JPH0911263A - Manufacture of decorative molding - Google Patents

Abstract

PURPOSE: To manufacture a decorated molding without defective inflow of resin which requires complicated correcting work when a decorative sheet layered molding is to be molded, by using a thermosetting molding material which contains specified rates of thermosetting resin and magnesium oxide. CONSTITUTION: Inflow of a melt of a molding material 12 on a decorating sheet 11 occurs due to inflow of a molding material resin which is melted and lowered in its viscosity into a small clearance between the edge of the decorating sheet and a mold. For the thermosetting molding material 12, a material which contains the thermosetting resin and 1.8-3.5 pts.wt. of magnesium oxide based on 100 pts.wt. of the resin and is made to be highly viscous is used. Accordingly, at the time of molding, the melting degree of the molding material 12 rises and the fluidity of the resin lowers. As a result, the molding material resin hardly flows in between the decorative sheet 11 and the mold, so that defective products caused by inflow of the resin are scarcely produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a decorative sheet and a thermosetting molding material which are stacked in a mold, and subjected to heat compression molding to integrate the decorative sheet and the molding material. The present invention relates to a method for producing a decorative molded product that exhibits a desired pattern or color with a decorative sheet.

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, in the field of FRP (glass fiber reinforced plastic), especially in the production of FRP bathtubs, bath unit floors, etc., a method called a hand lay-up molding method or a spray-up molding method has been widely adopted. However, these methods have taken a long time and a lot of man-hours to produce one product. Therefore, as a material for significantly improving these productivity, thermosetting molding materials such as sheet molding compound (hereinafter abbreviated as SMC) or bulk molding compound (hereinafter abbreviated as BMC) have been developed. A heat compression molding method using this is widely adopted at present. For example, “Composite Material Technology Compilation (edited by Makihiro and Shoji Shimamura, February 1st, 1976)
5 days issued by Industrial Technology Center Co., Ltd. "
A method is disclosed in which 0.1 to 1 part by weight of magnesium oxide is mixed with 0 part by weight to increase the viscosity to produce SMC, and compression molding is performed using the SMC to obtain a molded article.

However, in the heat compression molding of SMC or BMC using only the thermosetting molding material, the color of the entire molded article is limited to a single color. The only problem is that only red ones can be produced, and the freedom of patterns and colors is narrowed. 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 decorating sheet for expressing a desired pattern on a molded product has been proposed. For example, a decorative sheet formed by printing a desired pattern on a substrate such as glass cloth, glass mat, non-woven fabric, or woven fabric is placed on the SMC, placed in a mold, and subjected to heat compression molding, thereby applying heat. A method of decorating a molded product by integrating a decorative sheet and a molding material has been proposed. For example, in Japanese Unexamined Patent Publication No. 5-285973, SMC is superposed on a decorative 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 of obtaining a molded article is proposed.

However, in the above heat compression method, the emphasis is placed only on the development of the decorative sheet material to be laminated on the molding material, and it is premised that the conventional molding material as the base material is used as it is. However, no attempt has been made to improve the manufacturing process by attempting to improve the molding material.

That is, in the above-described heat compression method, a conventional SMC in which 0.1 to 1 part by weight of magnesium oxide is blended as a thickening agent with respect to 100 parts by weight of a resin content as a molding material as a base material. Was used as it was.

Here, if the amount of magnesium oxide contained in the molding material is too small, the resin composition does not thicken sufficiently, so that SMC becomes sticky and the workability deteriorates. On the contrary, if this amount is too large. Since the viscosity at the initial stage of compounding becomes high, a long time is required for the mixing of the resin composition and the impregnation step into the glass fiber, and when the mixing and impregnation step is short,
A molded product obtained by causing poor dispersion becomes inferior in hot water resistance and the like. Therefore, the SMC should be mixed in the above proportions.
Was manufactured.

[0009]

However, in the heat compression molding method as described above, during molding, the melt of the thermosetting molding material is transferred from the edge portion of the decorative sheet laminated thereon to the upper surface of the sheet. There is a problem that it goes around and stains the decorative part. For this reason, in the above method, after molding, the obtained molded product is corrected to hide the stain, and the corrected product is used as a product. However, this correction work requires manual labor and time, such as painting and drying manually.
The total cost is very high.

The present invention has been made to solve the above-mentioned drawbacks, and is a resin that requires complicated correction work when forming a decorative sheet laminated molded product having a design such as a free pattern and color. It is an object of the present invention to provide a method capable of producing a decorated molded product that does not have a flow-in defect.

