -1-
Methacryloyloxypropan-2-ylcarbamate, N- (4-isopropenyl-α, α-dimethylbenzyl) -1-acryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) ) -1,3-Diacryloyloxypropan-2-ylcarbamate, N- (3-isopropenyl-α, α-dimethylbenzyl) -1,3-dimethacryloyloxypropan-2-ylcarbamate, N- (3
-Isopropenyl-α, α-dimethylbenzyl) -1-
Acryloyloxy-3-methacryloyloxypropan-2-ylcarbamate, N- (4-isopropenyl-α, α-dimethylbenzyl) -1,3-diacryloyloxypropan-2-ylcarbamate, N- (3-
Isopropenyl-α, α-dimethylbenzyl) -2,2
-Diacryloyloxymethyl-3-acryloyloxypropylcarbamate, N- (4-isopropenyl-
α, α-dimethylbenzyl) -2,2-dimethacryloyloxymethyl-3-methacryloyloxypropylcarbamate. In addition, as a compound obtained by a reaction between an isocyanate compound and a mercapto group, a compound in which the above carbamate is converted to a thiocarbamate is used.

[0013] The monomer (B) is represented by the above formula (4) or (5)
And m (where m represents an integer of 1 to 6) at least one kind of functional group selected from the functional group group represented by (6), and an ester of acrylic acid or methacrylic acid;
Alternatively, it is a derivative of styrene.

Examples of m = 1 include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, methoxy Ethyl acrylate, methoxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate, glycidyl Acrylate, glycidyl methacrylate DOO, styrene, methyl styrene, chlorostyrene, bromostyrene, chloromethylstyrene, methoxystyrene, and the like.

Examples of the compound having m ≧ 2 include ethylene glycol diacrylate, ethylene glycol methacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol diacrylate, and dipropylene glycol diacrylate. Methacrylate, 2,2-bis (4-acryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, 2, 2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-acryloyloxypropyroylphenyl) propane 2,2-bis (4-methacryloyloxy propylonitrile yl) propane, 1,3
-Butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate,
1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, hydroxypentivalate neopentyl glycol ester diacrylate, spiro glycol diacrylate, spiro glycol dimethacrylate , Epoxy acrylate, epoxy methacrylate, 2-propenoic acid [2- (1,1-dimethyl-2-[(1
-Oxo-2-propenyl) oxy) ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl ester, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate Bis (acryloyloxyethyl) hydroxyethyl isocyanurate, bis (methacryloyloxyethyl) hydroxyethyl isocyanurate, tris (acryloyloxyethyl) hydroxyethyl isocyanurate, tris (methacryloyloxyethyl) hydroxyethyl isocyanurate, petaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentae Sri Tall hexa methacrylate, methyl tri (acryloyloxyethoxy) silane, glycerol diacrylate, glycerol dimethacrylate, dibromo neopentyl glycol diacrylate, divinylbenzene, urethane acrylates,
Urethane methacrylates, 1,1,3,3,5,5-
Hexa (acryloyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (methacryloyloxy) cyclotriphosphazene, 1,1,3,3
5,5-hexa (acryloylethylenedioxy) cyclotriphosphazene and the like.

The monomer (A) is a monomer that can be polymerized alone, and (Resin-a) can be obtained by homopolymerization. Further, (Resin-b) can be obtained by copolymerizing the monomer (A) and the monomer (B). The ratio of the monomers (A) and (B) in this copolymerization cannot be determined unconditionally depending on the type of the functional group of each monomer and the structure of the monomer. Is the monomer (A) based on 1 equivalent of the isopropenylphenyl group in the monomer (A).
A functional group represented by the formula (2) or (3), and
It is preferable that the total of the functional groups represented by the formula (4), (5) or (6) in the monomer (B) is in the range of 0.5 equivalent to 10 equivalent.

Next, a method of manufacturing a substrate used in the present invention will be described. The three-dimensional crosslinked resin substrate of the present invention is preferably a transparent resin substrate. In the method for producing a three-dimensionally crosslinked resin substrate of the present invention, when a monomer solution is injected into a casting polymerization mold and polymerization is cured, polymerization is temporarily stopped, removed from the mold, and a coating liquid is applied, followed by polymerization curing. Is to complete. The term “in the course of polymerization” used herein is not particularly limited as long as the monomer changes from a liquid to a solid and can be taken out of the mold, but is preferably 30 ° C. below the glass transition temperature (Tg) at the time of completion of the polymerization. It is preferable to take out from the mold at a Tg lower than or equal to ° C. Also, when expressed as a gel fraction of the obtained resin substrate, it is preferably 85% to 99%, more preferably 93% to 99%.
It is desirable to be 98%.

