JPH09207231A - Decorative molding sheet and method for manufacturing decorative molded article using the sheet - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a decorative molded product having a decorative surface with good surface gloss, good curability, and excellent chemical resistance, solvent resistance, and the like. Further, the present invention also provides a decorative molded product which has a good surface luster even in a large-sized molded product and is less likely to be contaminated on the surface. A decorative molding sheet in which a decorative base material is impregnated with a thermosetting resin composition containing a perhexyl organic peroxide. A decorative molding sheet in which a decorative base material is impregnated with a thermosetting resin composition containing an organic peroxide having a 1-hour half-life temperature of 100 to 130 ° C. Further, it is a method of arranging the decorative molding sheet having the above-mentioned configuration on a thermosetting molding material in a laminated form and performing heat compression molding of the molding material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a decorative molding sheet and a molding material by placing a decorative molding sheet and a thermosetting molding material in a molding die so as to overlap each other and performing heat compression molding. A decorative molding sheet that is used to obtain a decorative molded article that has a desired pattern, color, and other design characteristics by being integrated with the decorative molding sheet, and a decorative molded article using the same Regarding the method.

The decorative molded product thus obtained is suitably used for products having a pattern or color on the surface, such as bathtubs, wall materials for bathtubs, waterproof pans and counters.

[0003]

2. Description of the Related Art Conventionally, FRP (fiber reinforced plastic)
In the field of, especially in the production of FRP bathtubs, bath unit floors, etc., the method called hand lay-up molding method or spray-up molding method has been widely adopted, but these methods produce one product. It took a long time and a lot of work. Then, as a thing that greatly improves these productivity, sheet molding
A thermosetting molding material such as a compound (hereinafter abbreviated as SMC) or a bulk molding compound (hereinafter abbreviated as BMC) has been developed, and a heat compression molding method using the thermosetting molding material is currently widely used.

However, in heat compression molding using only a thermosetting molding material such as SMC or BMC, the color of the entire molded product is limited to a single color. Only red products can be produced as a whole, which reduces the degree of freedom of patterns and colors. Of course, if post-processing such as printing or painting is performed on the molded product, it is possible to add patterns or colors as appropriate, but in this case it is necessary to add complicated post-processing steps, which further increases productivity. descend.

Therefore, as a method of decorating these FRP products, a method of using a decorative molding sheet for expressing a desired pattern in a molded product has been proposed. For example, in Japanese Unexamined Patent Publication No. 5-285973, SMC is superposed on a decorative molding sheet formed by impregnating a titanium paper on which a desired pattern is printed with a thermosetting resin, and heat compression molding is performed. A method for obtaining a decorative molded article is disclosed.

In this publication, each component such as a curing agent contained in a thermosetting resin liquid when obtaining a decorative molding sheet obtained by impregnating the printed titanium paper with a thermosetting resin is specifically described. Although not disclosed, it is presumed that the manufacturing technology for impregnated paper, which has been conventionally used for wallpaper, decorative boards, etc. in building materials, has been diverted. On the other hand, as a conventional resin-impregnated paper used, for example, for producing a thermosetting resin decorative board, an example in which benzoyl peroxide is used as an organic peroxide that is a curing agent for an impregnated resin has been known (Japanese Patent Laid-Open Publication No. Sho. 57-
No. 126666).

[0007]

However, the inventors of the present invention have found that a decorative molding sheet obtained by impregnating a patterned printing paper with a thermosetting resin liquid containing benzoyl peroxide as a curing agent and SMC or the like. The product obtained by arranging in a laminated form and heat compression molding generally has a poor appearance such as gloss on the surface of the decorated part, and also has poor chemical resistance, solvent resistance, stain resistance, etc. I found the drawback of being easy. Specifically, radicals generated from benzoyl peroxide (PhCO
O.) is not particularly highly reactive and is 100%
No completely cured product was obtained. Therefore, the obtained molded product has a poor gloss of the decorated part, and has a drawback that it is inferior in chemical resistance, solvent resistance, etc., and although it is not a problem in normal use, it has durability against chemicals. It could not be used as a required product.

Further, the molded product obtained by the above method is a surface of the decorative portion particularly in the case of a large molded product having a long side of more than 1 m, such as a waterproof pan, a bathtub, and a bathtub with a washing room. In the above, subtle unevenness occurs over a wide range, the gloss at that part is poor, and
It had a defect that the surface was easily polluted.

The present invention remedies the above drawbacks,
The first purpose is to provide a decorative laminated sheet having a design such as a free pattern, a color, etc., which has good surface gloss at the decorative part and good curability. An object is to provide a decorated molded product having excellent chemical resistance, solvent resistance, and the like.

A second object of the present invention is to form a decorative sheet laminated molded product having a design such as a free pattern, a color, etc., even in the case of a large molded product, the surface of the decorated portion. Another object of the present invention is to provide a decorative molded article having good gloss and excellent surface properties such that the surface is unlikely to be contaminated.

[0011]

According to the first aspect of the present invention,
A sheet for decorative molding, which is devised so as to achieve the first object, wherein the decorative base material is impregnated with a thermosetting resin composition containing a perhexyl curing agent. .

The invention according to claim 2 is devised to achieve the second object, and is a thermosetting resin composition containing an organic peroxide having a one-hour half-life temperature of 100 to 130 ° C. The decorative forming sheet is characterized in that the decorative base material is impregnated with the product.

According to the invention of claim 3, the decorative molding sheet is placed on the thermosetting molding material in a laminated form and the compression molding of the molding material is carried out. A method for producing a decorated molded article, characterized in that the method described in 1 or 2 is used.

First, the invention according to claim 1 will be described in detail.

In the present specification, the "decorated base material" means a base material decorated by printing, coloring, or the like.

Examples of the above-mentioned base material, that is, an undecorated base material include fiber aggregates such as paper, cloth, non-woven fabric, glass mat and glass cloth, and porous synthetic resin sheets.

As the paper, various conventionally known papers are used. Specifically, thin paper, titanium paper, newspaper roll paper, high-quality paper, medium-quality paper, waste paper, gravure paper, art paper, coated paper, writing paper, drawing paper, etc. can be used. As the printing method, various conventionally known methods can be applied, and specifically, there are a gravure printing method, a gravure offset printing method, a silk screen printing method, a letterpress printing method, an offset printing method and the like. Further, as a coloring method, various conventionally known methods can be applied, and specifically, there are a method of mixing a pigment and the like at the time of paper making, a method of impregnating ink at the time of paper making, a method of applying paint or a paint.

