JPH0459320A - Manufacture of injection-molded product - Google Patents

Abstract

PURPOSE:To improve the surface hardness, weather resistance and appearance by a method wherein a thermosetting sheet in an uncrued or semicured state is stuck to the inside of a mold by a vacuum and/or air-pressure forming and injection molding of resin is performed within the mold. CONSTITUTION:A movable mold 10, possessing a molding recessed part 10a, a stationary mold 12 possessing protrusion 12a, a hot plate 14, which is arranged between both the molds 10, 12 and movable to the outside of a space between both the molds 10, 12 and a resin injection machine 15 are provided. A sheet 13 is arranged between the movable mold 10 and hot plate 14, the sheet 13 is heated, vacuum and/or air-pressure forming of the sheet 13 is performed and stuck to the inside of the protrusion 12a of the mold 12. The hot plate 14 is taken out of the space between both the molds 10, 12, then the movable mold 10 is moved to a stationary mold 12 side and the mold is clamped. The resin is injected within a cavity formed of both the molds 10, 12 through the resin injection molding machine 15. After molding, a molded product is taken out of the mold, the thermoplastic sheet is cured by an infrared heater under a fixed condition and an injection and an injection molded product is obtained.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention manufactures molded products such as vehicle bodies such as automobiles and bites, daily necessities such as bathtubs and buckets, etc. by injection molding, and further improves appearance and surface appearance. This invention relates to a method for manufacturing molded products in the field where painting, etc. are performed in a post-process to improve hardness and weather resistance.

(Prior Art) In recent years, the bodies of automobiles, motorcycles, etc. have been made of plastic, and daily necessities have been decorated with added value (print transfer, multilayer molding, etc.).

In the case of the former body made of plastic, FRP (1m fiber-reinforced plastic) is used for parts that require strength (impact resistance).

Moreover, when this is used outdoors, painting is performed in a post-process. For example, Japanese Patent Laid-Open No. 61-63424 proposes a method of injection molding a thermosetting resin and applying makeup at the same time.

For the latter method of decoration, a method is called two-color molding, in which a printed ABSSPVC sheet (film) is molded and adhered to the inside of a mold using vacuum or pressure, and then the thermoplastic sheet is pasted by injection molding. There are methods such as injecting resin twice. For example, JP-A No. 60-161122 proposes a method in which a sheet is introduced into a mold and injection molded in a state in which it is brought into close contact with the mold surface by vacuum or pressure forming. Japanese Patent No. 60-195515 proposes a method in which an antifogging treated sheet is introduced into the inside of a mold, and then injection molded and the sheet is affixed to a molded product.

(Problems to be Solved by the Invention) In the fiber-reinforced plastic molded article described above, materials with poor weather resistance, such as unsaturated polyester and styrene monomer, are used, so it is necessary to paint the surface. In that case, since painting is required in a post-process, the work environment deteriorates due to solvents and the like, and the investment cost for painting equipment becomes prohibitive.

Regarding the pasting method of thermoplastic sheets, printing and pasting of thermoplastic sheets are relatively possible, but when hardness is required for the performance of the final molded product, especially when trying to manufacture deep drawn molded products, It is impossible to increase the hardness of the surface.
There were restrictions on the shape of the molded product.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks, and its purpose is to obtain surface hardness, weather resistance, and appearance that are equivalent to or better than conventional coated products. An object of the present invention is to provide a method for manufacturing an injection molded product.

Still another object of the present invention is to provide a method for manufacturing injection molded products that does not require a post-painting step.

(Means for Solving the Problems) The method for manufacturing an injection molded product of the present invention includes a step of attaching an uncured or semi-cured thermosetting sheet to the inner surface of a mold by vacuum and/or pressure forming; and a step of injection molding a resin into the mold, thereby achieving the above object.

The method for producing an injection molded product of the present invention also includes a step of attaching an uncured or semi-cured thermosetting sheet to the inner surface of a mold by vacuum and/or pressure forming, and a step of applying a resin into the mold. The above object is achieved by including the steps of injection molding and curing the thermosetting sheet of the molded article.

Examples of the uncured or semi-cured thermosetting sheet used in the present invention include the following.

■Weight average molecular weight 50.000-1. Goo, 00
A thermosetting sheet in an uncured or semi-cured state whose main components are a reactive acrylic resin of 0.0 and a blocked isocyanate.

■Weight average molecular weight so, ooo~1.000.000
A thermosetting sheet in a semi-cured state, the main components of which are a reactive acrylic resin, a blocked isocyanate, and at least one of a crosslinking agent consisting of an unblocked incyanate, melamine, or epoxy.

The above-mentioned reactive acrylic resin is an acrylic resin having functional groups such as a hydroxyl group, an amine group, and a carboxyl group. For example, (meth)acrylic acid esters having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; 2-7minoethyl (meth)acrylate and 3-amino (meth)acrylic acid ester monomers having 7 amino groups such as propyl (meth)acrylate; (meth)
A monomer material selected from (meth)acrylic acid having a carboxyl group such as acrylic acid; generally, other (meth)acrylic acid esters, styrene derivative monomers, maleic acid monomers, etc. are combined with various peroxides or It is obtained by polymerization using a chain transfer agent or the like as a catalyst.

The above reactive acrylic resin has a weight average molecule jl (Mw)
is so, ooo to 1.000.000, more preferably 100,000 to 800.000.
It is 000.

If the weight average molecular weight is less than so or ooo, the thermosetting sheet will break during vacuum forming, for example, and become cracked, resulting in problems in formability. If the weight average molecular weight of the reactive acrylic resin exceeds 1.000.000, the melt viscosity during preparation will be high and the film forming properties will be poor.

In view of the surface hardness of the injection molded product after curing, for example, when obtaining an injection molded product with a surface hardness of 8 or more by the pencil hardness method, this reactive acrylic resin has a Tg (glass transition point)
is within the range of -20 to 80°C, and the functional group value (usually OH
Base value and NH2 base value (NHf value: NH2 added during polymerization
The amount of groups is calculated in the same way as the OH value, or determined by reacting NH2 groups with nitrous acid and converting them to OH groups) and C0OH
Those having a total base value (Coo) (Value: the amount of CoOH groups added during polymerization calculated in the same manner as the OH value or the value obtained by titrating COOH groups with KOH) are preferably in the range of 20 to 200.

However, when obtaining an injection molded product with a surface hardness that is not very high, for example, 2B or less (23° C.) by the pencil hardness method, it is possible to apply it even outside these ranges.

The reactive acrylic resin can also be used as a block copolymer in which the reactive portion of the acrylic resin is shaped into a block or comb shape. In this case, the materials to be blocked with these reactive acrylic resins include not only acrylic-based materials but also materials that are compatible with styrene-based, maleic acid-based, and imide-based acrylic resins, as well as silicone-based,
It may be combined with any material that can be made into blocks, such as fluorine-based materials. In this case, there are a method in which the weight average molecular weight of this material is within the above range and a method in which these block polymers are blended with the above-mentioned reactive acrylic resin.