[0011]

The method for producing a decorative molded product according to the present invention has been devised to achieve the above object, and a decorative sheet and a thermosetting molding material are stacked in a mold. Then, when the mold is clamped and the heat compression molding is performed, the thermosetting resin and the resin component 10 are used as the thermosetting molding material.
It is characterized by using a material containing 1.8 to 3.5 parts by weight of magnesium oxide with respect to 0 parts by weight.

Hereinafter, the present invention will be described in detail. First, the decorative sheet will be described. The decorative sheet used in the present invention means colored or printed paper, cloth, non-woven fabric, glass mat, glass cloth and the like. This decorative sheet can be appropriately impregnated with a thermosetting resin composition. When the thermosetting resin composition is impregnated, the thermosetting resin composition is hardened in the mold, and a decorative surface that is hard and has excellent durability can be obtained.

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. 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. Specifically, a method of weaving using a fiber dyed with a dye, a method of impregnating cloth with ink or the like after weaving, a paint There is also a method of applying a paint to a cloth.

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. 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, specifically, a method of forming a cloth by using a fiber colored with a dye, a method of impregnating an ink after forming the fiber into a cloth shape. , There is a method of applying paint or paint to a non-woven fabric.

The above-mentioned glass mat is chemically bonded to glass fiber by using an adhesive (binder),
It is possible to use a mat-shaped product obtained by depositing glass fibers and then punching them. 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, specifically, a method of forming a mat by using fibers colored with a dye, a method of impregnating a glass mat with ink or the like after weaving. , There is a method of applying paint or paint to the glass mat.

As the above-mentioned glass cloth, a conventionally known one obtained by weaving glass fibers can be used. Also,
As the printing method, various conventionally known methods can be applied, and specifically, the gravure printing method includes a gravure offset printing method, a silk screen printing method, a relief printing method, an offset printing method, and the like. Also, as the coloring method, various conventionally known methods can be applied, specifically, a method of weaving using a fiber dyed with a dye, a method of impregnating glass cloth with ink or the like after weaving, There is a method of applying paint or paint to the glass cloth.

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.

In the present invention, when the decorative sheet is impregnated with the thermosetting resin composition, examples of the thermosetting resin composition include unsaturated polyester resin, epoxy acrylate resin, urethane acrylate resin, diallyl phthalate resin, A composition containing various thermosetting resins such as melamine resin and phenol resin as a main component 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 the organic polyol used for producing the above unsaturated polyester resin include diol, triol, tetraol and a mixture 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, (anhydrous) itaconic acid and the like.

Examples of the aliphatic unsaturated polycarboxylic acid used for producing 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 resin is usually mixed with an epoxy resin by a known and conventional method.
It is produced from a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid.

As the epoxy resin used for producing the epoxy acrylate resin, bisphenol A type epoxy resin, epichlorohydrin and brominated bisphenol A produced from epichlorohydrin and bisphenol A by a well-known method.
Brominated bisphenol A type epoxy resin produced from, novolak type epoxy resin produced by glycidyl etherification of phenol novolac or orthocresol novolak, glycidyl amine type epoxy resin obtained by reacting various amines with epichlorohydrin (tetraglycidyl meta Xylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyl orthotoluidine, etc. are exemplified. It

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, polymethylene polyphenyl diisocyanate and the like.

Examples of the hydroxylalkyl (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.

Here, a solvent, a monomer and the like are added to the above various thermosetting resin compositions, if necessary. 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, various fillers, additives, etc. may be used.
Specifically, a suitable amount of a filler such as calcium carbonate, a polymerization initiator such as an organic peroxide, a polymerization inhibitor such as parabenzoquinone, an internal mold release agent such as zinc stearate, an antifungal agent and an antiseptic agent. Can be added.

Here, the amount of resin impregnated into the sheet base material is approximately the total amount of the impregnated sheet after drying when the base material is an organic material such as paper, cloth, or non-woven fabric. It is preferably blended so as to be 20 to 70% by weight, and more preferably 30 to 60% by weight.

Here, as the base material, glass cloth,
When an inorganic material such as a glass mat is used, it is approximately 10 with respect to the total weight of the impregnated sheet after drying.
It is preferable that it is blended so as to be about 50% by weight,
More preferably, it is 20 to 40% by weight.