As the cloth, various conventionally known cloths are used. Specifically, natural fibers such as silk, hemp, and cotton,
It is possible to use those obtained by weaving recycled fibers such as rayon fibers, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers. Further, as the printing method and the coloring method, the same methods as those for the above-mentioned paper can be applied.

As the non-woven fabric, various conventionally known ones are used. Specifically, natural fibers such as silk, hemp, cotton and wool, regenerated fibers such as rayon fibers, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers are chemically or thermally bonded or bonded to each other. It is possible to use a cloth-like material that is made by welding or the like. Further, as the printing method and the coloring method, the same methods as those for the above-mentioned paper can be applied.

As the above-mentioned glass cloth, a conventionally known one obtained by weaving glass fibers can be used. Also,
As the printing method and the coloring method, the same methods as those for the above-mentioned paper can be applied.

As the above-mentioned glass mat, it is possible to use a glass mat which is chemically bonded to glass fibers with an adhesive (binder) to form a mat. Further, as the printing method and the coloring method, the same methods as those for the above-mentioned paper can be applied.

Here, as a mode of coloring or printing,
It may be colored in a single color or a pattern such as a pattern may be formed by using a plurality of colors. That is, it is possible to apply a free pattern or color according to the purpose.

The thermosetting resin composition with which the decorative base material is impregnated contains a thermosetting resin as a main component, and may contain an inorganic filler and a coupling agent, if necessary.

As the thermosetting resin which is the main constituent of the thermosetting resin composition, various thermosetting resins such as unsaturated polyester resin, epoxy acrylate resin, urethane acrylate resin, diallyl phthalate resin, melamine resin and phenol resin can be used. Resin can be used.

The above-mentioned unsaturated polyester resin is usually produced by a known and commonly used method, usually an organic polyol, an aliphatic unsaturated polycarboxylic acid and, if necessary, an aliphatic saturated polycarboxylic acid and / or an aromatic polycarboxylic acid. Manufactured from etc.

Examples of organic polyols used for producing the above unsaturated polyester resin include diols, triols, tetraols and mixtures thereof.
Organic polyols are mainly divided into aliphatic polyols and aromatic polyols, and of these, typical aliphatic polyols include ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, dibromoneopentyl. Glycol, hexamethylene glycol, trimethylolpropane, hydrogenated bisphenol A, and the like. Typical aromatic polyols are bisphenol A or bisphenol S, or these bisphenol A or bisphenol S with ethylene oxide, propylene oxide, or butylene. Polyoxyalkylene bisphenol A or polyoxyalkylene bisphenol A obtained by adding an average of 1 to 20 aliphatic oxirane compounds such as oxides in one molecule There is a polyoxyalkylene bisphenol S and the like.

Examples of the aliphatic unsaturated polycarboxylic acid used for producing the above unsaturated polyester resin include (anhydrous) maleic acid, fumaric acid and (anhydrous) itaconic acid.

Examples of the aliphatic unsaturated polycarboxylic acid used in the production of the unsaturated polyester resin include sebacic acid, adipic acid, (anhydrous) succinic acid and the like.

Examples of the aromatic polycarboxylic acid used for producing the unsaturated polyester resin include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, methyltetrahydrophthalic anhydride and endomethylenetetrahydrophthalic anhydride. It

The above-mentioned epoxy acrylate (vinyl ester) resin is usually prepared by a known and commonly used method.
It is produced from an epoxy resin and a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid.

Further, as the epoxy resin used for producing the epoxy acrylate (vinyl ester) resin, bisphenol A type epoxy resin, epichlorohydrin and brominated bisphenol which are also produced from epichlorohydrin and bisphenol A by a known and conventional method. Brominated bisphenol A type epoxy resin produced from A, novolak type epoxy resin produced by glycidyl etherification of phenol novolac or orthocresol novolac, glycidyl amine type epoxy resin obtained by reacting various amines with epichlorohydrin (tetraglycidyl Metaxylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl diaminodiphenylmethane, triglycidyl p- aminophenol, triglycidyl -m- aminophenol, diglycidyl aniline, diglycidyl ortho-toluidine, etc.) and the like.

The urethane acrylate resin is usually
It is produced by reacting an organic polyol such as an alkylene diol, an alkylene diol ester, an alkylene diol ether, a polyether polyol or a polyester polyol with an organic polyisocyanate, and further reacting with a hydroxyalkyl (meth) acrylate.

As the polyol used for producing the urethane acrylate resin, alkylene diols such as ethylene glycol, propylene glycol, diethylene glycol, diisopropylene glycol, polyethylene glycol, polypropylene glycol, butane diol are used as polyether polyols. Is polyoxymethylene, polyethylene oxide,
Examples of polypropylene oxide include polyester polyols such as organic polyols such as alkylene diols and polycarboxylic acid condensation compounds.

Examples of the polyisocyanate used for producing the urethane acrylate resin include tolylene diisocyanate, isophorone diisocyanate and polymethylene polyphenyl diisocyanate.

Examples of the hydroxyalkyl (meth) acrylate used for producing the urethane acrylate resin include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. Is usually attached to the beta carbon of the alkyl group. Alkyl groups can usually contain up to 8 carbon atoms.

The diallyl phthalate resin is obtained by heating and polymerizing a diallyl phthalate monomer in the presence of a peroxide catalyst such as benzoyl peroxide to form a prepolymer.

The above melamine resin is obtained by condensing melamine and formaldehyde resin.

The above-mentioned phenol resin is obtained by reacting phenol alcohols with formalin. Two types are general-purpose: a resol type in which formaldehyde is excessive with respect to phenol and reacted with an alkali catalyst, and a novolac type in which formaldehyde is excessively reacted with an acid catalyst.

The thermosetting resin is usually styrene,
α-methylstyrene, divinylbenzene, vinyltoluene, diallyl phthalate, various acrylate monomers,
An appropriate amount of a polymerizable monomer such as various methacrylate monomers is added.

Among them, styrene and methyl methacrylate are preferably used because they are excellent in price and various performances.

