JPH04353411A - Manufacture of molded item - Google Patents

Abstract

PURPOSE:To obtain a molded item having a cubic shape which has high surface hardness and excellent chemical resistance. CONSTITUTION:A hardening sheet 1 having a hardening resin layer formed from hardening resin composition containing acrylic resin having weight-average molecular weight of 50000-1000000 and glass transition point of 40-100 deg.C, compound with reactive vinyl group, initiator for said compound, and microcapsule, in which hardener for activating initiator is sealed, is prepared. Said sheet 1 is attached to the inner surface of a mold 5, following which resin is injected into the mold 5. Since the microcapsule is broken by the pressure of the resin, the hardener sealed in the microcapsule is delivered therefrom to activate the initiator, so that the compound is polymerized.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing molded products that have excellent appearance and surface hardness (scratch resistance) and can be used as office automation equipment, home appliances, sanitary products, etc.

0002

[Prior art] As a method of decorating the surface of plastic products at the same time as molding, there is a method of attaching a pattern to the surface of the mold in advance, and a method of attaching a transfer film to the inner surface of the mold and molding the pattern of the film at the same time as molding. Some methods have been proposed, including a method of transferring the function onto the outer surface of the product, and a method of attaching a functionalized or printed sheet to the inner surface of the mold and then attaching the sheet to the surface of the molded product at the same time as molding.

[0003] Regarding the latter, for example, Japanese Patent Application Laid-Open No. 60-2
No. 50925, Special Publication No. 59-36841,
A method has been proposed in which a weather resistant sheet or a printed sheet is attached to the inner surface of a mold by molding, and then a molded product whose surface is covered with the sheet is injection molded with a molding resin.

0004

[Problem to be solved by the invention] The above-mentioned Japanese Patent Application Laid-Open No. 30-25
In the methods proposed in No. 0925 and Japanese Patent Publication No. 59-36841, decoration and functionality are imparted using thermoplastic sheets or printing transfer, so the surface hardness of the resulting molded products is insufficient. Met. For example, JP-A-60-25092
In the method disclosed in No. 5, when imparting weather resistance to a molded product, a highly weather resistant sheet made of polyvinylidene fluoride (PVDF) or the like may be used, but since this sheet is thermoplastic, it does not have sufficient surface resistance. There is a problem that hardness cannot be obtained. On the other hand, when trying to obtain a molded product with a high surface hardness, it is possible to use a sheet that is cross-linked in advance and has a high hardness, but in this case, the flexibility of the sheet is insufficient, so the three-dimensional It is not possible to produce shaped molded products.

[0005]

[Object of the Invention] The present invention was made to solve the above-mentioned problems, and its purpose is not only to be able to use general-purpose molding resins but also to have high surface hardness, chemical resistance, etc. The object of the present invention is to provide a method for manufacturing a molded article having properties equivalent to or superior to conventional coating performance. Another object of the present invention is to provide a method for manufacturing a molded article that can produce a three-dimensional molded article without any problems.

[0006]

[Means for Solving the Problems] The method for producing a molded article of the present invention has a weight average molecular weight of 50,000-1,000.0.
00, microcapsules encapsulating an acrylic resin with a glass transition point of 40-100°C, a compound having a reactive vinyl group, a polymerization initiator for the compound, and a curing accelerator for activating the polymerization initiator. The above object is achieved by mounting a curable sheet having a curable resin layer formed of the curable resin composition (a) containing the above onto the inner surface of a mold and performing injection molding.

The curable sheet used in the present invention comprises an acrylic resin having a weight average molecular weight of 50,000-1,000,000 and a glass transition point of 40-100°C, a compound having a reactive vinyl group, It has at least one curable resin layer formed of a curable resin composition (a) containing microcapsules encapsulating a polymerization initiator for the compound and a curing accelerator for activating the polymerization initiator. The curable sheet may be, for example, a sheet in which the above-mentioned curable resin layer and a release sheet are laminated, or a sheet in which the above-mentioned curable resin layer and a thermoplastic resin sheet are laminated.