The polymerization of the resin used in the present invention is radical polymerization, and not only thermal polymerization but also photopolymerization using ultraviolet rays or γ-rays is possible, and polymerization can be performed by combining these. Although there is no particular limitation on the polymerization method, more preferably, a method of first performing polymerization using light irradiation (preferably ultraviolet light), removing the mold from the mold, applying a coating agent, and then completing the polymerization by heat,
This is preferable as a method for obtaining an adhesive film in a shorter time. The radical polymerization initiator when performing the thermal polymerization is not particularly limited, and known benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropylperoxycarbonate, di-2-ethylhexylperoxycarbonate, t-butylperoxypivalate And azo compounds such as azobisisobutyronitrile. The amount used is from 0.01% by weight to 5% by weight based on the total amount of the monomers. The heating temperature in the thermal polymerization is usually 50 ° C. to 200 ° C., and the heating time is 1 hour to 8 hours. In the method of the present invention, the Tg is 30 ° C. or more lower than the Tg temperature at the time of completion of the polymerization. Thus, the polymerization is stopped at a level lower than the conditions of the respective compositions.

There is no particular limitation on the photosensitizer in the case of curing by ultraviolet light. Known benzoin compounds, benzoin methyl ether, benzoin ethyl ether, 2-hydroxy-2-benzoin propane, azobisisobityronitrile, benzyldimethyl Ketal, diphenyl disulfide and the like can be used, and the amount used is 0.01% by weight to 5% by weight based on the total amount of the monomers. When radiation such as γ-rays is used, generally, a polymerization initiator or the like is not necessarily required. The curing time using ultraviolet rays, γ-rays or the like is not particularly limited as long as it is lower than the conditions of the respective compositions as in the case of thermal polymerization.

In order to prevent the resin substrate of the present invention from being colored or deteriorated with time, and to prevent electrification, an antioxidant,
Alternatively, an antistatic agent or the like can be added. The monomer liquid thus adjusted is subjected to a defoaming treatment, if necessary, to prepare for polymerization.

The casting polymerization mold used in the production of the resin substrate includes two plates selected from glass, metal, FRP and the like, and a sheet of soft vinyl chloride, elastomer, silicone rubber or Teflon (registered trademark) or the like. It comprises a gasket in the shape of a tube or a tube, and a fixture for fixing them. In order to obtain a resin substrate having excellent surface accuracy, a glass plate or an FRP plate preferably has a polished surface, and a metal plate has a plated surface. In the case of thermal polymerization, the material should not be degraded by heat or lack in dimensional stability. The fixing tool may be in any form, but a stationery binder clip or the like can be easily used. As a method for holding the substrate after coating, a method of using a jig that does not impair the shape of the resin or a method of suspending the substrate is simple.

In the production of the resin substrate of the present invention, a release agent is not necessarily required. However, in the case of manufacturing a relatively thin and large-sized resin substrate, a release agent can be used for smoother and better release. At this time, any of an external release agent and an internal release agent can be used as the release agent, but from the viewpoint of rationalization of the molding process, the internal release agent is preferable. The internal release agent can be selected from commonly used internal release agents such as a silicone type, a wax type, a fatty acid metal soap type, a fluorine type, and an acidic phosphate ester type. The amount used is not generally determined by the type of the release agent or the type of the monomer of the resin, but usually, based on the total amount of the monomer,
0.02% by weight to 0.3% by weight. 0.02% by weight
In the following, the effect of the release agent cannot be expected, and even if 0.3% by weight or more is used, there is no change in the releasability. Excessive use tends to cause a decrease in the pot life of the monomer, a change in the resin properties, and the like, and is not preferred. A more preferred internal release agent is an acidic phosphate ester system which has particularly good release performance and is inexpensive and easy to handle. When using an internal release agent,
It is added simultaneously with the addition of the radical initiator and other additives.