If desired, an organic peroxide can be used as a radical reaction initiator in the thermosetting resin. Specifically, for example, ketone peroxides such as methyl ethyl ketone peroxide, diacyl peroxides such as isobutyryl peroxide, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, and tertiary Alkyl peresters such as butyl peroxy-2-ethylhexanoate, carbonates such as tertiary butyl peroxy isopropyl carbonate, peroxy ketals such as 1,1-dibutyl peroxycyclohexane, etc. For example, tertiary butyl peroxybenzoate, tertiary butyl peroxy isopropyl carbonate, etc. can be used.

The thermosetting resin composition contains, as a curing agent, a perhexyl organic peroxide which is a radical polymerization initiator. The perhexyl organic peroxide has the general formula [C
₃ H ₇ C (CH ₃ ) ₂ OOR],
Reactive tertiary hexyloxy radical [C
₃ H ₇ C (CH ₃ ) ₂ O ·] is generated, and a crosslinking agent reacts with a resin having an unsaturated double bond to cure the resin.

The perhexyl organic peroxides are roughly classified into perhexyl peroxyesters, perhexyl hydroperoxides and perhexyl peroxyketals.

Specific examples of such organic peroxides include, for example, peroxyesters: tertiary hexylperoxy neodecanoate (1 hour half-life temperature 64.8 ° C.) tertiary hexylper Oxypiparate (1 hour half-life temperature 71.3 ° C) -Tertiary hexyl peroxy-2-ethylhexanoate (1 hour half-life temperature 90.1 ° C) -Tertiary hexyl peroxyisopropyl carbonate (1 hour half-life) There is a tertiary hexyl peroxybenzoate (1 hour half-life temperature 119.2 ° C.) and the like, and as hydroperoxides: tertiary hexyl hydroperoxide (1 hour half-life temperature 188. 5 ° C) and as peroxyketals: 1,1-bis (ta -Sharily hexyl peroxy)-
3,3,5-trimethylcyclohexane (1 hour half-life temperature 106.4 ° C.) and 1,1-bis (tert-hexylperoxy) cyclohexane (1 hour half-life temperature 107.3 ° C.).

Of the above-mentioned perhexyl organic peroxides,
The one-hour half-life temperature is 100 to 130 ° C, and more preferably 1
Those having a temperature of 03 to 126 ° C, more preferably 105 to 120 ° C are preferably used. If the 1-hour half-life temperature is too low, pre-gel tends to occur during the molding because the reaction starts too early. Conversely, if the 1-hour half-life temperature is too high, the reaction rate is too slow and the curing tends to be insufficient or the molding time is too long. May take too long.

As such a suitable organic peroxide, specifically, for example, as peroxyesters: tertiary hexyl peroxy isopropyl carbonate (1 hour half-life temperature 114.6 ° C.) tertiary hexyl per There are oxybenzoates (1 hour half-life temperature 119.2 ° C.) and the like, and as peroxyketals, 1,1-bis (tertiary hexyl peroxy)-
3,3,5-trimethylcyclohexane (1 hour half-life temperature 106.4 ° C.) and 1,1-bis (tert-hexylperoxy) cyclohexane (1 hour half-life temperature 107.3 ° C.). These organic peroxides are advantageous in terms of safety, handleability, cost, etc., and are preferably used as a curing agent.

The amount of the above-mentioned perhexyl organic peroxide used is preferably 0.1 to 100 parts by weight in total of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer.
8 parts by weight, more preferably 0.3 to 6 parts by weight, and further preferably 0.5 to 5 parts by weight. If this amount is too small, it may be difficult for the sheet to completely cure during molding, and if it is too large, the sheet may easily turn yellow during molding.

The thermosetting resin composition further comprises
If necessary, an organic peroxide other than the perhexyl type can be included. Specific examples of the organic peroxides other than perhexyl-based compounds include: benzoyl peroxide, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peroxybenzoate, 1,1-bis (tertiary butyl peroxy)-
Examples are 3,3,5-trimethylcyclohexane and the like.

When an organic peroxide other than the perhexyl type is used together, the amount of the organic peroxide is 100 parts by weight of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer. The total amount of oxides is preferably 0.1-8
It is preferable that the amount is adjusted to be parts by weight, more preferably 0.3 to 6 parts by weight, and further preferably 0.5 to 5 parts by weight. If the amount used is too small, it may be difficult for the sheet to completely cure during molding, while if it is too large, the sheet may easily yellow.

A solvent, a monomer and the like are added to the thermosetting resin composition as needed. For example, in the case of a resin having a high viscosity, a solvent or the like is added to improve the impregnating property and the viscosity is lowered. Further, in a resin having low reactivity, a monomer or the like can be added to improve the reactivity. When a solvent is used to reduce the viscosity, if it remains, it tends to cause defects such as bubbles during molding. Therefore, a step of volatilizing and drying the solvent after impregnating the resin is required.

The above various thermosetting resin compositions also include
If necessary, an appropriate amount of an inorganic filler such as calcium carbonate, a polymerization inhibitor such as parabenzoquinone, an internal mold release agent such as zinc stearate, a fungicide and a preservative can be added.

The amount of the thermosetting resin composition impregnated into the decorative substrate is preferably 30 to 75% by weight, more preferably 30 to 75% by weight, based on the total weight of the impregnated sheet after drying. It is preferably blended so as to be 40 to 65% by weight.

The resin can be impregnated into the base material by a conventionally known method. That is, for example, a method in which the base material is immersed in the resin in the impregnation tank to impregnate the resin, the base material is pressed by a roll or the like to remove excess resin, and dried in a drying furnace as necessary, or There is a method of flowing a base material on a belt, placing a resin on the base material, and pressing the base material with a roll or a blade.

Next, the thermosetting molding material will be described. In the invention described in claim 1, as the thermosetting molding material, those conventionally used as various thermosetting molding materials such as SMC and BMC can be used.

An example of preparation of the thermosetting molding material is as follows. That is, an unsaturated polyester resin, an epoxy acrylate resin, a urethane acrylate resin or the like is used as the thermosetting resin, and if necessary, an inorganic filler,
Reinforcing materials, additives, etc. are added, and by a conventionally known method,
A thermosetting resin composition having a form such as SMC or BMC is prepared.

The thermosetting resin used for preparing the thermosetting molding material may be the same as that used for preparing the decorative molding sheet. The thermosetting resin is as described in detail in the description of the decorative molding sheet.