[0008] The above mold release sheet can be used as a sheet for protecting molded products, if necessary. In this case, since it is used after being stretched, it is preferable to use at least a film that is malleable under heating (for example, a thermoplastic resin film or a rubber film).

Examples of the thermoplastic resin film include polyvinyl chloride, polyurethane, acrylic resin, polyester, ethylene-vinyl acetate copolymer, polyethylene, and polypropylene. Examples of the rubber film include natural rubber, styrene-butadiene rubber, nitrile-butadiene rubber, isoprene rubber,
Examples include butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, and acrylic rubber.

[0010] The thermoplastic resin sheet used as the base material of the curable sheet is preferably one that has good adhesion to the injection molding resin, as will be described later.
Examples include BS (acrylonitrile-butadiene-styrene copolymer), vinyl chloride resins, polyolefins such as polystyrene and polypropylene, and fluororesins. Furthermore, if it is desired to increase the surface hardness of the resulting molded product, double bonds such as vinyl groups, (meth)acryloyl groups, and acyl groups may be introduced into some of these materials.

The acrylic resin contained in the curable resin composition (a) is methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (
BMA), methacrylic acid (MAA), or other methacrylate as a main component, and those having a Tg adjusted to 40-100°C are preferably used.

[0012] Furthermore, in order to improve the adhesion between the curable sheet or thermosetting resin layer formed from the curable resin composition (a) and the molding resin, the curable resin composition (a)
It is also possible to include a monomer having a functional group, such as 2-ethylhexyl methacrylate (2-HEMA), 4-hydroxybutyl methacrylate (4-HBMA), etc., as a constituent component.

[0013] Regarding the above-mentioned compound having a reactive vinyl group, it is desirable to use an aliphatic compound having a small number of double bonds per molecular weight, considering the weather resistance of the surface of the molded product obtained. Furthermore, in consideration of the hardness of the surface of the molded product, it is desirable that the number of double bonds per molecular weight is large. For example, allylated cyclohexyl diacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipetaerythritol hexaacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, ditrimethylpropane tetraacrylate, trimethylolpropane triacrylate Examples include modified products and aliphatic urethane acrylates. In particular, those having a molecular weight of 200-600, a number of double bonds of 2-6, and containing a cyclohexyl ring or the like in the structure are more desirable. In addition, in order to improve adhesion and flexibility with the molded product body formed from molded resin, a long-chain monomer containing a hydroxyl group with only one double bond, such as caprolactone-modified 2-HEA, is added. You may.

Regarding the above polymerization initiator, in consideration of the combination with the curing accelerator described below, ketone peroxide, hydroperoxide, diacyl peroxide, which easily undergoes a redox reaction, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, etc. ,
Thermal polymerization initiators such as t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide, and benzoyl peroxide are preferably used. This polymerization initiator is usually stable at room temperature, and even when it coexists with the above compound in the curable resin composition (a), it does not change the compound.

As the curing accelerator used to activate the polymerization initiator, it is preferable to use a redox curing accelerator. As the redox curing accelerator, reducing metal soaps such as cobalt naphthenate, tertiary amines such as dimethylaniline and toluidine are effective, and these are used in microcapsule form.

[0016] This microcapsule is a material that is sufficiently destroyed under the injection molding conditions (resin temperature, injection pressure), and its particle size should be determined by taking into account the sheet film thickness, but it is approximately the pigment particle size (10-20 μm). (below) is preferable, and if the particle size is within this range, there will be no problem in terms of appearance.

In addition to the above-mentioned thermosetting, curable resin composition (
A photopolymerization initiator may be added to a) and the surface hardness may be increased by irradiating with ultraviolet rays after molding. In this case, as the photopolymerization initiator, when the curable resin composition (a) is transparent (that is, when the film formed on the surface of the molded article is transparent), 1-(4-dodecylphenyl) -2-hydroxy-2methylpropane-1
-one, 1-hydroxycyclohexyl phenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylpher)-2-hydroxy-2-methyl-propan-1-one Preferably used.