The thickness of the resin substrate obtained in the present invention is generally 0.1 to 10 mm, preferably 0.2 to 2.0 mm. When the resin substrate is less than 0.1 mm,
Due to lack of rigidity, handling is difficult, and when it is 10 mm or more, problems such as uneven polymerization are likely to occur.

The coating agent for the coating film provided on both sides or one side of the resin substrate of the present invention is not particularly limited, and any coating agent may be used depending on the application. Examples include acrylic resins, epoxy resins, polyester resins, polyamide resins, urethane resins, phenolic resins, fluorine resins, silicone resins, ethylene-vinyl alcohol polymers, acrylonitrile-butadiene resins ( At least one resin selected from, for example, an ABS resin) and a vinyl chloride-vinyl acetate resin-based polymer, and among them, a silicone-based resin which is difficult to obtain adhesion with a three-dimensional crosslinked resin is useful. . The silicone-based resin is generally used as a primer for providing an inorganic film on plastic, and is generally an organosilicon compound represented by the following general formula (7), a hydrolyzate thereof, and R _n Si (OR ′). _4-n (7) (R and R 'are organic groups having 1 to 10 carbon atoms, n is an integer of 1 to 4) as main components, and if necessary, colloidally dispersed metal oxide fine particles, cured It is obtained by mixing a catalyst, an organic solvent, and the like, preparing, applying, and curing. As the organosilicon compound obtained by the general formula (7), γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane , Γ-mercaptopropyltriethoxysilane,
(3,4-epoxycyclohexyl) ethyltriethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxysilane), trimethylmethoxysilane, dimethyldimethoxysilane, Methyltrimethoxysilane and the like can be mentioned. These can be used alone or in combination of two or more. These organosilicon compounds may be used as they are, but are preferably used as hydrolysates. The hydrolyzate is a product in which part or all of an alkoxy group or an acyloxy group in the silicon compound is substituted with a hydroxyl group, and also includes a product in which the substituted hydroxyl groups partially condense naturally. These hydrolysates are obtained, for example, by hydrolysis in a mixed solvent such as water and alcohol in the presence of an acid.

[0025] These film-forming components containing a silicone resin as a main component include acrylic resins, polyurethane resins, epoxy resins, melamine resins, and polyolefin resins as long as their properties are not impaired. It is also possible to add a polyvinyl alcohol-based resin, a urea resin, a polycarbonate-based resin, or the like.

The coating film is applied by a usual coating method, that is, dip coating, spin coating, spray coating, roll coating, bar coating, flow coating, brush coating or the like. After coating by such a method, usually 50 ° C to 250 ° C, preferably 100 ° C
The curing is completed in the range of -200 ° C. If the resin substrate is subjected to a surface treatment such as an alkali treatment, a plasma treatment, and a sanding process before the application, the adhesion to the substrate is further improved.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not particularly limited thereto. The gel fraction in the examples is J
It was measured by a method according to IS-K-7114 (test method for chemical resistance of plastics). The tests in the examples were conducted by the following methods. A) Appearance: When observed with the naked eye, those having no cracks, rough surfaces or other defects in the coating film were evaluated as (（), and the others were evaluated as (x). B) Adhesion of the coating film: According to JIS-K-5400 (cross-cut peeling test), the sample having 0 squares was evaluated as (○), and the one having peeled was evaluated as (x).

[Adjustment of coating agent] 178.2 parts by weight of isopropyl alcohol was added to 18 parts by weight of vinyltriethoxysilane, and while stirring,
1.28 parts by weight of a 0.01% hydrochloric acid aqueous solution was gradually added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to obtain a coating agent 1. . .Gamma.-glycidoxypropyltrimethoxysilane 10
6.2 parts by weight kept at 10 ° C.
24.3 parts by weight of a 2% aqueous hydrochloric acid solution were gradually added dropwise. After the completion of the dropwise addition, the cooling was stopped to obtain a silane hydrolyzate. To this solution, 125.4 parts by weight of methanol-dispersed colloidal silica (“Methanol Silica Sol” manufactured by Nissan Chemical Co., Ltd., solid content: 30%, average particle diameter: 13 ± 1 μm) was added with stirring, and then 43.5 parts by weight of methanol Parts, 12.5 parts by weight of diethylene glycol dimethyl ether, 0.4 parts by weight of a silicone-based surfactant, 3.8 parts by weight of aluminum acetylacetonate were further added, and the mixture was sufficiently stirred to obtain a coating agent 2.