The above-mentioned blocked isocyanate is an isocyanate having two or more incyanate groups in the molecule, such as monomeric or modified incyanate groups such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and inphorone diisocyanate. It is blocked (masked). In addition to phenols, block components include oximes, lactams, malonic acid esters, and the like.

This blocked incyanate is one in which blocks are removed by heating and the incyanate group becomes active, and acts as a curing agent for the above-mentioned reactive acrylic resin. The blending ratio of blocked isocyanate and reactive acrylic resin is usually determined by the total number of functional groups in the reactive acrylic resin (
Total functional group value)/Number of isocyanate groups (NC0 value) =
0.5-2.0, preferably 0.8-1.
Make it 2.

The unblocked isocyanate is an incyanate compound having two or more incyanate groups in the molecule. For example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, toridine diisocyanate, triphenylmethane triisocyanate, tris(incyanate phenyl) thiophosphite, p-phenylene diisocyanate, xylylene diisocyanate, bis(isocyanatemethyl)cyclohexane, dicyclohexylmethane Monomers such as diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, or trimethylolpropane adducts of these monomers, incyanurate modified products, biuret modified products, carbodiimide modified products, urethane There are modified forms, allophanate modified forms, etc. The amount of isocyanate added varies depending on the sheet molding method, but NGO has a functional value: NC0 = 1:0.01 with respect to the functional value of the reactive acrylic resin.
It is about 0.3.

In the above thermosetting sheet (■), the melamine crosslinking agents include melamine, urea, thiourea, guanidine, guanamine, acetoguanamine, bensoquanamine,
trimethylolmelamine, hexamethylolmelamine, which is obtained by reacting formaldehyde with a material having polyfunctional amide 7 groups such as dicyandiamide and guanamine;
There are etherified melamine resins made by reacting dimethylolurea, dimethylolguanidine, dimethylolacetoguanamine, dimethylolbensoquanamine, etc. with alcohols such as butyl alcohol and propyl alcohol. The amount of these melamine-based crosslinking agents to be added is difficult to set based on the functional group value of the reactive acrylic resin, unlike isocyanate, so when adding them, conduct a preliminary experiment before making the sheet to determine the amount to be added. is preferable. The amount of the melamine crosslinking agent added is based on the functional value of the reactive acrylic resin: OR (!-f value) = 1: 0.1 to 0
A value of about 3° is preferable.

Examples of the epoxy crosslinking agent include glycidyl compounds, which are polyhydric alcohols containing a plurality of EBO groups, and are usually used together with a Lewis acid catalyst.

The Lewis acid is preferably one that is microencapsulated in order to delay the reaction. For example, butadiene dioxide, diglycidyl ester of hexacindiocytate and phthalic acid, diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, triglycidyl ether amine of para-aminophenol, diglycidyl ether of aniline, phenylene diamine. glycidyl compounds such as tetraglycidyl ether of sulfonamide, diglycidyl ether of sulfonamide, triglycidyl ether of glycerin, polyether-modified diglycidyl, polyester-modified diglycidyl, urethane-modified diglycidyl compound (polymer), vinylcyclohexene dioxide, dicyclopentadiene dioxide, etc. Oxide etc. The amount of this epoxy crosslinking agent added is based on the functional group value of the reactive acrylic resin: CH2CH2O(
Epoxy group ") = 1: 0.01 to 0.2 degree is preferable. Also, since this epoxy crosslinking agent reacts with functional groups to generate OH groups, the amount of blocked isocyanate added at the same time is as follows: It is preferable to add about 30 to 80% of the remaining functional groups of the reactive acrylic resin and the generated OH groups.

Regarding the amount of these crosslinking agents added, the amounts described above are preferred, but in reality, depending on the reactivity with the reactive acrylic resin used, the functional groups of the reactive acrylic resin and the crosslinking agent may interact with each other, for example, melamine-based crosslinking agents may interact with each other. Since a reaction occurs between the crosslinking agent and the epoxy crosslinking agent, it is preferable to conduct a preliminary experiment before making a decision.

Furthermore, when adding an unblocked incyanate, melamine, or epoxy crosslinking agent, it is necessary to reduce the amount of the blocked isocyanate added so that the amount of crosslinking agent in the entire resin sheet does not increase. The ratio is calculated from the above-mentioned functional group value: amount of functional group of the crosslinking agent.

In order to produce the thermosetting sheets described in (1) and (2) above, each of the above-mentioned materials is sufficiently dissolved in an organic solvent, etc., stirred, and processed using a casting method such as a knife coater, comma-futaya, or reverse coater. It is created by coating PET (polyethylene terephthalate, paper, etc.) that has been subjected to mold release treatment, and then drying it to remove the solvent.

Further examples of thermosetting sheets used in the present invention include those shown in the following (1) to (0).

■The main components are a reactive vinyl material having at least a plurality of reactive vinyl monomers and/or oligomers having functional groups, a photopolymerization initiator, and at least one crosslinking agent consisting of (block) incyanate, melamine, and epoxy. A thermosetting sheet in an uncured or semi-cured state is obtained by casting this resin composition and then irradiating it with light to form a film.

■In addition to the resin composition of ■ above, thermoplastic resin and/or
Or a thermosetting sheet obtained by containing a reactive resin.

The above-mentioned reactive vinyl material has a vinyl group, such as (meth)acrylic material, styrene material, and vinyl acetate.

For example, for acrylics, methyl (meth)acrylate,
Monofunctional types such as ethyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxydielene glycol (meth)acrylate; 1,6-hexadiol di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, polyethylene glyfur di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Multifunctional types such as acrylate and dipentaerythritol hexa(meth)acrylate can be applied.

Styrene-based products include styrene, α-methylstyrene, α-
Various styrene derivatives such as ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene, and 0-chlorostyrene may be used.

The reactive vinyl monomer having the above-mentioned functional group is a (meth) having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate.
Acrylic acid ester monomers, (meth)acrylic acid ester monomers having 7 amino groups such as 2-aminoethyl (meth)acrylate and 3-aminopropyl (meth)acrylate; and carboxyl groups such as (meth)acrylic acid. Examples include (meth)acrylic acid.

As the above polymerization initiator, commonly known ones can be used, but
Benzoin alkyl ether, acetophenone, benzophenone, thioxanthone and the like are preferably used. Benzoin ethers include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.; acetophenones include 2,2°-jethoxyacetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methyl Propiophenone, p-ter-butyltrichloroacetophenone, etc.; benzophenone type,
Benzophenone, 4-chlorobenzophenone, 4,4°
-dichlorobenzophenone, 3.3°-dimethyl-4-
Methoxybenzophenone, dibenzosuberone, etc.; thioxanthone types include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, etc. The appropriate amount of the polymerization initiator to be added differs depending on each material, but it is within the range of o, s-s, o parts by weight (hereinafter simply referred to as parts) based on 100 parts by weight of the reactive vinyl monomer. is preferred. Moreover, the polymerization initiator is not limited to one type, but can be used in combination of two or three types.