In addition, when the curable resin composition (a) is colored (that is, when the coating formed on the surface of the molded article is colored), acylphosphine oxide, benzoin isobutyl ether, thioxanthone Benzyl, camphorquinone, etc. are preferably used.

The amount of the compound (monomer) having a reactive vinyl group added is 30 parts by weight per 100 parts by weight of the acrylic resin.
-100 parts by weight is preferred. Regarding the amount of the polymerization initiator and curing accelerator added, if the amount added is large, the storage stability of the curable resin composition (a) will decrease, so it is desirable that the monomer molar ratio is about 1 to 5%. . Further, when a photopolymerization initiator is added, the amount added is preferably about 1 to 5% by weight in view of curability.

The curable resin composition (a) may contain various pigments or colorants such as dyes. Generally known colorants are used, and the amount added is appropriately determined in consideration of the relationship between the hidden film thickness of the coating film formed on the surface of the molded product and the coating film thickness of the molded product. Note that the half-life of peroxide may vary depending on the type of pigment used, so care must be taken.

The method for manufacturing the curable sheet used in the present invention is to thoroughly dissolve and stir the curable resin composition (a) in an organic solvent, etc., and apply the resulting resin liquid to a knife coater, a comma coater, By a casting method such as a reverse coater, 1) a method of casting on a releasable polyethylene terephthalate film (hereinafter referred to as PET film) and drying it, and 2) a method of coating the above resin liquid on a thermoplastic resin sheet and drying it. There is a way to create it. In addition, when coating the above resin liquid on a thermoplastic resin sheet made of polyolefin such as polyethylene (PE) or polypropylene (PP), in order to increase the adhesion between the sheet and the curable resin layer, Apply a primer made of low molecular weight polyolefin onto the resin sheet. Activate the sheet surface in advance by corona discharge, etc. Since it is expensive, it is preferable to do it a little before coating.) The thickness of the thermoplastic resin sheet used in method 2) above varies depending on the injection conditions and solvent resistance, but for example,
ABS (acrylonitrile) is used as a thermoplastic resin sheet.
When using a butadiene-styrene copolymer (butadiene-styrene copolymer) sheet, the thickness is preferably about 200 to 500 μm.

Next, a method for manufacturing a molded article using the curable sheet thus manufactured will be explained. The method can be performed using an apparatus as shown in FIG. This device includes a movable mold 4 having a molding recess 41 and a suction port 42, a sheet cutting device 3, and an air blowing port 21.
It also includes a heating plate 2 having a heater 22, a fixed mold 5, and an injection molding machine 7. A roll 8 is arranged around the movable mold 4 for placing the curable sheet 1 in the recess 41 of the movable mold 4 and moving it sequentially. Above hot plate 2
is configured to be movable between a position near the recess 41 of the movable mold 4 and a position away from the movable mold 4.

[0023] In order to produce a molded product using this apparatus, the curable sheet 1 is formed by forming a curable resin layer 1b and a mold release sheet 1a.
In the case of forming the mold, the curable sheet 1 is first placed at the position of the recess 41 of the movable mold 4, as shown in FIGS. 1(A) and 1(B). Here, the sheet 1 is arranged so that its curable resin layer 1b is located on the molding resin side and the mold release sheet 1a is located on the mold 4 side. Next, move the heating plate 2 to the movable mold 4.
The sheet 1 is moved to the side to soften it, and the sheet 1 is cut into a predetermined size by the cutting device 3. Next, the sheet 1 is attached to the inner surface of the movable mold 4 by blowing out air from the air blowing port 21 of the heating platen 2 toward the sheet 1 side and simultaneously sucking the sheet 1 from the suction port 42 of the movable mold 4. Next, hot plate 2
is moved to the side of the movable mold 4, and the movable mold 4 is moved to the fixed mold 5 side and clamped, and in this state, molding resin is transferred from the injection molding machine 7 to the movable mold 4 and the fixed mold. The molded product is injected and filled into the cavity formed between the mold 5 and the mold 5 to obtain a molded product having a coating made of the sheet 1 formed on the surface.