Example 1 3-Isopropenyl-α, α
-46.7 parts by weight of dimethylbenzyl isocyanate and tris (acryloyloxyethyl) isocyanurate 3
After mixing 2.7 parts by weight, 0.03 parts by weight of dibutyltin dilaurate was added, the internal temperature was maintained at 60 ° C, and 27.0 parts by weight of 2-hydroxyethyl acrylate was gradually added thereto. For 2 hours, and then 13.9 parts by weight of neopentyl glycol dimethacrylate was mixed. 1.16 parts by weight of t-butylperoxy-2-ethylhexanoate was added to the obtained monomer,
Defoaming was performed while mixing. Next, the de-processed monomer liquid is poured into a space of a mold prepared by using two glass plates having a size of 200 mm × 300 mm with a silicon rubber sheet gasket so that the space distance becomes 0.4 mm. After the addition, polymerization was carried out by heating at a temperature of 60 ° C. to 120 ° C. for 3 hours.
A 4 mm resin substrate was obtained. The glass transition temperature of the obtained resin substrate was 180 ° C., and the gel fraction was 93%. The coating agent 1 was applied to this resin substrate with a dip coater and cured in a hot air drying oven at 200 ° C. for 3 hours to obtain a substrate having a coating film with a glass transition temperature of 260 ° C. (gel fraction: 100) %). Table 1 shows the test results of the obtained substrates.

Example 2 The same procedure as in Example 1 was carried out except that coating agent 2 was used as a coating agent.
A substrate having a coating film was obtained. Table 1 shows the test results of the obtained substrates.

Example 3 3-Isopropenyl-α, α
-30.2 parts by weight of dimethylbenzyl isocyanate,
Mix 42.3 parts by weight of tris (acryloyloxyethyl) isocyanurate, and maintain the internal temperature at 50 ° C.
Stir for 0 minutes. Next, dibutyltin dilaurate 0.0
2 parts by weight and 2-hydroxyethyl methacrylate
5 parts by weight were added, and the reaction was carried out for 5 hours while maintaining the internal temperature at 50 ° C. Thereafter, 6.0 parts by weight of diisopropenylbenzene was added to the reaction solution and stirred, and further, Irgacure 65 was added.
1 (manufactured by Ciba Geigy) 0.2 parts by weight, perbutyl O
0.05% (manufactured by NOF CORPORATION) and 0.2 part by weight of an acidic phosphoric acid ester-based internal release agent (trade name: Zelec UN, manufactured by Du Pont) were mixed and then defoamed. This monomer was poured into the same mold as in Example 1, and 3
An 80 W / cm metal halide lamp was irradiated from a distance of 0 cm for 240 seconds. The glass transition temperature of the obtained resin substrate was 130 ° C., and the gel fraction was 97%. The coating liquid 1 was applied to both sides of the resin substrate by a spin coater, and then cured in a hot air drying oven at 200 ° C. for 2 hours to obtain a substrate having a coating film. The glass transition temperature of the obtained substrate was 280 ° C (gel fraction was 10
0%). Table 1 shows the test results.

Example 4 A substrate having a coating film was obtained in the same manner as in Example 3 except that an epoxy overcoating agent (AC5100, manufactured by Nissan Chemical Industries, Ltd.) was used as a coating agent. The glass transition temperature of the obtained substrate was 280 ° C. Table 1 shows the test results.

(Comparative Example 1) The same monomer as in Example 1 was injected into the space of a mold prepared with a silicon rubber sheet gasket, and then placed in a hot air oven and heated from 60 ° C to 120 ° C. Polymerization was performed by heating for 3 hours, removed from the mold, and cured in a hot air drying oven at 200 ° C. for 3 hours.
A resin substrate having a glass transition temperature of 260 ° C. and a gel fraction of 100% was obtained. The obtained substrate was dip-coated with the coating agent 1 and cured in a hot-air drying oven at 120 ° C. for 1 hour to obtain a substrate having a coating film with a glass transition temperature of 260 ° C. Table 1 shows the test results.