Like the thermosetting resin for the decorative molding sheet, the molding material is usually styrene, α-methylstyrene, divinylbenzene, vinyltoluene, diallylphthalate, various acrylate monomers, various methacrylate monomers and the like. An appropriate amount of copolymerizable monomer is added.

Among them, styrene and methyl methacrylate are preferably used because they are excellent in price and various performances.

When the above-mentioned copolymerizable monomer is used, the amount thereof is preferably 1 to 70% by weight, more preferably 3 to 50% by weight, based on the resin content. If the amount used is too small, the viscosity of the molding material becomes high, so sufficient fluidity cannot be obtained at the time of molding. On the contrary, if it is too large, the adhesion tends to decrease, and in either case, it is preferable. Absent.

In the present specification, the "resin component" means a component such as a thermosetting resin such as an unsaturated polyester or a thermoplastic resin, which can be chemically reacted into a resin such as a copolymerizable monomer. Means the total amount including.

Further, the molding material includes, as a low-shrinking agent, polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, ethylene-vinyl acetate copolymer, vinyl acetate-styrene copolymer, polybutadiene, saturated polyesters, saturated polyester. A thermoplastic resin such as polyethers may be added in an appropriate amount as needed.

When the above-mentioned thermoplastic resin is used, the amount thereof is preferably 0.1 to 30% by weight, more preferably 0.3 to 20% by weight, based on the resin content. . If the amount used is too large, the viscosity of the molding material increases, so it is difficult to obtain sufficient fluidity during molding,
On the other hand, if the amount is too small, it is difficult to obtain a sufficient shrinkage improving effect, which is not preferable in any case.

If desired, an organic peroxide as a radical reaction initiator can be used in the thermosetting resin. Specific examples of the organic peroxide are the same as the organic peroxide of the thermosetting resin composition used for preparing the decorative molding sheet.

When the above organic peroxide is used, its amount is preferably 0.3 parts by weight based on 100 parts by weight of the sum of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer.
To 5 parts by weight, more preferably 0.5 to 3 parts by weight. If the amount used is small, the curing speed of the molding material tends to be slow, and conversely, if the amount is too large, the molding material tends to yellow during curing, which is not preferable.

Further, an appropriate amount of inorganic filler can be added to the molding material depending on the purpose and application. Examples of usable inorganic fillers include the following.
That is, elemental minerals such as graphite and diamond,
Halide minerals such as rock salt and potassium rock salt, carbonate minerals such as calcium carbonate, phosphate minerals such as cyanite, vanadate minerals such as carnotite, barite (barium sulfate), gypsum (calcium sulfate), etc. Sulfate minerals, borate minerals such as borax, titanate minerals such as perovskite, mica, talc (talc), pyrophyllite, kaolin, quartz, silicate minerals such as feldspar, titanium oxide, corundum ( Aluminum (oxide), metal hydroxides such as aluminum hydroxide, glass products such as (hollow) glass spheres, etc., natural or artificial minerals, or those obtained by treating, purifying or processing them, and those A mixture is used.

The amount of the above-mentioned inorganic filler added is 100
It is preferably 0.5 to 60 parts by weight, and more preferably 1 to 40 parts by weight with respect to parts by weight. If the addition amount is too small, it is difficult to obtain the effect of adding a sufficient inorganic filler for the improvement of abrasion resistance or the adjustment of gloss, and if it is too large, the viscosity of the thermosetting resin composition is high. Since it becomes too much, it becomes difficult to impregnate this with the substrate, which is not preferable in any case.

Further, a coloring pigment may be used in an appropriate amount in the molding material, if necessary. A conventionally known pigment is used as the color pigment. For example, titanium oxide, benzine yellow, anthraquinone yellow, titanium yellow, Hansa yellow, molybdate orange,
Yellow lead, disazo yellow, benzine orange, quinacridone red, quinacridone magenta, naphthol violet, chrome green, phthalocyanine green, alkali blue, cobalt blue, phthalocyanine blue, iron oxide (red iron oxide), copper azo brown, aniline black, carbon black, iron Various well-known and commonly used ones such as black, aluminum flakes, nickel powder, gold powder, silver powder and the like are used.

Among them, titanium oxide, titanium yellow, quinacridone red, quinacridone magenta, phthalocyanine blue, iron oxide (red iron oxide), carbon black,
Iron black, aluminum flakes and the like are preferably used because they have little influence on the curability of the molding material.

The amount of the color pigment used in the molding material is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the resin component. Further, the addition amount of the inorganic filler is preferably 0 to 300 parts by weight, and more preferably 0 to 250 parts by weight with respect to 100 parts by weight of the resin content. The total amount of the color pigment and the inorganic filler is preferably 30 to 320 parts by weight, more preferably 40 to 200 parts by weight. If the addition amount of the inorganic filler and the color pigment is too small, it is difficult to obtain sufficient hiding property, and if the addition amount is too large, the viscosity of the composition becomes high, so that sufficient fluidity in the mold at the time of molding is obtained. Is difficult to obtain, and in any case, it is not preferable.

Various reinforcing fibers, that is, glass fibers, carbon fibers and the like can be added to the molding material as a reinforcing material, if necessary.

When reinforcing fibers are used as the molding material, the amount used is preferably 1 to 100 parts by weight, and more preferably 3 to 90 parts by weight, based on the resin content. If the amount used is too small, it is difficult to obtain a sufficient reinforcing effect. On the contrary, if the amount is too large, the viscosity of the composition becomes high, so it is difficult to obtain sufficient fluidity in the mold during molding. Either case is not preferable.

If necessary, the molding material further comprises
Dimethylaniline, known curing accelerators such as cobalt naphthenate, polymerization inhibitors such as parabenzoquinone, azo dyes and anthraquinones, indigoids, dyes such as stilbene, conductivity imparting agents such as carbon black, emulsifiers,
A metal soap such as zinc stearate, an aliphatic phosphate, a release agent such as lecithin and the like can be added in an appropriate amount depending on the use and purpose.