Further, the curable sheet 1 has a curable resin layer 1a.
and a thermoplastic resin sheet 1b, FIG.
As shown in (A) and (B), first, the recess 4 of the movable mold 4 is
The curable sheet 1 is placed at position 1. Here, the sheet 1 is arranged so that its curable resin layer 1a is located on the mold 4 side and the thermoplastic resin sheet 1b is located on the molding resin side. Next, the hot platen 2 is moved to the movable mold 4 side to soften the sheet 1, and the sheet 1 is cut into a predetermined size by the cutting device 3. Next, air is blown out to the sheet 1 side from the air outlet 21 of the heating plate 2, and at the same time air is blown out from the suction port 42 of the movable mold 4 to the sheet 1 side.
By suctioning the sheet 1, the sheet 1 is attached to the inner surface of the movable mold 4. Next, the hot platen 2 is moved to the side of the movable mold 4, and the movable mold 4 is moved to the fixed mold 5 side to clamp the mold, and in this state, molding resin is injected from the injection molding machine 7 into the cavity. A molded article having a coating made of sheet 1 formed on the surface is obtained by injection filling.

[0025] The temperature of the heating platen 2 depends on the release sheet, the thermoplastic resin sheet, the type of molding resin, the reaction temperature of the thermal polymerization initiator, and the shape of the mold. 50-12 when formed from a layer and a release sheet
When the curable sheet is formed from a curable resin layer and a thermoplastic resin sheet, the temperature is preferably about 100-200°C. Further, the injection conditions may be normal molding conditions.

After that, after opening the movable mold 4, taking out the molded product and removing the release sheet etc.
Sheet 1 is completely cured by standing at 1-2 days at .degree. In addition, when the curable resin composition (a) contains a photopolymerization initiator, the surface hardness can be further increased by irradiating it with 1000 to 10,000 mJ using the ultraviolet irradiation lamp 12 shown in FIGS. 2 and 3. can. In addition,
In FIGS. 2 and 3, 10 is a belt for conveying the molded product 9, 11 is an ultraviolet filter, and 13 is a reflecting plate.

The surface hardness of the molded product obtained in this way depends on the composition of the sheet used, but the surface hardness is HB on a pencil hardness scale.
The above results indicate good chemical resistance.

[0028]

[Operation] The curable resin layer of the curable sheet used in the present invention is a curable resin layer containing pressure-ruptured microcapsules in which an acrylic resin, a compound having a reactive vinyl group, a polymerization initiator, and a curing accelerator are encapsulated. It is formed from a synthetic resin composition (a).

[0029] Accordingly, when the microcapsules in the resin layer collapse due to pressure, the curing accelerator comes out from the microcapsules and activates the polymerization initiator (for example, peroxide). Then, this activated polymerization initiator reacts with the vinyl group of the above compound (monomer) to cause chain polymerization of the compound, and each monomer is crosslinked and cured (for example, the reaction between the curing accelerator and the polymerization initiator The radicals generated by this process start the polymerization reaction of the vinyl compound).

Furthermore, since the molded product is obtained by injecting the resin into the mold with the curable sheet attached to the inner surface of the mold, the pressure at the time of injection is used at the same time as the resin is molded. The curable sheet can be cured by the reaction mechanism described above. Therefore, it is relatively easy to form a coating, and a cured coating can be formed using a curable sheet that is malleable.

Furthermore, a general-purpose resin can be used as the resin for injection molding, and a resin with a weight average molecular weight of 50,000-1,000 can be used as the resin compounded in the curable resin composition.
By using an acrylic resin having a glass transition point of 40 to 100° C., it is possible to form a film that is hard and has excellent chemical resistance.