Comparative Example 2 A substrate having a coating film was obtained in the same manner as in Comparative Example 1 except that the coating agent was changed to the coating agent 2. Table 1 shows the test results.

Comparative Example 3 The same monomer as in Example 3 was injected into a similar mold, and irradiated with a metal halide lamp of 80 W / cm from a distance of 30 cm from above and below the mold for 240 seconds. The substrate was removed from the mold and cured in a hot air drying oven at 200 ° C. for 2 hours to obtain a resin substrate. The glass transition temperature of the obtained resin substrate is 280 ° C., and the gel fraction is 1
00%. The coating agent 2 is applied on both sides of this resin substrate by spin coating, and is applied in a hot air drying oven for 120 minutes.
The composition was cured at a temperature of 1 ° C. for 1 hour to obtain a substrate having a coating film having a glass transition temperature of 280 ° C. Table 1 shows the test results.

Comparative Example 4 3-Isopropenyl-α, α
To 45.6 parts by weight of dimethylbenzyl isocyanate and 4.7 parts by weight of ethylene glycol, 0.02 parts by weight of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was carried out for 1 hour while maintaining the internal temperature at 40 ° C. To this reaction solution was added 9.8 of 2-hydroxyethyl methacrylate.
The reaction was carried out for 2 hours while maintaining the internal temperature at 50 ° C. Thereafter, 39.9 parts by weight of pentaerythritol tetraacrylate was added to the reaction solution, and the mixture was stirred well. Further, 0.100 part by weight of t-butylperoxy-2-ethylhexanoate was added, and the mixture was stirred well. Foam went. This monomer liquid was poured into the same mold as in Example 1, placed in a hot air oven, and then heated from 60 ° C to 180 ° C.
Polymerization was performed for 3 hours by heating to a temperature of up to ℃ to obtain a resin substrate having a glass transition temperature of 300 ℃ and a gel fraction of 100%. Coating agent 2 was applied on both sides of the obtained resin substrate by spin coating, and cured at 120 ° C. for 1 hour in a hot air drying furnace to obtain a substrate having a coating film having a glass transition temperature of 300 ° C. Table 1 shows the test results.

[0037]

[Table 1]

[0038]

The coating film produced by the method of the present invention can obtain excellent adhesion to a three-dimensionally crosslinked resin substrate.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F203 AG03 AH74 DA12 DB01 DC01 DC08 DJ29 DK02 DL19 4J100 AB02Q AB04Q AB07Q AB08Q AB09Q AL03Q AL08Q AL09Q AL10Q AL62Q AL63Q AL66Q AL67Q AL74P BA02Q BA03Q BA05Q BA34P BA43Q BC34 BC04 BC04 JA44

Claims (5)

[Claims] 1. During the production of a three-dimensional crosslinked resin substrate, the substrate is taken out of a mold before curing of the substrate is completed, a coating film is applied on the substrate, and then the curing is completed. A method for manufacturing a resin substrate. 2. The method for producing a resin substrate according to claim 1, wherein the substrate is cured by light irradiation, removed from the mold, coated with a coating liquid, and then cured by heat. 3. The method for producing a resin substrate having a coating film according to claim 1, wherein the resin substrate is transparent. 4. The coating film generally comprises an organosilicon compound represented by the following general formula (1) and a hydrolyzate thereof: R _n Si (OR ′) _4-n (1) (R, R ′ 4. An organic group having 1 to 10 carbon atoms, wherein n is an integer of 1 to 4). A method for producing a resin substrate having the coating film as described above. 5. The three-dimensional crosslinked resin substrate according to claim 1, wherein
A monomer (A) having both a functional group represented by the following general formula (2) and a functional group represented by the following general formula (3) or (4) (formula 1) is polymerized. Resin (resin-
a), embedded image (In the above formula, R ₁ represents a hydrogen atom or a methyl group, and X represents an oxygen atom or a sulfur atom.) Alternatively, the monomer (A) and the following formulas (5), (6) and (7) A resin obtained by copolymerizing a monomer (B) having m (m is an integer of 1 to 6) at least one kind of functional group selected from the group of functional groups represented by (Formula 2) Resin-b)
A method for producing a resin substrate having a coating film according to any one of claims 1 to 4. Embedded image