The materials mentioned above are used as the incyanate, melamine, and epoxy crosslinking agents, and the amount of these crosslinking agents is determined based on the number of functional groups (functional group value). amount (NGO and OR (ether value) and CH2CH20 (
total of epoxy groups) = 〇. About 8 to 1.5 is preferable.

The thermoplastic resin is preferably a material that dissolves in a portion of the reactive vinyl monomer and has good compatibility with the reactive vinyl monomer. For example, there are polyacrylic esters, polystyrene materials, etc., and usually polymethyl methacrylate or polymethyl methacrylate copolymer, polystyrene, polyvinyl acetate, polyvinyl chloride, etc. are used. The amount of the thermoplastic resin added is preferably about 1:0, s to 2 relative to the reactive vinyl monomer.

To obtain a thermosetting sheet, the above resin composition is applied by ordinary casting, and then heated using a high-pressure mercury lamp or
Light is irradiated using a metal halide lamp or a xenon lamp.

A thermosetting sheet in an uncured or semi-cured state, the main components of which are a zero-reactive vinyl monomer and/or oligomer, a thermoplastic resin and/or a vinyl group-containing polymer, and a peroxide.

As the reactive monomers used here, the same reactive monomers as those described above can be used. The same applies to thermoplastic resins.

Any known organic peroxide type peroxide can be used as the peroxide. Preferably, from the viewpoint of storage stability at room temperature,
For example, 2,2-bis(tert-butylperoxy)butane, tert-butylperoxybenzoate, di-t
er-butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, di-ter-butyl peroxide, cyclohexane peroxide, cumene hydroperoxide, benzoyl peroxide, perhexaperoxide, ter-
Butyl peroxy acetate, ter-butyl peroxy isobutyrate, ter-butyl peroxy-3,5
, 5-)limethylhexanoate and the like can be used. The appropriate amount of peroxide to be added varies depending on the material used, but the amount of reactive vinyl monomer 100
parts, preferably within the range of 0.5-4.0 parts. Moreover, the peroxide is not limited to one type, but can be used in combination of two or three types.

This thermosetting sheet is made into a process paper by thoroughly dissolving it in an organic solvent, stirring it, etc., and using a casting method such as a knife coater, comma coater, or reverse coater, in the same way as in the above
Usually, it is made by coating PET (polyethylene terephthalate, paper, etc.) that has been subjected to mold release treatment with silicone, and drying it to remove the solvent.

■Weight average molecular weight 20. Goo~3. Goo, 0
A thermosetting sheet in a semi-cured state whose main components are a reactive silicone resin having a plurality of 00 hydroxyl groups, amino groups, and carboxyl groups and a blocked isocyanate.

■A reactive silicone resin having a plurality of hydroxyl groups, amine groups, and carboxyl groups with a weight average molecular weight of 20.000 to 3.000.000, a block isocyanate, and at least one crosslinking agent consisting of incyanate, melamine, and epoxy; A semi-cured thermosetting sheet whose main component is

■Weight average molecular weight so, ooo~1. Goo, 00
A thermosetting sheet in an uncured or semi-cured state, the main components of which are a reactive fluororesin having a plurality of zero hydroxyl groups, amino groups, and carboxyl groups, and a blocked isocyanate.

■Weight average molecular weight so, ooo~1,000.000
A thermosetting sheet in a semi-cured state, the main component of which is a reactive fluororesin having a plurality of hydroxyl groups, amino groups, and carboxyl groups, and at least one crosslinking agent selected from block incyanate, isocyanate, melamine, and epoxy. .

[Phase] Weight average molecular weight 20.000-2.000.00
An uncured or semi-cured thermosetting sheet whose main components are a reactive polyester resin having a plurality of zero hydroxyl groups, amino groups, and carboxyl groups and a blocked isocyanate.

0 weight average molecular fi20,000~2.000.000
A semi-cured thermosetting material whose main components are a reactive polyester resin having a plurality of hydroxyl groups, amino groups, and carboxyl groups, a block incyanate, and at least one crosslinking agent selected from incyanate, melamine, and epoxy. sheet.

For these materials ① to 0, the main chains are silicone-based, for example, siloxane polymer, etc., and fluorine-based, for example, polyethylene trifluoroethylene, alternating polyethylene and difluoroethylene, etc. Polymers: Introducing hydroxyl, amino, or carboxyl groups into the side chains of various materials such as polyesters, saturated ether types of terephthalic acid and ethylene glycol materials, unsaturated types of terephthalic acid and butadiene, etc. This is what I did.

The relationship between each functional group value and the crosslinking agent is the same as in the above items ① and ②.

Further, the thermosetting sheet obtained in steps 1 to 0 above may contain colorants such as pigments and dyes. As the coloring agent, pigments, dyes, etc. used in ordinary painting can be used. for example,
Examples of pigments include titanium oxide, iron oxide, carbon black, and cyanine pigments; examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes.

Metal powders such as aluminum flakes, nickel powder, gold powder, and silver powder may also be used. Regarding the amount of colorant, when obtaining a thermosetting sheet with high hiding properties, the total amount of colorant is 2 to 40 parts per 100 parts of solid content of the sheet material.
A range of 0 parts is preferred. Furthermore, the thermosetting sheet has
A reaction control catalyst, an inorganic filler, a metal material, an anti-aging agent, a rust preventive agent, etc. may be included for surface control, high functionality, etc.

The thickness of the thermosetting sheet used in the present invention can be determined by the degree of unevenness on the surface of the molded product obtained.

From the viewpoint of sheet formability and cost, a range of about 20 to 500 μm is preferable. Further, the thermosetting sheet may have a plurality of layers laminated. For example, there are combinations of transparent layer/colored layer, transparent layer/thermoplastic resin, etc.

Further, the surface of this sheet may be patterned with printing or unevenness.

Further, these thermosetting sheets may be provided with an adhesive layer on the surface to improve adhesion to the injected resin. Materials constituting the adhesive layer include, for example, EVA (ethylene-vinyl acetate copolymer)-based HM (hot melt) adhesive, 5IS (styrene isoprene-styrene)-based HM adhesive, acrylic-based HM adhesive, unsaturated Examples include uncrosslinked polyester adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, and the like.

Furthermore, a support sheet may be laminated to protect the surface of the thermosetting sheet. The material constituting the support sheet is preferably a material that has heat resistance and excellent vacuum and pressure moldability, such as polyethylene terephthalate, silicone materials, fluorine materials, and the like.

As the injected resin used in the present invention, commonly known injection molding materials are used. For example, polystyrene, acrylic polymer polycarbonate, polyvinyl chloride, polyethylene, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer), modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, polyether ether ketone, polyethylene sulfide, liquid crystal polymer There are thermoplastic resins such as nylon, and thermosetting resins such as glass fiber reinforced polyester, glass fiber reinforced epoxy resin, and glass fiber reinforced acrylic resin.

The injection molded product can be manufactured by the commonly used insert injection molding, for example, as follows.

First, a thermosetting sheet is cut into a predetermined size, placed inside a mold, and brought into close contact with the inner surface of the mold by vacuum and/or pressure forming at room temperature, preferably under heating.