The sheet base material can be impregnated with the resin by a conventionally known method. That is, for example, a method of immersing a sheet base material in a tank containing the resin to impregnate the resin, pressing the base material with a roll or the like to remove excess resin, and drying in a drying furnace as necessary, or There is a method in which a sheet base material is flown on a belt, a resin is placed on the base material, and the base material is pressed by a roll or a blade.

Next, the thermosetting molding material will be described. In the present invention, 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, various fillers,
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 sheet. The thermosetting resin is as described in detail in the description of the decorative sheet.

In the present invention, a molding material thickened with magnesium oxide is used. As the magnesium oxide, powdery ones are usually used, those having an average particle diameter of 0.01 to 100 μm are preferable, and powders having an average particle diameter of 0.1 to 10 μm are more preferably used.
If the particle size is too small, it becomes difficult to uniformly disperse the resin in the resin, and if the particle size is too large, it is difficult to uniformly increase the viscosity of the molding material, which is not preferable.

The amount of magnesium oxide used is the resin content 1
The amount is 1.8 to 3.5 parts by weight, preferably 2.0 to 3.3 parts by weight, and more preferably 2.2 to 3.1 parts by weight with respect to 00 parts by weight. If the amount of magnesium oxide used is too small, it is difficult to obtain a sufficient flow-in improvement effect, and if it is too large, the viscosity of the molding material becomes too high and the fluidity in the molding die becomes insufficient, resulting in lack of wall thickness. Since it is easy to cause defects such as, it is not preferable in any case.

In the present specification, the "resin component" means a thermosetting resin such as unsaturated polyester, a thermoplastic resin which is added as a low-shrinking agent as the case requires, and styrene and methyl methacrylate described later. It means the total amount including components that can chemically react to form a resin, such as a copolymerizable monomer.

As the low-shrinking agent to be added in an appropriate amount as necessary, polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, ethylene-vinyl acetate copolymer, vinyl acetate-styrene copolymer, polybutadiene, saturated polyesters Thermoplastic resins such as saturated polyethers and the like.

Further, the molding material is usually added with an appropriate amount of a polymerizable monomer such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, diallyl phthalate, various acrylate monomers and various methacrylate monomers. Among them, styrene and methyl methacrylate are preferably used because they are excellent in price and various performances.

If necessary, an organic peroxide as a radical reaction initiator can be used in the molding material. 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.

When the above-mentioned thermoplastic resin is used, its amount is 0.1 to 30% by weight of the resin content.
Is preferable, and more preferably 0.3 to 20% by weight. If the amount used is too large, the viscosity of the molding material becomes high, so that it is difficult to obtain sufficient fluidity during molding, and if it is too small, it is difficult to obtain a sufficient shrinkage improving effect. Is also not preferable.

When the above-mentioned various copolymerizable monomers are 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.

When the above organic peroxide is used, its amount is 0.3 to 5 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. Part is preferred, and 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 are as follows.
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.

Further, a coloring pigment can 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 addition 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 2 parts by weight.
The amount is adjusted to be 00 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.

As a reinforcing material, various reinforcing fibers, that is, glass fibers, carbon fibers and the like can be added to the molding material in appropriate amounts.

When reinforcing fibers are used as the molding material, the amount of the reinforcing fibers used is 1 to 250 with respect to the resin component.
It is preferable to set it as a weight part, More preferably, it is 3-20.
It is 0 part. 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.

Furthermore, if necessary, the molding material may also include
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.

The preferred embodiment of the present invention is as follows. More specifically, the molding material used in the present invention is, for example, an unsaturated polyester resin liquid (styrene concentration 3
0 to 70 parts by weight) 60 to 100 parts by weight, and 0 to 40 parts by weight of a styrene solution (styrene concentration of about 30 to 70% by weight) is added to 100 parts by weight of a resin solution, and calcium carbonate is added thereto. , 30 to 300 parts by weight of fillers such as aluminum hydroxide and glass powder, 5 to 20 parts by weight of pigments such as titanium oxide, iron oxide, carbon black and titanium yellow, organic peroxides such as tertiary butyl peroxybenzoate 0.5 to 3 parts by weight, 1.8 to 3.5 parts by weight of magnesium oxide, and 0.5 to 5 parts by weight of a release agent such as zinc stearate are added and kneaded. It is preferable to use 5 to 180 parts by weight of the reinforcing material such as SMC or BMC in the form of impregnation.

The production method of the present invention is carried out using the above-mentioned materials, 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.

In general, the upper and lower molds are preferably used as the form of the mold. In this case, the upper mold is usually used as a movable mold and the lower mold as a fixed mold.