More specifically, the molding material used in the invention of claim 1 is, for example, 60 to 100 parts by weight of an unsaturated polyester resin liquid (styrene concentration: 40 to 70% by weight) and a styrene solution such as polystyrene resin ( (Styrene concentration 40 to 70% by weight) 0 to 40 parts by weight is added to 100 parts by weight, and 60 to 160 parts by weight of inorganic fillers such as calcium carbonate, aluminum hydroxide and glass powder, titanium oxide, iron oxide, Coloring pigments such as carbon black and titanium yellow 5 to 20 parts by weight, organic peroxides such as tertiary butyl peroxybenzoate 0.7 to 2.5 parts by weight, thickeners such as magnesium oxide 0.5 to 3 parts by weight Of a total of 70 to 180 parts by weight of an inorganic component is kneaded to form a compound, which is added to 5 to 80 parts by weight of a reinforcing material such as glass fiber. Soaked is preferably used that the SMC or BMC of forms.

Next, the invention according to claim 2 will be described.

In the invention according to claim 2, the thermosetting resin composition with which the decorative base material is impregnated contains an organic peroxide having a specific one-hour half-life temperature.

The organic peroxide has a one-hour half-life temperature of 100 to 130 ° C., preferably 103 to 126 ° C.
And more preferably 105 to 120 ° C. If the 1-hour half-life temperature is too low, the reaction will start too early.
If pregel is liable to be generated during molding, and if it is too high on the contrary, the reaction speed is too slow, which may result in insufficient curing or the molding time may be too long.

Such organic peroxides are roughly classified into peroxyesters and peroxyketals when classified regardless of whether they correspond to the perhexyl-type organic peroxide in the first aspect of the invention. It

Specifically, for example, as peroxyesters: tertiary hexyl peroxyisopropyl carbonate (1 hour half-life temperature 114.6 ° C.) tertiary butyl peroxyisopropyl carbonate (1 hour half-life temperature 118. 4 ° C) -tert-butyl peroxymaleic acid (1 hour half-life temperature 119.0 ° C) -tert-butyl peroxy-3,3,5-trimethylhexanoate (1 hour half-life temperature 119.3 ° C) ) -Tertiary butyl peroxy laurate (1 hour half-life temperature 118.2 ° C) ・ 2,5-Dimethyl-2,5-di- (methatoruloylperoxy) hexane (1 hour half-life temperature 117.3 ° C) ) Tertiary butyl peroxy-2-ethylhexyl carbonate (1 hour half-life temperature Degree 119.3 ° C.)-Tertiary hexyl peroxybenzoate (1 hour half-life temperature 119.2 ° C.) 2,5-Dimethyl-2,5-di- (benzoylperoxy) hexane (1 hour half-life temperature 118 .8 ° C.)-Tert-butyl peroxyacetate (1 hour half-life temperature 120.9 ° C.)-Tertiary butyl peroxybenzoate (1 hour half-life temperature 124.7 ° C.)-Di-tert-butyl peroxyisophthalate (1
Time half-life temperature 126.7 ° C.) and the like.

Further, as peroxyketals, 1,1-bis (tertiary hexyl peroxy)-
3,3,5-Trimethylhexane (1 hour half-life temperature 1
0,6.4 ° C.)-1,1-bis (tertiary hexyl peroxy) cyclohexane (1 hour half-life temperature 107.3 ° C.) 1,1-bis (tertiary butyl peroxy)-
3,3,5-Trimethylcyclohexane (1 hour half-life temperature 109.2 ° C) ・ 1,1-bis (tert-butylperoxy) cyclohexane (1 hour half-life temperature 111.1 ° C) ・ 2,2-bis (4,4-ditert-butylperoxycyclohexyl) propane (1 hour half-life temperature 11
・ 1,1-bis (tert-butylperoxy) cyclododecane (1 hour half-life temperature 114.0 ° C) ・ 2,2-bis (tert-butylperoxy) butane (1 hour half-life) Temperature 121.7 ° C.) Butyl 4,4-bis (tertiary butyl peroxy) parerate (1 hour half-life temperature 126.7 ° C.) and the like.

Of the above organic peroxides, tertiary hexyl peroxyisopropyl carbonate, tertiary butyl peroxyisopropyl carbonate, tertiary hexyl peroxybenzoate, tertiary butyl peroxybenzoate, 1,1-bis (tertiary) Hexylperoxy)-
3,3,5-Trimethylcyclohexane ・ 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, etc.
It is advantageously used in terms of handleability and cost.

Further, the one-hour half-life temperature is 100 to 130.
Among the organic peroxides having a temperature of ℃, those having a tertiary hexyl group are particularly preferable because they have particularly good gloss of the decorative portion.

The amount of the organic peroxide used is preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer. It is preferably 0.3 to 6 parts by weight, and more preferably 0.5 to 5 parts by weight. If this amount is too small,
In some cases, it may be difficult for the sheet to completely cure during molding. On the other hand, if the amount is too large, the sheet may easily turn yellow during molding.

If necessary, an organic peroxide having a 1-hour half-life temperature of 100 ° C. or lower can be used in combination with the thermosetting resin composition. When such an organic peroxide is used, its amount is preferably 0.5 parts by weight or less, more preferably 0.5 parts by weight or less, based on 100 parts by weight of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer. It is preferably 0.3 part by weight. If the amount used is too large, the surface properties of the molded product may deteriorate.

If necessary, an organic peroxide having a 1-hour half-life temperature of 130 ° C. or higher can be used in combination with the thermosetting resin composition. When such an organic peroxide is used, the amount thereof is preferably 7 parts by weight or less, and more preferably 100 parts by weight of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer. Is 4 parts by weight or less. If the amount used is too large, the sheet may easily turn yellow during molding.

As described above, the one-hour half-life temperature is 100
When an organic peroxide having a temperature of ℃ or less or 130 ℃ or more is used in combination, the amount of the organic peroxide is 100 parts by weight of the total amount of the thermosetting resin having a reactive unsaturated bond and the copolymerizable monomer. The total amount of peroxide is adjusted to preferably 0.1 to 8 parts by weight, more preferably 0.3 to 6 parts by weight, and even more preferably 0.5 to 5 parts by weight. If the amount used is too small, it may be difficult for the sheet to completely cure during molding, while if it is too large, the sheet may easily turn yellow during molding.

The other structure of the invention described in claim 2 is the same as that described in the invention described in claim 1.

Next, the invention according to claim 3 will be described. The method for producing a decorative molded product according to the invention of claim 3 is carried out using the decorative molding sheet of claim 1 or 2, and the specific operation is as follows.