Next, the mold is closed and resin is injected into the mold. The mold temperature may vary depending on the resin used, and when the above-mentioned thermoplastic resin is used as the resin, it may be room temperature. When using a thermosetting resin, it is heated to a predetermined temperature. After that, if the thermosetting sheet is not completely cured,
If necessary, heat the molded product (infrared rays, hot air, etc.) to completely cure the thermosetting sheet. The molded product may be heated within the mold, or may be heated after being removed from the mold. This is usually done by removing the molded product from the mold. The heating temperature and time may be changed as appropriate depending on the composition of the thermosetting sheet.

Applications of the injection molded product obtained by the present invention include automobiles,
Vehicle bodies such as Bites, storage sheds, daily necessities, boats, gardening cases, various housings, doors, etc.

(Effects) According to the present invention, painting is performed simultaneously during the manufacturing process of a molded article. Therefore, the painting of the surface of the molded product, which was conventionally done in the post-process, can be omitted, eliminating the environmental problems associated with painting.
Furthermore, no equipment for painting and heating is required. In addition, an injection molded product with excellent weather resistance and appearance and high surface hardness can be obtained. Therefore, injection molded products suitable for vehicle bodies such as automobiles and motorcycles can be manufactured at low cost.

(Margin below) (Example) The present invention will be explained below based on examples.

■Preparation of thermosetting sheet (1) 300 parts of ethyl acetate, reactive acrylic resin (methyl methacrylate and butyl methacrylate, copolymer of methacrylic acid and 2-aminoethyl acrylate, M w
= 75.000.7g 35℃, Co0H (iifi
20 and NH2 value 40) as a solid content, blocked isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate XB-7)
2. Oxime block of incyanurate of hexamethylene diisocyanate (N CO = 10.1%, solid content 70%) is 31 parts by solid content (this crosslinking agent has 1. 0 equivalents of incyanate groups) were mixed with good stirring. This mixture was applied with an applicator to the release surface of a silicone release-treated polyethylene terephthalate film (hereinafter referred to as PET film), and dried at 70°C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 50 μm.

(2) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and ethyl acrylate,
M w = 250.000.7g 15℃, 08 valence 40
and CoOH value 40) in solid content, and blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-815N).
, hydrogenated para-phenylene diisocyanate ketoxime block NGO = 7.3%, solids content 60%) in a solid content of 59 parts (this crosslinking agent is 1.2 equivalents of the functional group of the above-mentioned reactive acrylic resin). (having an incyanate group) and 2 parts of dibutyltinwaurilate were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 70°C for 30 minutes to obtain a thermosetting sheet. The thickness of the sheet was 200 μm.

(3) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and 4-aminobutyl methacrylate, M w = 368.000 ST g1
0°C, 100 parts solid content of 08 valence 40 and NH2 valence 40), block acrylic polycarboxylic acid (copolymer of stearyl methacrylate and methacrylic acid, Mw = 25,
000, Tg20°C1 acid value 20) in solid content, 10 parts,
Blocked isocyanate (manufactured by Nippon Polyurethane Industries, Ltd.)
Coronate 2513, ethyl acetoacetate block of incyanurate of hexamethylene diisocyanate, NC
0=10.2%, solid content 80%) (this crosslinking agent has 1.0 equivalent of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 70° C. for 15 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(4) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4-aminoethyl methacrylate, M w = 360
．． 000. T g 35°C5OH value 20 and CoOH
20 and NH2 value 40) as a solid content, and blocked isocyanate (manufactured by Ota Pharmaceutical Co., Ltd., Takenate B-8).
15N) (this crosslinking agent has 1.2 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) were mixed with thorough stirring. Add this mixture to PET
It was coated on the release surface of the film with an applicator, dried at 80°C for 5 minutes, and further subjected to initial curing treatment at 160°C for 2 minutes to create a thermosetting sheet.

The initial curing of this thermosetting sheet was determined by infrared absorption analysis (I
From the quantitative determination of R), etc., 10% of the total functional groups were initially cured. The thickness of the sheet was 50 μm.

(5) 400 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, methacrylic acid and 3-aminopropyl acrylate, Mw
= 621. Goo, 7g 10℃, C00H value 40 and N
100 parts of solid content of H2 value 40), block incyanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-815N) 59
(this crosslinking agent has 1.2 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and 100 parts of titanium oxide were mixed with thorough stirring.

This mixture was applied to the release surface of the PET film using an applicator and dried at 80° C. for 5 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(6) 300 parts of ethyl acetate, reactive acrylic resin (methyl methacrylate and butyl methacrylate, copolymer of methacrylic acid and 2-aminoethyl acrylate, M w
= 492.000, Tg35'C, CoOH value 40
and N82 value 40) in solid content, 100 parts of blocked isocyanate (manufactured by Ota Pharmaceutical Co., Ltd., Takene) B-87ON
, oxime block of inphorone diisocyanate keto NC0 = 10.6%, solid content 60%) 23 parts (this crosslinking agent has 0.8
equivalent amount of isocyanate groups), epoxy crosslinking agent (
Manufactured by Civer Geigy, Araldite CY175, Evo Gyushi To 41160. Epoxy value 220 corresponding to functional group value
) 4.9 parts (10% of the functional groups of the reactive acrylic resin are initially cured) were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 80° C. for 5 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(7) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid, M w
= 90.000, Tg15°C1OH number 40 and C0
0H value 40) in solid content, 100 parts blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B-815N) 5
9 parts (this crosslinking agent has 1.2 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and incyanate (manufactured by Nippon Polyurethane Industry ■, Coronate LSNCO = 13.0) in solid content. 15 parts of the reactive acrylic resin (30% of the functional groups of the reactive acrylic resin were initially cured) were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 80° C. for 5 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(8) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and 4-aminobutyl methacrylate, M w = 368.000, Tg 10
℃, OH value 40 and NH2 value 40), solid content 100 parts,
Block copolymer reactive acrylic resin (copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, M w = 36.000, T g 95°C, O
10 parts of solid content of H value 40), blocked isocyanate (manufactured by Nippon Polyurethane Industries ■, Coronate 2513) 4
0 parts (this crosslinking agent is added to the functional groups of the reactive acrylic resin and the flock reactive acrylic resin).

0 equivalent of incyanate groups) and ison-a-fuichito (manufactured by Nippon Polyurethane Industries ■, Coronate L, a polyisocyanate prepared by reacting 3 moles of tolylene diisocyanate and 1 mole of trimethylolpropane NC0
= 13.0%, solid content 75%) and 2.4 parts solids (10% of the total functional groups of the above reactive acrylic resin and block reactive acrylic resin are initially cured) with thorough stirring. did. This mixture was applied to the release surface of the PET film using an applicator and dried at 70° C. for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 60 μm.