[0032]

EXAMPLES The present invention will be specifically explained below based on examples. In addition, "part" means "part by weight."

Example 1 Acrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet G1
P8, Mw=approx. 100,000-200,000, Tg
= 80°C), 100 parts of acrylic monomer (Kayarad DPCA-20, manufactured by Nippon Kayaku Co., Ltd., M = 807, number of double bonds: 6), and 30 parts of peroxide (manufactured by Nippon Oil & Fats Co., Ltd., Niper B, 1.6 parts of M = 242) and 0.9 parts of dimethylaniline-encapsulated microcapsules (wall material: gelatin, particle size 20 μm, content weight % = 93%, M = 121) were dissolved in 500 parts of ethyl acetate and mixed. did. This mixture was applied to an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., film thickness 500 μm, hereinafter referred to as the base material) using an applicator, and then dried at 80°C for 30 minutes to form a transparent layer of 50 μm + base material of 500 μm. A curable sheet was created. After heating the sheet thus obtained at 130°C for 30 seconds on a heating plate, it was heated to a size of 100 x 100 x 10 mm.
After vacuum forming into a box-shaped mold, ABS resin was injected to obtain a molded product. This molded article was left at 50° C. for one day to completely cure the sheet.

Example 2 Acrylic polyol (copolymer of methyl methacrylate, butyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate, Mw=360,000, T
g = 70°C, OH value = 20) 100 parts and acrylic monomer (Nippon Kayaku Co., Ltd., Kayarad DPCA-20, M
= 807, double bond number 6), 30 parts of peroxide (manufactured by NOF Corporation, Perloil L, M = 398), and dimethylaniline-encapsulated microcapsules (wall material: gelatin,
Particle size 20 μm, content weight % = 93%, M = 121) 0.
9 parts were dissolved in 500 parts of ethyl acetate and mixed. This mixture was applied to an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., film thickness 5).
00 μm) using an applicator and then dried at 80° C. for 30 minutes to create a curable sheet with a transparent layer of 50 μm and a base material of 500 μm. After heating the sheet obtained in this way at 130℃ for 30 seconds on a heating plate,
The molded product was vacuum-formed into a box-shaped mold with a diameter of 1.5 m, and ABS resin was injected to obtain a molded product. This molded article was left at 20° C. for 3 days to completely cure the sheet.

Example 3 Acrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet G1
P8) 100 parts of acrylic monomer (manufactured by Nippon Kayaku Co., Ltd., Kayarad DPCA-20, M = 807, number of double bonds 6) and 30 parts of peroxide (manufactured by Nippon Oil & Fats Co., Ltd., Niper B
, M = 242) and 0.9 parts of dimethyl para-toluidine-encapsulated microcapsules (wall material: gelatin, particle size 15 μm, content weight % = 93%, M = 135) were dissolved in 500 parts of ethyl acetate. , mixed. This mixture was applied to an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., film thickness 500 μm) using an applicator, and then dried at 80°C for 30 minutes to create a curable sheet with a transparent layer of 50 μm + base material of 500 μm. did. The sheet thus obtained was heated to 130°C and 3
After heating for 0 seconds, the product was vacuum-formed into a box-shaped mold of 100 x 100 x 10 mm to obtain an ABS resin injection molded product. This molded article was left at 50° C. for one day to completely cure the sheet.