The above mold is attached to the above molding machine,
After heating to 80 to 180 ° C., the decorative sheet, which is the material to be compressed, and the molding material are placed in a predetermined position in the mold while the mold is open.

Here, the temperature of the mold is 80 to 180 ° C, preferably 85 to 155 ° C. Especially, general-purpose S
When a molding material for high temperature such as MC and BMC is used, the temperature is preferably 100 to 155 ° C., and when a molding material for low temperature molding, which is so-called low temperature SMC, is used, it is 85 to 85 ° C. The temperature is preferably 100 ° C. If the mold temperature is too low, the molding material is difficult to solidify sufficiently, and if the mold temperature is too high, it is difficult to obtain sufficient fluidity of the molding material.

As for the vertical relationship between the decorative sheet and the molding material, the decorative sheet is placed on the mold surface of the lower mold, and the molding material is placed on the decorative sheet. Less and better. However, if necessary, the molding material may be on the lower side.

In the present invention, a decorative sheet laminated with a peeling film may be used.

Here, the surface on which the decorative sheet is placed on the lower mold is usually a decorative surface that is more printed or colored, but if necessary, the molding material side is applied. It can be used as a decorative surface.

Here, the size of the decorative sheet may be large so as to decorate the entire surface of the molded product, or may be small so as to decorate only a part of the surface of the molded product. It doesn't matter. That is, the size of the decorative sheet is an arbitrary size according to the desired pattern or color,
It can be shaped.

Further, in the present invention, if necessary,
A glass mat, a glass cloth, a non-woven fabric, a cloth, a paper or the like impregnated with a resin or the like may be appropriately inserted between the decorative sheet and the molding material.

In this way, the decorative sheet and the thermosetting molding material are placed in the mold in a laminated form, and then the mold is clamped. Then 1
By performing compression molding at a pressure of 0 to 120 kg / cm 2 for 30 seconds to 15 minutes to cure the object to be molded, the mold is opened, and the product is demolded to obtain a laminated decorative molded product.

Here, the molding pressure is 10 to 120 k.
g / cm ² , preferably 20 to 120 kg / cm ^2.
It is. In particular, when a molding material such as general-purpose SMC or BMC is used, it is preferably 50 to 120 kg / cm ^2, and when a molding material for low pressure molding, which is so-called low pressure SMC, is used. , 10-4
It is preferably 0 kg / cm ² . If the molding pressure is too low, it is difficult to obtain sufficient fluidity in the molding material,
On the other hand, if it is too high, the mold tends to deteriorate during mass production, which is not preferable in any case.

[0071]

Function The flow of the molding material melt onto the decorative sheet is caused by the flow of the melted and low-viscosity molding material resin into the slight gap between the edge of the decorative sheet and the mold. In the production method of the present invention, since a molding material having a high viscosity due to the inclusion of a required amount of magnesium oxide is used, the melt viscosity of the molding material increases during molding, and the fluidity of the resin decreases. As a result, it becomes difficult for the molding material resin to flow into the space between the decorative sheet and the mold, which makes it difficult to generate defective products due to the resin flowing.

[0072]

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.

As a mold, a mold for molding a 100 cm × 100 cm square flat plate was prepared.

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 decorative sheet The decorative sheet was prepared as follows.

1) Preparation of impregnating resin liquid (1) Unsaturated polyester resin (number average molecular weight of about 2000)
(1) Dissolved isophthalic acid-based unsaturated polyester resin in styrene, styrene concentration 40% by weight) 100 parts by weight (2) Polymerization initiator (tertiary butyl peroxybenzoate) 1 part by weight Above (1), (2) Were mixed and sufficiently stirred to obtain a resin solution for impregnation.

2) Preparation of decorative sheet Decorative sheet 1: titanium paper (thickness 0.1 mm, basis weight 80 g)
/ M ² , PM11P: manufactured by Kojin Co., Ltd.), the one with a stone pattern printed on it is dipped in the above resin solution to impregnate the resin, and then this is pressed by a roll to remove excess resin and decorated. Sheet 1 was obtained. The weight ratio of the base material (paper) in this decorative sheet is 5
It was 0% by weight.

Decorative sheet 2: cloth (made of nylon, thickness 0.
A decorative sheet 2 was obtained in the same manner as the decorative sheet 1 except that a stone pattern was printed on 1 mm, basis weight 90 g / m ² , manufactured by Toyobo Co., Ltd.). The weight ratio of the base material in this decorative sheet was 45% by weight.