(9) 300 parts of ethyl acetate, reactive acrylic resin (methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid and 4 parts of methacrylic acid)
-Copolymer with aminoethyl, MW=480.000
．． 7g 35℃, 100 parts solid content of OH value 2o, CoOH value 2o, NH2 value 40), blocked isocyanate (
Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.) 39 parts (
This cross-linking agent is used for the functional groups of the above-mentioned reactive acrylic resin.
0.8 equivalent of isocyanate group) and a melamine crosslinking agent (Dainippon Ink Chemical Co., Ltd., Super Beckamine (butylated melamine resin) J-820-60) at a solid content of 4.
．． 6 parts (an amount for initial curing of 5% of the functional groups of the reactive acrylic resin) were mixed with stirring.
Coat it on the release surface of the ET film with an applicator,
A thermosetting sheet was obtained by drying at °C for 5 minutes. after that,
Polyhexamethylene terephthalate sheet (50μm)
was heated and laminated. The thickness of the thermosetting sheet is 60
It was μm.

(10) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, methacrylic acid and 3-aminopropyl acrylate, M
w = 621.000, TglO”C, CoOH value 4
0 and NH2 value 40) in solid content, acrylic polycarboxylic acid oligomer (copolymer of ethyl acrylate and acrylic acid, M w = 25.000. T g
-30°C, C00H value 100) in a solid content of 20 parts, and a blocked isocyanate (manufactured by Nippon Polyurethane Kogyo ■, Coronate 2513) in a solid content of 58 parts (this crosslinking agent combines the functional groups of the above-mentioned reactive acrylic resin with acrylic polycarbonate). The solid content of isocyanate (Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) with 1.0 equivalent of incyanate group relative to the carboxyl group in the acid oligomer is 4.4.
(10% of the functional groups of the reactive acrylic resin and the carboxyl groups of the acrylic polycarboxylic acid oligomer are initially cured) 50 parts of phthalocyanine blue were mixed while thoroughly kneading with a triple roll.

Coat this mixture on the release surface of the PET film and
It was dried at C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(11) 70 parts of methyl methacrylate, 15 parts of balanolylphenoxydiethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, 2,4.6-trimethylbenzoyldiphenylphosphine oxide,
8 parts of blocked isocyanate (manufactured by Nippon Polyurethane Kogyo ■, 100% solid content of Coronate 2513, NC0 = 12.8%) 34 parts (1 equivalent of incyanate per total functional group!) This mixture was applied to the release surface of the PET film and irradiated with a metal halide lamp (100 W/cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 80 μl.

(12) 70 parts of methyl methacrylate, 15 parts of balanonylphenoxydiethylene glycol acrylate, 2-
Hydroxyethyl acrylate) 15 parts, 2.4゜6-
2.8 parts of dolimethylbenzoyldiphenylphosphinol and 31 parts of incyanate (manufactured by Shikinichi Pharmaceutical Co., Ltd., Takenate D17ON, incyanurate of hexamethylene diisocyanate NC0 = 20.8%) (total functional groups) 1.2 equivalents of incyane) 1
t) was thoroughly stirred. This mixture was applied to the release surface of the PET film, and a metal halide lamp (100W/cm) was applied.
) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(13) 70 parts of methyl methacrylate, 15 parts of paranonylphenoxydiethylene glycol acrylate, 2-
15 parts of hydroxyethyl acrylate, 2.4°6-drimethylbenzoyldiphenylphosphine oxide
．． 8 parts and incyanate (Shikiichi Yakuhin Kogyo Kousei, Takenate D17ON, incyanurate of hexyl diinocyanate NC0 = 20.8%) 26 parts (1 equivalent of isocyanate based on the total functional group) , 0.01 part of dibutyltin laurylate were thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a metal halide lamp (100 W/cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(14) 70 parts of methyl acrylate, 15 parts of paranonylphenoxydiethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, 2.4.6-)limethylbenzoyldiphenylphosphine oxide 2.8
1 part and 30 parts of melamine crosslinking agent (100% solid content of Super Beckamine (butylated melamine resin) J-820-60, manufactured by Dainippon Ink Chemical Co., Ltd.) (the mixture was thoroughly stirred to ensure sufficient reaction and curing. was coated on the release surface of the PET film and irradiated for 20 seconds with a metal halide lamp (100 W/am) to obtain a thermosetting sheet.The thickness of the sheet was as follows:
It was 100 μm.

(15) 70 parts of methyl acrylate, 15 parts of balanoylphenoquine diethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, 2.8 parts of 2,4.6-drimethylbenzoyldiphenylphosphine oxide
and 52 parts of an epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY175, epoxy weight: jl 160, epoxy value corresponding to the functional group value: 220) (1 equivalent of epoxy to total functional groups) were thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a metal halide lamp (100 W/cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(16) 60 parts of methyl acrylate, 20 parts of phenolic diethyl acrylate, 20 parts of acrylic acid, 2.8 parts of 2,4-diethylthioxanthone and 5.6 parts of isoaminoester of valadimethylaminobenzoic acid, blocked isocyanate (Japan Polyurethane Made by the industrial side, 100% solid content of Fronate 2513, NC0 = 12.8%) 90
(1 equivalent amount of incyanate based on the total functional groups) was stirred well. This mixture was applied to the release surface of the PET film, and a metal halide lamp (100W/
am ) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(17) 60 parts of methyl acrylate, 20 parts of phairoxyethyl acrylate, 10 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 2.8 parts of 2.4-diethylthio bovine santhone and iso-valadimethylaminobenzoic acid 5.6 parts of amino ester and incyanate (Shikinichi Yakuhin Kogyo ■
Takenate D 17ON, Incyanurate of Beef Methylene Diisocyanate NC0=20.8%)
46 parts (1 equivalent of incyanate based on the total functional groups) was stirred. This mixture was applied to the release surface of the PET film, and heated with a high pressure mercury lamp (100 W/cm).
) for 25 seconds to obtain a thermosetting sheet. The thickness of the sheet is 100. It was cxm.

(18) 60 parts of methyl methacrylate, 20 parts of paranonylphenoxydiethylene glycol acrylate, 20 parts of acrylic acid, 2 parts of 2,4-diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid isoamino ester, and incyanate (Ota Pharmaceutical Co., Ltd.) (manufactured by bamboo) D
17ON, hexamethylene diisocyanate 7
NuL/-) NC0 = 20.8%) 55 parts (inocyanate amount of 1 equivalent with respect to the total functional groups) and 0.01 part of dibutyltin laurylate were thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a metal halide lamp (100 W/cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(19) 60 parts of methyl methacrylate, 20 parts of phenoxyethyl acrylate, 20 parts of acrylic acid, 2 parts of 2,4-diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid isoamino ester, and a melamine crosslinking agent (manufactured by Dainippon Ink Chemical Co., Ltd.) , 20 parts (100% solid content of Super Beckamine (phthylated melamine resin) J-820-60) (ff1 which is finally fully reacted and cured) were thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a high-pressure mercury lamp (100 W/cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(20) 60 parts of methyl acrylate, 20 parts of phenoxyethyl acrylate, 20 parts of methacrylic acid, 2.4°6
- 2.8 parts of trimethylbenzoyl diphenylphosphine oxide and 59 parts of epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY 175. Epoxy equivalent INgo, epoxy value 22o corresponding to the functional group value) (1 An equivalent amount of 1 part of epoxy was thoroughly stirred.This mixture was applied to the release surface of the PET film.
A thermosetting sheet was obtained by irradiating for 20 seconds with a high-pressure mercury lamp (100 W, /cm). The thickness of the sheet was 60 μm.