Example 4 Acrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet G1
P8) 100 parts of red organic pigment (Lionogen Red YFK, manufactured by Toyo Ink Co., Ltd.) and acrylic monomer (Kayarad DPCA-20, manufactured by Nippon Kayaku Co., Ltd.)
M = 807, number of double bonds: 6), 100 parts of peroxide ((Nipper B, manufactured by NOF Corporation, M = 242), 5.3 parts of dimethylaniline-encapsulated microcapsules (wall material: gelatin, particle size 20 μm, content weight % = 93%, M = 121)
3 parts were dissolved in 500 parts of ethyl acetate and mixed. This mixture was applied to an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., film thickness 5).
00 μm) using an applicator and then dried at 80° C. for 30 minutes to create a curable sheet with a transparent layer of 50 μm and a base material of 500 μm. After heating the sheet obtained in this way at 130℃ for 30 seconds on a heating plate,
The molded product was vacuum-formed into a box-shaped mold with a diameter of 1.5 m, and ABS resin was injected to obtain a molded product. This molded article was left at 20° C. for 3 days to completely cure the sheet.

Example 5 Acrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet G1
P8) 100 parts and red organic pigment (manufactured by Toyo Ink Co., Ltd.,
Lionogen Red YFK) 100 parts and acrylic monomer (Nippon Kayaku Co., Ltd., Kayarad DPCA-20, M
= 807, number of double bonds 6), 100 parts of peroxide (manufactured by NOF Corporation, Niper B, M = 242), and dimethylaniline-encapsulated microcapsules (wall material: gelatin,
Particle size 20 μm, content weight % = 93%, M = 121) 3 parts and a photopolymerization initiator (BASF Corporation, Lucirin TPO,
M=348) was dissolved in 500 parts of ethyl acetate and mixed. This mixture was applied to an ABS sheet (manufactured by Sanpo Jushi Kogyo Co., Ltd., film thickness 500 μm) using an applicator, dried at 80°C for 30 minutes, and a transparent layer of 50 μm +
A curable sheet with a base material of 500 μm was prepared. After heating the sheet thus obtained at 130°C for 30 seconds on a heating plate,
Vacuum formed into a box-shaped mold of x100 x 10mm, ABS
A molded article was obtained by injecting the resin. This molded product was heated to 50℃ for 1
After standing for a day, the surface of the ABS board was irradiated with 5000 mJ of ultraviolet light using a UV irradiation device to completely cure the sheet.

Example 6 Acrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet G1
P8) 100 parts of acrylic monomer (manufactured by Nippon Kayaku Co., Ltd., Kayarad DPCA-20, M = 807, number of double bonds 6) and 30 parts of peroxide (manufactured by Nippon Oil & Fats Co., Ltd., Niper B
, M = 242) and 0.9 parts of dimethylaniline-encapsulated microcapsules (wall material: gelatin, particle size 20 μm, content weight % = 93%, M = 135), and 50 parts of ethyl acetate.
0 parts and mixed. This mixture was applied to a release PET film (manufactured by Lintec Corporation, film thickness: 40 μm) using an applicator, and then dried at 80° C. for 30 minutes to prepare a curable sheet with a transparent layer of 100 μm. After peeling the sheet obtained in this way from the PET film, it was
After heating at °C for 20 seconds, the product was vacuum-formed into a box-shaped mold of 100 x 100 x 10 mm, and ABS resin was injected to obtain a molded product. This molded article was left at 50° C. for one day to completely cure the sheet.

Example 7 Acrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet G1
P8) 100 parts of acrylic monomer (manufactured by Nippon Kayaku Co., Ltd., Kayarad DPCA-20, M = 807, number of double bonds 6) and 30 parts of peroxide (manufactured by Nippon Oil & Fats Co., Ltd., Niper B
, M = 242) and dimethylaniline-encapsulated microcapsules (wall material: gelatin, particle size 20 μm, content wt.
%=93%, M=121) 0.9 part was added to 500 ml of ethyl acetate.
and mixed. This mixture was applied to a release PET film (manufactured by Lintec Corporation, film thickness: 40 μm) using an applicator, and then dried at 80°C for 30 minutes. A cured sheet with a transparent layer of 100 μm was produced by laminating the sheets (20 μm thick). After peeling the sheet obtained in this way from the PET film, it was
After heating at 0° C. for 30 seconds, the product was vacuum-formed into a box-shaped mold of 100×100×10 mm to obtain an ABS resin injection molded product. After peeling off the ethylene-methyl methacrylate film,
This molded article was left at 50° C. for one day to harden the sheet.