As the molding machine used in the present invention, a conventionally known press molding machine can be used. Further, as the molding die, conventionally known dies, casting dies and the like can be used.

As the mold type, generally, the upper and lower molds are preferably used. In this case, the upper mold is usually used as a movable mold and the lower mold as a fixed mold.

The above molding die is attached to the above molding machine,
After heating, a decorative molding sheet, which is a material to be compressed, is placed in the mold. The mold heating temperature is preferably 120 to 170 ° C.,
More preferably 130 to 155 ° C, most preferably 13
5 to 150 ° C. If the temperature of the mold is too low, it takes a long time to completely cure, and if it is too high, the surface gloss of the decorated portion is deteriorated and the surface is easily contaminated.

Then, the molding material is placed on the decorative molding sheet. The mounting work of the molding material is a normal FRP
Similar to the placing work in press molding, it is efficient to carry out by an automated device, but it may be carried out manually. For example, after the decorative molding sheet is placed on the mold, the placement of the molding material is completed preferably within 2 minutes, more preferably within 1.5 minutes, and most preferably within 1 minute. If the mounting time of the decorative molding sheet is too long, the surface gloss of the decorative portion is deteriorated and the surface is easily contaminated.

As for the vertical relationship between the decorative molding sheet and the molding material, as described above, it is common to first arrange the decorative molding sheet in the mold and then stack the molding material on top of it. However, if necessary, first place the molding material in the mold,
Then, a decorative molding sheet may be placed on top of it.

After closing the mold in this way,
At a pressure of 120 kg / cm @ 2, preferably 40 seconds to 7 minutes, more preferably 2 to 6 minutes, most preferably 1.5.
After performing pressure molding for 5 minutes to cure the molding target,
When the mold is opened and the product is demolded, a laminated decorative molded product is obtained. If this molding time is too long, the work efficiency will decrease and the cost will increase.

Regarding the direction of the decorative surface of the decorative molding sheet in the molding die, it is usual to orient the decorative surface toward the molding die side so that the surface of the obtained molded product comes to the decoration surface. However, the decorative surface may be directed to the molding material side, if necessary.

Here, the size of the decorative molding sheet may be large so that the entire surface of the molded product is decorated with it, or small so that only a part of the surface of the molded product is decorated. It doesn't matter. That is, a decorative molding sheet having an arbitrary size and shape is used according to the desired design.

If necessary, a glass mat, a glass cloth, or a glass cloth may be placed between the decorative molding sheet and the molding material.
A cloth, a non-woven cloth, or a material obtained by impregnating these with a resin may be laminated as an intermediate layer.

[0097] Since the present invention is constructed as described above for the operation, the following effects are exhibited. When obtaining a conventional decorative molding sheet,
For example, as disclosed in JP-A-57-126666, printing paper is impregnated with an impregnating solution containing benzoyl peroxide as a curing agent in a curable resin solution to obtain a decorative molding sheet, which is In the case of diverting to JP-A-5-285973 and performing heat compression molding in a laminated state with SMC, the reactivity of radicals (PhCOO.) Generated from benzoyl peroxide is not particularly high. Then, a 100% completely cured product could not be obtained, and the molded product was inferior in chemical resistance, solvent resistance and the like.

In order to improve this point, the thermosetting resin composition contains a perhexyl-based organic peroxide as a curing agent. Hexyloxy radical [C ₃
H ₇ C (CH ₃ ) ₂ O.] is generated. This radical has a higher reactivity to double bonds than radicals generated from other organic peroxides, and produces a cured product with a small amount of residual monomers and a high cross-linking density.
It is presumed that a molded product having good chemical resistance and solvent resistance can be obtained.

In the invention according to claim 2, the conventional decorative molding sheet has a property that, for example, as described in JP-A-5-285973, the decorative molding sheet is provided on a substrate. It was arranged in layers and brought into contact with the hot plate, and at the same time, curing started.

However, if this conventional method is used as it is,
In the decorative molding of FRP press, especially in the molding of large-sized products such as waterproof pans, bathtubs, and bathtubs with a washroom,
It takes time to put the molding material on the decorative molding sheet after placing it on the mold, and especially for large molded products, it takes a long time.That is, tighten the mold in the meantime. The decorative molding sheet is cured before being pressed by the pressure. As a result, the decorative molding sheet will cure without pressure, and curing will proceed with the surface irregularities left intact during production of the impregnated paper, resulting in a so-called pregel with a poor surface property. To be

In order to improve this point, the thermosetting resin composition according to the second aspect of the present invention contains an organic peroxide having a specific one-hour half-life temperature. After that, the curing does not start while the molding material is placed on it, and thereafter the curing of the decorative molding sheet starts after the mold is tightened. Therefore, unfavorable surface properties such as pregel do not occur during molding, and a molded product having good surface properties can be obtained. The 1-hour half-life temperature of organic peroxide is 13
When the temperature is 0 ° C. or less, the decorative molding sheet is sufficiently cured during heat and pressure molding, and performance deterioration such as gloss reduction and strength reduction due to insufficient curing does not occur.

[0102]

Embodiments of the present invention will be described below. 1. Preparation of molding machine and mold As the molding machine, an 800-ton press molding machine manufactured by Kawasaki Yuko Co., Ltd. was used.

Two molds were prepared: a mold for molding a 100 cm × 100 cm square flat plate and a mold for molding a 30 cm × 30 cm flat plate.

The upper mold and the lower mold both have an electric heater and a cooling water pipe embedded therein. This mold was attached to the above press molding machine. The upper mold was a movable mold and the lower mold was a fixed mold.

2. Preparation of Sheet for Decorative Molding A sheet for decorative molding was prepared as follows. 1) Preparation of impregnating resin liquid Impregnating resin liquid 1: (1) Unsaturated polyester resin liquid (number average molecular weight of about 200)
50 parts by weight of an isophthalic acid-based unsaturated polyester resin of 0 dissolved in acetone, acetone concentration 40% by weight (2) diallylphthalate resin liquid (number average molecular weight of about 700)
A solution of the diallyl phthalate resin in
Acetone concentration 45% by weight) 50 parts by weight (3) Tertiary hexyl peroxyisopropyl carbonate (1 hour half-life temperature 114.6 ° C) 2 parts Mix the above components (1) to (3) and stir thoroughly. The resin liquid 1 for impregnation was obtained.