(21) 70 parts of methyl methacrylate, 10 parts of paranonylphenoxydiethylene glycol acrylate, 2-
5 parts of hydroxyethyl acrylate, reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4-aminoethyl methacrylate, M w = 4
80.000.7g 35°C, OHH2O2C00H value 20 and NH2H2O4 solid content 100%) 15 parts, 2,
4.6-) 2.8 parts of lymethylbenzoyldiphenylphosphine oxide and blocked isocyanate (manufactured by Nippon Polyurethane Industries ■, Coronate 2513, solid content 10
0%, NGO=12°8%) 21 parts (1 equivalent of incyanate based on the total functional groups) were thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a metal halide lamp (100 W/cITl) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet is
It was 60 μm.

(22) 40 parts of methyl methacrylate, 15 parts of paranonylphenoxydiethylene glycol acrylate, 2
- 15 parts of hydroxyethyl acrylate, reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, methacrylic acid and 2-aminoethyl acrylate, M w = 492.000, T g 35°C, C0
0H value 40 and NH2H2O4 solid content 100%) 30 parts,
2, 4.6-) 2.8 parts of lymethylbenzoyl diphenylphosphine oxide and incyanate (manufactured by Shikinichi Pharmaceutical Co., Ltd., Takenate D17ON, incyanurate of hexamethylene diisocyanate NC0 = 20.8%)
35 parts (1 equivalent of incyanate based on the total functional groups) were thoroughly stirred. This mixture was applied to the release surface of the PET film, and a metal halide lamp (100W) was applied.
/cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 120 μm.

(23) 40 parts of methyl methacrylate, 15 parts of paranonylphenoxydiethylene glycol acrylate, 2-
15 parts of hydroxyethyl acrylate, reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-methacrylate, diethyl methacrylate, acrylic acid, and 4-aminoethyl methacrylate, M w =
480.000.7g 35℃, OHH2O2C00H value 20 and NH2H2O4 solid content 100%) 30 parts, 2, 4
．． 2.8 parts of 6-trimethylbenzoyldiphenylphosphine oxide and 35 parts of incyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate DI7ON, incyanurate of hexamethylene diisocyanate NC0 = 20.8%) (based on the total functional groups) , 1 equivalent of isocyanate) and 0.01 part of dibutyl lamp urilate were thoroughly stirred. Coat this mixture on the release surface of the PET film,
A thermosetting sheet was obtained by irradiating with a metal halide lamp (100 W/am) for 20 seconds. The thickness of the notebook was 80 μm.

(24) 40 parts of methyl acrylate, 10 parts of paranonylphenoxydiethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, reactive acrylic resin (methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, and methacrylic acid) Copolymer of 4-aminobutyl, M w =368.000.7g
10℃, 08 value 40 and NH2 value 40, solid content 100%)
35 parts, 2.4.6-) 100% solids of 2.8 parts of lymethylbenzoyl diphenylphosphine oxide and melamine crosslinking agent (manufactured by Dainippon Ink Chemical Co., Ltd., Super Beckamine (butylated melamine resin) J-820-60) minute) 60
part (N which finally reacts and hardens sufficiently) was thoroughly stirred. This mixture was applied to the release surface of the PET film and irradiated with a metal halide lamp (100 W/cm ) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(25) 40 parts of methyl acrylate, 15 parts of paranonylphenoxydiethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, reactive acrylic resin (methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, and methacrylic acid) 4-aminobutyl copolymer, Mw=368.000.7g10
°C, 08 value 40 and NH2 value 40, solid content 100%) 35
2.8 parts of 2,4.6-drimethylbenzoyldiphenylphosphine oxide and an epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY175, epoxy equivalent: 160
, epoxy value 220 corresponding to the functional group value) and 45 parts (an amount of epoxy equivalent to 1 equivalent to the total functional group) were thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a metal halide lamp (100 W/cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet is 80μ
It was m.

(26) 60 parts of methyl acrylate, 20 parts of acrylic acid,
Thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpet S)
R8500) 20 parts, 2.8 parts of 2.4-diethylthioxanthone and 5.6 parts of paradimethylaminobenzoic acid isoamino ester, blocked isocyanate (manufactured by Nippon Polyurethane Industry ■, Solid content of Coronate 2513 100
%, NGO = 12.8%) were thoroughly stirred. Coat this mixture on the release surface of the PET film,
A thermosetting sheet was obtained by irradiating with a metal halide lamp (100 W/cm) for 20 seconds. The thickness of the sheet was 80 μm.

(27) 60 parts of methyl acrylate, 10 parts of acrylic acid,
1-10 parts of 2-hydroxyethyl acrylate, thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpet 5R820)
0) 20 parts, 2.4-diethylthioxanthone 2.8
Part and paradimethylaminobenzoic acid isoamino ester 5
．． 6 parts and 46 parts of isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate D17ON, incyanurate of hexamethylene diisocyanate NGO=20.8%) were thoroughly stirred. Coat this mixture on the release surface of the PET film,
A thermosetting sheet was obtained by irradiating the mixture with a high-pressure mercury lamp (100 W/cm2) for 25 seconds. The thickness of the sheet is 100μm
Met.

(28) 60 parts of methyl methacrylate, 20 parts of paranonylphenoxydiethylene glycol acrylate, 20 parts of methacrylic acid, 20 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpet S R8200), 2.4-
2 parts of diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid isoamino ester, and isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate D17ON, incyanurate of hexamethylene diisocyanate NGO = 20゜8
%) and 0.01 part of dibutyl lamp urilate were thoroughly stirred. This mixture was applied to the mold release surface of the PET film, and a metal halide lamp (100W/cm) was applied to the mixture for 20 minutes.
A thermosetting sheet was obtained by irradiation for seconds. The thickness of the sheet is 80
It was μm.

(29) 60 parts of methyl acrylate, 5 parts of phenoxyethyl acrylate, 20 parts of acrylic acid, thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpera) SR8200) 1
5 parts, 2 parts of 2,4-diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid isoamino ester, and 100% of melamine crosslinking agent (Dainippon Ink Chemical Co., Ltd., Super Beckamine (butylated melamine resin) J-820-60)
20 parts (solid content) was stirred. This mixture was applied to the release surface of the PET film, and heated with a high-pressure mercury lamp (100 W/
cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 1100u.

(30) 60 parts of methyl acrylate, 20 parts of methacrylic acid
Part, polystyrene (manufactured by Asahi Kasei Corporation, HI Styron 4
03R) 20 parts, 2.4.6-) 2.8 parts of lymethylbenzoyldiphenylphosphine oxide and an epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY175,
59 parts (epoxy equivalent: 160, epoxy value (corresponding to functional group value: 220)) were thoroughly stirred. Add this mixture to PET
Coat it on the release surface of the film and heat it with a high pressure mercury lamp (100W).
/am) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 300 μm.