Example 8 Acrylic resin (manufactured by Kyowa Gas Chemical Co., Ltd., Parapet G1
P8) 100 parts of acrylic monomer (manufactured by Nippon Kayaku Co., Ltd., Kayarad DPCA-20, M = 807, number of double bonds 6) and 30 parts of peroxide (manufactured by Nippon Oil & Fats Co., Ltd., Niper B
, M = 242) and 0.9 parts of dimethylaniline-encapsulated microcapsules (wall material: gelatin, particle size 20 μm, content weight % = 93%, M = 121), 50 parts of ethyl acetate.
0 parts and mixed. Spread this mixture on an ABS sheet (
After coating with an applicator on a film made by Sanpo Jushi Kogyo Co., Ltd. (film thickness 500 μm), it was dried at 80°C for 30 minutes and laminated with ethylene-methyl acrylate film (PE2255 made by Chevron Chemical, film thickness 20 μm). A curable sheet having a transparent layer of 50 μm and a base material of 500 μm was prepared. The sheet thus obtained was heated on a hot plate at 130° C. for 30 seconds, vacuum-formed into a box-shaped mold of 100×100×10 mm, and ABS resin was injected to obtain a molded product. Ethylene-
After peeling off the methyl methacrylate film, the molded article was left at 50° C. for one day to completely cure the sheet.

Comparative Example A vinyl chloride resin sheet (manufactured by Sekisui Chemical Co., Ltd., Tack Paint Red 50 μm) was coated with an acrylic adhesive (Soken Chemical Co., Ltd.).
ABS sheets (manufactured by Sanpo Jushi Kogyo Co., Ltd., film thickness 5
00 μm), and this laminated sheet was heated to 1
After heating at 30° C. for 30 seconds, vacuum molding was performed into a box-shaped mold of 100×100×10 mm, and ABS resin was injected to obtain a molded product.

Next, Table 1 shows evaluations of the hardness and chemical resistance of the molded products obtained in Examples 1 to 8 and Comparative Examples. In addition, in Table 1, acid resistance is 0.1N sulfuric acid 2
The results of the 4-hour spot test (20°C) were visually observed. Alkali resistance was determined by visually observing the results of a 24-hour spot test (20°C) using 0.1N sodium hydroxide. The hot water resistance was determined by visually observing the results after immersion at 40° C. for 10 days.

[0043]

[Table 1]

[0044]

[Effects of the Invention] According to the present invention, it is possible to produce a molded product having a film that is hard and has excellent chemical resistance, and it is also possible to produce a three-dimensional molded product using a general-purpose resin as an injection molding resin. can be manufactured.

[Brief explanation of drawings]

FIG. 1 (A) is a schematic cross-sectional view of a molded article manufacturing apparatus used in the present invention. (B) is a sectional view of the main parts of the device.

FIG. 2 is a cross-sectional view when a molded article is irradiated with an ultraviolet irradiation lamp to cure its curable sheet.

FIG. 3 is a cross-sectional view when a molded article is irradiated with an ultraviolet irradiation lamp to cure its curable sheet.

[Explanation of symbols]

1 Curable sheet 2 Heat plate 3 Sheet cutting device 4 Movable mold 5 Fixed mold 7 Injection molding machine 8 roll 21 Air outlet 22 Heater 41 Recess for molding 42 Suction port

Claims (1)

[Claims] Claim 1: Weight average molecular weight is 50,000-1,00
0,000, an acrylic resin with a glass transition point of 40-100°C, a compound having a reactive vinyl group, a polymerization initiator for the compound, and a curing accelerator for activating the polymerization initiator were sealed. A method for manufacturing a molded article, which comprises mounting a curable sheet having a curable resin layer formed of a curable resin composition (a) containing microcapsules on the inner surface of a mold and performing injection molding.