Impregnating resin liquid 2: (1) 50 parts by weight of unsaturated polyester resin liquid (similar to impregnating resin liquid 1) (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) 1,1-bis (tertiary hexyl peroxy)
Cyclohexane (1 hour half-life temperature: 107.3 ° C.) 2 parts The components (1) to (3) were mixed and sufficiently stirred to prepare a resin solution 2 for impregnation.

Impregnating resin liquid 3: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) tertiary hexyl peroxybenzoate (1
Time half-life temperature 119.2 ° C.) 0.7 part The components (1) to (3) above were mixed and sufficiently stirred to prepare a resin solution 3 for impregnation.

Impregnating resin liquid 4: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) 1,1-bis (tertiary hexyl peroxy)
-3,3,5-Trimethylcyclohexane (1 hour half-life temperature 106.4 ° C) 1 part The components (1) to (3) above were mixed and sufficiently stirred to prepare a resin solution 4 for impregnation.

Impregnating resin liquid 5: (1) 100 parts by weight of unsaturated polyester resin liquid (the same as the impregnating resin liquid 1) (2) 1,1-bis (tertiary hexyl peroxy)
Cyclohexane (1 hour half-life temperature 107.3 ° C.) 2 parts The components (1) and (2) above were mixed and sufficiently stirred to prepare a resin solution 5 for impregnation.

Resin solution for impregnation 6: (1) 100 parts by weight of diallyl phthalate resin solution (the same as the resin solution for impregnation 1) (2) Tertiary hexyl peroxyisopropyl carbonate (1 hour half-life temperature 114.6 ° C.) ) 0.7 parts The components (1) and (2) above were mixed and sufficiently stirred to prepare a resin solution 6 for impregnation.

Impregnating resin liquid 7: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) benzoyl peroxide (1 hour half-life temperature 9
2.0 ° C.) 1 part The components (1) to (3) described above were mixed and sufficiently stirred to prepare a resin liquid 7 for impregnation.

Impregnating resin liquid 8: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) Tertiary butyl peroxyisopropyl carbonate (1 hour half-life temperature 118.4 ° C) 2 parts The above components (1) to (3) are mixed and sufficiently stirred to obtain the impregnating resin liquid 8 did.

Impregnating resin liquid 9: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) Tertiary butyl peroxyisopropyl carbonate (1 hour half-life temperature 118.4 ° C.) 1 part The components (1) to (3) above are mixed and sufficiently stirred to obtain the impregnating resin liquid 9 did.

Impregnating resin liquid 10: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) Tertiary butyl peroxybenzoate (1 hour half-life temperature 124.7 ° C.) 1.5 parts The components (1) to (3) above are mixed and sufficiently stirred to obtain a resin solution for impregnation 10 And

Impregnating resin liquid 11: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) 1,1-Bister shary butylperoxy-3,
2,5-Trimethylcyclohexane (1 hour half-life temperature 109.2 ° C.) 2 parts The components (1) to (3) were mixed and sufficiently stirred to obtain a resin solution 11 for impregnation.

Immersion Resin Liquid 12: (1) 100 parts by weight of unsaturated polyester resin liquid (the same as the impregnation resin liquid 1) (2) Curing agent (tertiary butyl peroxyisopropyl carbonate) 0.8 parts (1) and (2) were mixed and stirred to prepare a resin liquid 12 for impregnation.

Impregnating resin liquid 13: (1) 100 parts by weight of unsaturated polyester resin liquid (similar to impregnating resin liquid 1) (2) Hardener (tertiary butyl peroxyisopropyl carbonate) 2 parts Above (1 ) To (2) were mixed and stirred to prepare a resin solution 13 for impregnation.

Impregnating resin liquid 14: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) 1 part of tert-hexyl peroxide (1 hour half-life temperature 144.1 ° C.) 1 part The above (1) to (3) were mixed and stirred to prepare a resin solution 14 for impregnation.

Impregnating resin liquid 15: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) Tertiary hexyl peroxypivalate (1 hour half-life temperature 71.3 ° C.) 1 part The above (1) to (3) were mixed and stirred to prepare a resin solution 15 for impregnation.

Impregnating resin liquid 16: (1) Unsaturated polyester resin liquid (similar to impregnating resin liquid 1) 50 parts by weight (2) Diallyl phthalate resin liquid (similar to impregnating resin liquid 1) 50 Parts by weight (3) Tertiary hexyl hydroperoxide (1
Time half-life temperature 188.5 ° C.) 4 parts The above (1) to (3) were mixed and stirred to obtain a resin solution 16 for impregnation.

2) Preparation of Decorative Base Material Decorative Base Material 1 Overlay paper (thickness 0.1 mm, basis weight 100 g /
m ² ) with black granite-like stone pattern printed Decorative base material 2 Nylon cloth (thickness 0.1 mm, basis weight 90 g / m ² , manufactured by Toyobo Co., Ltd.) black granite-like stone pattern Decorative base material 3 Nonwoven fabric made of polyester (thickness 0.36 mm, basis weight 40.
7 g / m ² , Sontara # 8000: manufactured by DuPont Toray Co., Ltd., with a black granite-tone stone pattern printed on it 3) Preparation of a decorative molding sheet 1 Decorative molding sheet 1 80 cm × decorative base material 1 After cutting into a size of 80 cm and immersing the cut piece in the impregnating resin liquid 1 to impregnate the resin, the cut piece is pressed by a roll to remove excess resin,
A decorative molding sheet 1 was obtained. The weight ratio of the base material (titanium paper) in this decorative molding sheet was 45% by weight.

Decorative molding sheets 2 to 32 Decorative molding sheet 2 is the same as decorative molding sheet 1 except that the decorative base material and impregnating resin are used in the combinations shown in Tables 1 to 4 below. ~ 32. The weight ratio of the base material in these decorative molding sheets is shown in Tables 1 to 4.