(31) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delpet S R8200) 100
parts, 40 parts of 1.6-hexadiol dimethacrylate, 40 parts of neopentyl glycol dimethacrylate,
2.5 parts of ter-butyl peroxyisobutyrate was mixed with good stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 6°C for 30 minutes to obtain a thermosetting sheet. The thickness of the sheet is 60
It was μm.

(32) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delpet S R8200) 100
parts, 50 parts of pentaerythritol trimethacrylate, 40 parts of neopentyl glycol dimethacrylate,
3.5 parts of ter-butylperoxyisobutyrate was mixed with good stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 60°C for 30 minutes to obtain a thermosetting sheet. The thickness of the sheet is 80
It was μm.

(33) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delpet S R8200) 100
parts, p-methoxystyrene 4ow, p-phenylstyrene 40 parts, neopentyl glycol dimethacrylate-1
-20 parts, ter-butyl peroxyisobutyrate 3
．． 5 parts were mixed with good stirring. This mixture is PE
Apply to the release surface of the T film with an applicator and tilt at 60°.
C. for 30 minutes to obtain a thermosetting sheet.

The thickness of the sheet was 60 μm.

(34) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delpet S R+]200) 10
0 parts, pentaerythritol trimethacrylate) 20
part, dipentaerysotol hexamethacrylate 3
0 parts, neopentyl glycol dimethacrylate) 40
1 part, and 4.0 parts of ter-butylperoxyisobutyrate were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator, and heated to 60℃ for 30 minutes.
It was dried for a minute to obtain a thermosetting sheet.

The thickness of the sheet was 80 μm.

(35) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delpet S R'8200) 16
(1 part, 1,6-bexasiol dimethacryle-64
0 parts, neopentyl glycol dimethacrylate 40
1 part, 2.5 parts of ter-butylperoxy-3,5,5-trimethylhexanoate, and 60 parts of titanium oxide were mixed while thoroughly kneading with a triple roll. Add this mixture to PET
It was applied to the release surface of the film using an applicator and dried at 60° C. for 30 minutes to obtain a thermosetting sheet. The thickness of the sheet was 60 μm.

(36) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delpet S R8200) 100
parts, 50 parts of pentaerythritol trimethacrylate, 40 parts of neopentyl glycol dimethacrylate,
3.5 parts of ter-butyl peroxyisobutyrate and 40 parts of iron oxide were mixed while thoroughly kneading with a triple roll.

This mixture was applied to the release surface of the PET film using an applicator and dried at 60°C for 30 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(37) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delpet S R8200) 100
40 parts of p-methoxystyrene, 40 parts of p-phenylstyrene, 40 parts of neopentyl glycol dimethacrylate, 3.5 parts of ter-butylperoxy-3,5,5-trimethylhexanoate, 20 parts of phthalocyanine blue. Mix by thoroughly kneading. This mixture is PE
Apply to the release surface of T film with an applicator and heat at 60℃.
The mixture was dried for 30 minutes to obtain a thermosetting sheet.

The thickness of the sheet was 60 μm.

(38) 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delvet S R8200) 100
parts, pentaerythritol trimethacrylate 20 parts, dipentaerythritol hexamethacrylate 30 parts
parts, 40 parts of neopentyl glycol dimethacrylate, 4.0 parts of ter-butylperoxyisobutyrate,
50 parts of titanium oxide was mixed while thoroughly kneading with a triple roll. This mixture was applied to the release surface of the PET film using an applicator and dried at 60° C. for 30 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(39) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4-aminoethyl methacrylate, MW = 480. 00
0, Tg3S℃, 08 value 20, CoOH value 20 and NH2
100 parts of solid content of 40), blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takene) B-815N) 39
part (this crosslinking agent has 0.8 equivalent of incyanate group with respect to the functional group of the above-mentioned reactive acrylic resin), melamine crosslinking agent (manufactured by Dainippon Ink Chemical Co., Ltd., Super Beckamine (butylated melamine resin) J -820-60) in solid content (an amount for initial curing of 5% of the functional groups of the reactive acrylic resin) was mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 80°C for 5 minutes to form a resin layer. The thickness of the resin layer was 20 μm. This was used as the surface layer.

Next, 500 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delvet S R8200), 40 parts of 1.6-hexadiol dimethacrylate,
Neopentyl glycol dimethacrylate 40 parts, t
2.5 parts of er-butylperoxyisobutyrate were mixed with good stirring.

This mixture was applied over the above-mentioned surface layer using an applicator and dried at 60°C for 30 minutes to form a resin layer. The thickness of the resin layer was 60 μm, and the total thickness of the sheet was 80 μm.

(40) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4-aminoethyl methacrylate, Mw = 360. 00
0.7g35℃, 08 valence 20 and Coo) (valence 20 and NH
100 parts of solid content of divalent 40), blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B-815N) 59
(this crosslinking agent has 1,2 equivalents of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 80° C. for 5 minutes to form a resin layer. The thickness of the resin layer was approximately 20 μm. This was used as the surface layer.

Next, 300 parts of ethyl acetate, a reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, methacrylic acid and 3-aminopropyl acrylate, M w
= 621. Goo, 7g10℃, Coo) (value 4
0 and NH2 value 40) in solid content, blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-815N)
>59 parts (this crosslinking agent has 1.2 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin),
100 parts of titanium oxide was mixed with good stirring.

This mixture was applied over the above-mentioned surface layer using an applicator and dried at 70°C for 20 minutes to form a resin layer. The thickness of the resin layer was 100 μm, and the total thickness of the sheet was 120 μm.

(41) 60 parts of methyl methacrylate, 20 parts of paranonylphenoxydiethylene glycol acrylate, 20 parts of acrylic acid, 2 parts of 2,4-diethylthioxanthone, 4 parts of isoaminoester of valadimethylaminobenzoic acid, and incyanate (Shikinichi Pharmaceutical Co., Ltd. ■Made by Takenate D 1
7ON, incyanure of hexamethylene diisocyanate (NGO = 20.8%) 55 parts (1 equivalent of isocyanate to total functional groups) and 0.01 part of dibutyltinwaurilate were stirred well. This mixture was applied to the release surface of the PET film and irradiated with a metal halide lamp (100 W/cm) for 5 seconds to form a resin layer. The thickness of the resin layer was 20 μm. This was used as the surface layer. Next, 60 parts of methyl methacrylate, 20 parts of phenoxyethyl acrylate, 20 parts of acrylic acid, 2
．． 2 parts of 4-diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid isoamino ester, and a melamine crosslinking agent (
Dainippon Ink Chemical Co., Ltd., Super Beckamine (butylated melamine resin) J-820-60 (100% solids) 2
0 parts (finally fully reacted and cured), 40 parts of titanium oxide was well kneaded with a triple roll. This mixture was coated over the above-mentioned surface layer with an applicator, and then heated with a metal halide lamp (100 W/cm). ) to form a resin layer.The thickness of the sheet was 100 μm.