Decorative sheet 3: non-woven fabric (made of polyester,
Thickness 0.36 mm, basis weight 40.7 g / m ² , Sontara #
A decorative sheet 3 was obtained in the same manner as the decorative sheet 1 except that a stone pattern was printed on the product (8000: manufactured by Toray Dipon). The weight ratio of the base material in this decorative sheet is 50.
% By weight.

Decorative sheet 4: glass cloth (thickness 0.2
5 mm, basis weight 200 g / m ² , plain weave, WF23010
0BS6: Nitto Boseki Co., Ltd.) was used to obtain a decorative sheet 4 in the same manner as the decorative sheet 1 except that a stone pattern was printed. The weight ratio of the glass cloth in this decorative sheet is 3
It was 5% by weight.

Decorative sheet 5: glass mat (thickness 0.3
A decorative sheet 5 was obtained in the same manner as the decorative sheet 1 except that a grain pattern was printed on 0 mm, basis weight 300 g / m ² , MC300A104: Nitto Boseki Co., Ltd.). The weight ratio of the glass mat in this decorative sheet was 35% by weight.

3. Preparation of molding material The following materials were used as the molding material. Molding material 1: (1) Unsaturated polyester resin liquid (number average molecular weight of about 200)
70 parts by weight of a styrene concentration of 40 wt% 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 ) 6 parts by weight of color pigment (titanium oxide powder, SR-1: manufactured by Sakai Chemical Industry Co., Ltd.) (6) 2.3 parts by weight of magnesium oxide powder (average particle size of about 3 μm, Kyowamag 150: manufactured by Kyowa Chemical Industry Co., Ltd.) (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) are mixed and sufficiently kneaded, and then the obtained kneaded product is 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
Obtained SMC.

Molding material 2: Same as the method for forming molding material 1 except that the amount of magnesium oxide was 3 parts by weight.
I got MC.

Molding material 3: The amount of magnesium oxide was 2.
SMC was obtained in the same manner as in the molding material 1 except that the amount was 5 parts by weight.

Molding material 4: Same as the method of forming molding material 1 except that the amount of magnesium oxide was 1 part by weight.
I got MC.

Molding material 5: Same as the method of forming molding material 1 except that the amount of magnesium oxide was changed to 5 parts by weight.
I got MC.

4. Molding method The SMC and the decorative sheet thus obtained were molded as follows. Example 1 After heating the upper mold to 140 ° C. and the lower mold to 150 ° C., the sheet 1 was placed on the lower mold as a decorative sheet. 8 pieces of the above SMC cut into a size of 50 cm x 50 cm
I charged it. Tighten the upper mold at a mold clamping speed of 4 mm / sec,
After the mold was closed, compression molding was performed at a pressure of 70 kg / cm ² for 240 seconds. Then, the mold was opened and demolded to obtain a decorative molded product. This molding was repeated 10 times to obtain 10 molded products. As shown in the attached FIGS. 1 to 3, the decorative sheet (1
A molded product having a desired shape can be obtained depending on the sizes of 1) and the molding material (12).

Examples 2 to 10 and Comparative Examples 1 to 10 Molding was carried out in the same manner as in Example 1 except that the decorative sheet was changed to that shown in Table 2.

5. Evaluation Method The molded articles obtained in the above-mentioned respective Examples and Comparative Examples were visually evaluated for the presence or absence of deficiency. Further, the area of the molding material flowing into the upper surface of the edge portion of the decorative sheet was visually measured.

The results are summarized in Tables 1 and 2.

[0093]

[Table 1]

[Table 2] As is clear from the comparison between Table 1 and Table 2, the molded articles of the examples had no resin inflow, whereas the molded articles of the comparative example had resin inflow or lack of wall. It was

[0094]

Since the method for producing a decorative molded product according to the present invention is configured as described above, it is possible to eliminate defects caused by resin flowing into the upper surface of the edge portion of the decorative sheet.
Therefore, unlike the conventional product, it is not necessary to manually and defectively correct the defective product, and the total cost can be reduced.

[Brief description of the 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): Decorative sheet (22): Molding material

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Claims (1)

[Claims] 1. When a decorative sheet and a thermosetting molding material are stacked in a mold and the mold is clamped for heat compression molding, a thermosetting resin is used as the thermosetting molding material, and
A method for producing a decorated molded article, which comprises using 1.8 to 3.5 parts by weight of magnesium oxide based on 100 parts by weight of a resin component.