3. Preparation of molding material The following colored molding material was used as a molding material. Molding material 1 (1) Unsaturated polyester resin liquid (number average molecular weight about 200)
70 parts by weight of a styrene concentration of 40% by weight even when an isophthalic acid-based unsaturated polyester resin of 0 was dissolved in styrene (2) Polystyrene resin solution (polystyrene resin having a weight average molecular weight of about 95,000 was dissolved in styrene) (Styrene concentration 65% by weight) 30 parts by weight (3) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight (4) Calcium carbonate powder (NS-100: Nitto Koka Co., Ltd.) 120 parts by weight (5 ) Color pigment (titanium oxide powder, SR-1: manufactured by Sakai Chemical Industry Co., Ltd.) 6 parts by weight (6) Thickener (magnesium oxide powder, average particle size about 3 μ)
m, Kyowamag 150: Kyowa Chemical Industry Co., Ltd.) 1 part by weight (7) Internal mold release agent (zinc stearate: Sakai Chemical Industry Co., Ltd.)
3 parts by weight (8) 70 parts by weight of glass fiber (roving made by Asahi Fiber Glass Co., Ltd .: ER4630LBD166W cut into a length of 25 mm)

Of the above-mentioned compounding materials, the compounding materials (1) to (7) were mixed and sufficiently kneaded, and then the obtained kneaded product was mixed with S.
The glass fiber of (8) was impregnated with MC manufacturing equipment, and 40
Colored (white) with a thickness of about 2 mm after aging at ℃ for 24 hours
A molding material 1 was obtained.

4. Molding method A decorative molded article was molded from the thus obtained decorative molding sheet and molding material as follows.

Example 1 The upper die of a 30 cm × 30 cm flat plate was placed at 140 ° C.
After heating the lower mold to 150 ° C., a decorative molding sheet 1 cut into 25 cm × 25 cm was placed on the lower mold as a decorative molding sheet. Molding material 1 on it 20 cm x 20
Charged 6 pieces cut into cm. After the decorative molding sheet was placed, the time until the placement of the molding material was completed was 20 seconds. After that, tighten the mold to 100 kg / c
Pressure molding was performed for 180 seconds at a pressure of m ² . After molding, the mold was opened and demolded to obtain a decorated molded product.

As shown in the attached FIGS. 1 to 3, a molded article having a desired shape can be obtained depending on the sizes of the decorative molding sheet (11) and the molding layer (12) made of a colored molding material.

Examples 2 to 9 and Comparative Examples 1 to 6 Molding was performed in the same manner as in Example 1 except that the decorative molding sheets and molding materials shown in Tables 1 and 2 were used.

Example 10 Example 1 was repeated except that the decorative molding sheet and molding material shown in Table 1 were used, and the mold was clamped and pressure was applied for 480 seconds.
Molding was performed in the same manner as in.

Examples 11 to 20 and Comparative Examples 7 to 12 As the mold, a 100 cm × 100 cm flat plate mold was used.

As the decorative molding sheet, those shown in Tables 3 and 4 were used in a size of 80 cm × 80 cm.

Six molding materials having a size of 50 cm × 50 cm were used.

The time from the placing of the decorative molding sheet to the completion of placing the molding material was 50 seconds.

The time for clamping and pressurizing the mold was 180 seconds.

Molding was performed in the same manner as in Example 1 except for the above.

[0136] 5. Evaluation Method The molded articles obtained in the above Examples and Comparative Examples were subjected to evaluation tests of the following items.

1) Gloss Test For the decorative parts of the molded articles obtained in Examples 1 to 20 and Comparative Examples 1 to 12, the gloss was measured using a gloss meter (“Gloss Checker IG100” manufactured by Horiba Ltd.). The obtained measured values are shown in Tables 1 to 4.

Shown in.

2) Solvent Resistance Test The molded articles obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were measured for gloss after immersion in a solvent by the following method. That is, 4 cm × 4 cm gauze was impregnated with ethyl acetate, and this was placed on the surface of the molded product, and the molded product was covered with a petri dish and left for 15 minutes. Then, the petri dish was removed to remove the gauze, and ethyl acetate on the surface of the molded product was wiped off with a new dry case. After the surface was treated with the solvent in this manner, the gloss of the surface was measured using a gloss meter (“Gloss Checker IG100” manufactured by Horiba Ltd.). The obtained measurement values are shown in Tables 1 and 2.

3) Contamination resistance test The molded articles obtained in Examples 11 to 20 and Comparative Examples 7 to 12 were evaluated for contamination resistance by the following method. That is, an oily black magic ink was uniformly applied to a 5 cm × 5 cm portion of the surface of the molded product, and left for 1 minute. Then, the coated portion on the surface of the molded product was wiped with a gauze impregnated with ethyl acetate, and the ink wiping condition was examined. The obtained measured values are shown in Tables 3 and 4.

[0141]

[Table 1]

[0142]

[Table 2]

[0143]

[Table 3]

[0144]

[Table 4]

As is clear from Tables 1 to 4, the molded articles of Examples were better than those of Comparative Examples in terms of glossiness, solvent resistance and stain resistance.

[0146]

The present invention is configured as described above. In the invention according to claim 1, since the perhexyl organic peroxide is used as the curing agent, the surface gloss of the decorated portion is good, and It is possible to provide a decorative molded article having high curability and excellent chemical resistance, solvent resistance and the like.

Further, in the invention described in claim 2, since the organic peroxide having a one-hour half-life temperature of 100 to 130 ° C. is used, the surface gloss of the decorated portion is good and the organic peroxide is in a short time. Thus, it is possible to obtain a decorative molded article having excellent surface properties that the curing is completed and the surface is less likely to be contaminated.

[Brief description of drawings]

FIG. 1 is a vertical sectional view showing an example of a molded product obtained by the present invention.

FIG. 2 is a vertical cross-sectional view showing another example of the molded product obtained by the present invention.

FIG. 3 is a vertical sectional view showing still another example of the molded product obtained according to the present invention.

[Explanation of symbols]

 (11): Sheet for decorative molding (12): Molding material

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08L 67:06

Claims (3)

[Claims] 1. A decorative molding sheet, wherein a decorative base material is impregnated with a thermosetting resin composition containing a perhexyl organic peroxide. 2. A decorative molding sheet, wherein a decorative base material is impregnated with a thermosetting resin composition containing an organic peroxide having a one-hour half-life temperature of 100 to 130 ° C. 3. The decorative molding sheet according to claim 1 or 2 is used as a decorative molding sheet when the decorative molding sheet is laminated on a thermosetting molding material and the molding composition is subjected to heat compression molding. A method for producing a decorated molded article, which is characterized by the following.