(42) ) 300 parts of toluene, reactive silicone resin (polymethylpolyol siloxane, weight average molecular weight s
o, ooo, oHHBO2100 parts, blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-, 815N)
47 parts (this crosslinking agent contains 1.
0 equivalents of incyanate groups), titanium oxide 10
0 parts were mixed while thoroughly kneading with three rolls. This mixture was applied to the release surface of the PET film using an applicator and dried at 90° C. for 10 minutes to obtain a thermosetting sheet.

The thickness of the sheet was 100 μm.

(43) 300 parts of toluene, reactive fluororesin (alternating copolymer of ethylene and hydroxytrifluoroethylene,
Weight average molecule j1100,000.08 valence 455) 1
00 parts, 140 parts of blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takefu B-815N) (this crosslinking agent has 0.5 equivalent of incyanate groups with respect to the functional groups of the resin) were stirred well. while mixing. Apply this mixture to the release surface of the PET film using an applicator, and
It was dried at 0°C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(44) 300 parts of toluene, reactive fluororesin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecule j 1250,000.08 valence 455)
100 parts, blocked isocyanate (Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.) 140 parts (this crosslinking agent has 0.5 equivalent of isocyanate group with respect to the functional group of the resin), incyanate (Nippon Polyurethane Kogyo ■) (This crosslinking agent has 0.1 equivalent of incyanate group with respect to the functional group of the resin) was mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 90°C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(45) The sheet obtained in (43) above has a film thickness of 20 μm.
It was manufactured by applying the film to the release surface of the PET film using an applicator so that the film had a thickness of m. Next, 300 parts of toluene, a reactive fluororesin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecule j! 100.0)
00.08 value 455) 100 parts, blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-815N) 1
40 parts (this crosslinking agent is 0.5 parts based on the functional group of the resin)
(having an equivalent amount of incyanate groups) and 20 parts of phthalocyanine blue were mixed while thoroughly kneading with a triple roll.

Coat this mixture onto the above-mentioned sheet with an applicator,
It was dried at 90°C for 10 minutes to form a thermosetting resin layer. The thickness of the resin layer is 100 μm, and the thickness of the sheet is 12 μm.
It was 0 μm.

(46) ) 300 parts of toluene, reactive fluorine resin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight 250.000, O) (value 455
) 100 parts, blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takene) B-815N) 140 parts (this crosslinking agent has 0.5 equivalent of incyanate group with respect to the functional group of the resin), incyanate (Japan) 26 parts of Coronate L (manufactured by Polyurethane Kogyo ■) (this crosslinking agent has 0.1 equivalent of incyanate groups with respect to the functional groups of the resin) were mixed with thorough stirring.

This mixture was applied to the release surface of the PET film using an applicator and dried at 90°C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(47) 300 parts of xylene, reactive polyester resin (
Copolymer of 2-aminoterephthalic acid and hexamethylene glycol, weight average molecular weight 65,000, amide valence 2
26) 100 parts and 111 parts of blocked isocyanate (Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.) (this crosslinking agent has 0.8 equivalents of incyanate groups with respect to the functional groups of the resin) were mixed with thorough stirring. Mixed. This mixture was applied to the release surface of the PET film using an applicator and dried at 90°C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

■Manufacture of injection molded products■-1. Sheet: In Examples 1 to 47, each thermosetting sheet obtained in the above items (1) to (47), which was obtained by peeling off the PET sheet in advance, was used.

In Comparative Examples 1 to 4, the following thermoplastic sheets were used instead of the thermosetting sheets used in the examples.

■PV-C sheet (manufactured by Sanpo Jushi Kogyo■, 0 for vacuum forming)
．． 5 Hard PVC sheet) ■Polystyrene sheet (manufactured by Mitsubishi Monsanto Kasei ■, HT
0.7-extruded sheet of 516) ■ABS sheet (manufactured by Sumitomo Nauga Tabuku ■, 1+o of Talalastic KU-670
m extrusion sheet) ■Acrylic resin sheet (manufactured by Asahi Kasei Corporation, Delvet 5R6500 extrusion sheet) ■-2,
The injection resins Niacrylic resin (polymethyl methacrylate, manufactured by Asahi Kasei Corporation, Delpet 560F) and polycarbonate (manufactured by GE, Lexan 2014) were used as shown in the table below.

■-3, Injection molding Injection molding is performed using the injection molding machine shown in Figure 1.
-I went along the street. This injection molding machine has a recess 10 for molding.
a movable mold 1o having a shape, a fixed mold I2 having a convex portion 12a, and a hot plate 14 disposed between both molds 10.12 and movable outward from between both molds 10.12. , and a resin injection machine 15.

First, as shown in FIG. 1(b), a sheet 13 is placed between the movable mold 10 and the hot plate 14, the sheet 13 is heated, and the sheet 13 is formed by vacuum and/or pressure forming. It was brought into close contact with the inner surface of the convex portion 12a of the mold worker 2. Next, see Figure 1 (
As shown in C), the hot plate 14 is taken out from between the two molds 1o and 12, and then the movable mold 1o is moved to the fixed mold 12.
Move it to the side and close the mold. Next, resin injection machine 1
From step 5, resin was injected into the cavities formed by both molds 10 and 12. The injection molding conditions include a nozzle tip temperature of the resin injection machine of 250°C when injecting acrylic resin and 290°C when injecting polycarbonate.
Polyester resin (manufactured by Showa Kobunshi ■, RN)
C-505) injection molding is performed at a mold temperature of 150℃ after filling.
It was allowed to harden for minutes. After molding, the molded product was taken out from the mold, and the thermosetting sheet was cured using an infrared heater under the conditions shown in the table below to obtain an injection molded product.

In Comparative Examples 1 to 4, the above thermoplastic sheets were used in place of the thermosetting sheets used in the Examples, and injection molded products were obtained by molding under the conditions shown in Table 5.

(2) Measurement of surface performance of injection molded product: The hardness, adhesion, weather resistance, and sharpness of the injection molded product obtained in section [■] were measured.

Performance evaluation Hardness: Pencil hardness (JISK5400) Adhesion second base adhesion test Weather resistance: Sunshine weather meter -Evaluate appearance after 1,000 hours Sharpness: Sharpness gloss test Gd value These measurement results are shown in Tables 1-5.

(The following is a blank space) 4/ Figures 1 (a) to (d) are process diagrams showing the method for manufacturing an injection molded product of the present invention.

that's all

Claims (1)

[Claims] 1. A step of attaching an uncured or semi-cured thermosetting sheet to the inner surface of a mold by vacuum and/or pressure forming, and a step of injection molding a resin into the mold. A method for producing an injection molded product, including: 2. A process of attaching an uncured or semi-cured thermosetting sheet to the inner surface of a mold by vacuum and/or pressure forming, a process of injection molding the resin into the mold, and a process of molding the molded product. A method for producing an injection molded article, comprising: curing the thermosetting sheet.