JPH08150618A - COMPRESSION MOLDING SHEET AND METHOD FOR PRODUCING MOLDED ARTICLE USING THE SHEET - Google Patents

Abstract

PURPOSE: To provide a sheet for compression molding which is free from the bleeding of a thermosetting molding material onto the sheet for compression molding when performing thermal compression molding, and also from the running-out of the resin blend of the sheet into a molding material layer. CONSTITUTION: A resin composition containing an unsaturated polyester resin liquid, t-butylperoxybenzoate (T10h 105 deg.C) and 0.5 part of 2-hydroxy-2-methyl-1- phenylpropane is applied to a PET film. In addition, a chopped strand mat which is impregnated with a resin composition, is laminated on the resin composition-applied layer, and the PET film is laminated on one side of the mat. Further, one side of the resin composition of the laminate is irradiated with a sterilization lamp and the other side of the layer also with the lamp to manufacture a sheet for compression molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compression molding sheet and a method for producing a molded article using the sheet, and more particularly to a method for producing a decorative molded article having a pattern on its surface. Specifically, the compression-molding sheet is preferably used for manufacturing bathtubs, bathtub wall materials, waterproof pans, counters, and the like, particularly those molded products having a pattern on the surface.

[0002]

2. Description of the Related Art Conventionally, as a method for manufacturing a molded article of this type, a method as described below is disclosed in JP-A-2-2793.
Thirteen methods were known. That is, a mixture of a surface pattern forming granular material and a surface pattern forming resin is applied to a surface sheet, and an impregnating sheet is superposed on the mixture coating layer to form a compression molding sheet. Then, this sheet is set in the mold with the surface sheet side being the mold side, and a thermosetting molding material is placed on the compression molding sheet, and heat compression molding is performed by the mold. Then, the surface sheet is peeled off from the cured molded product to produce a patterned molded product.

[0003]

However, in such a conventional manufacturing method, since the resin impregnated in the compression molding sheet is not cross-linked, the compression molding sheet is soft, and therefore the sheet is The thermosetting molding material exuded on the surface of the compression molding sheet when the molding materials were stacked and subjected to heat compression molding, or the resin mixture impregnated in the sheet flowed out into the molding material layer.

An object of the present invention is that the thermosetting molding material does not exude on the surface of the compression molding sheet during the above-mentioned heat compression molding, and the resin mixture of the compression molding sheet flows into the molding material layer. It is to provide a compression-molding sheet that does not have the above, and to provide a method for producing a molded product using the sheet.

[0005]

A compression molding sheet of the present invention comprises a thermosetting resin as a main component, and a thermosetting resin composition containing a high temperature curable organic peroxide and a radical cleavage type photoinitiator. Is impregnated into a sheet-shaped reinforcing material, and the composition is semi-cured by irradiation with preliminary light.

The method for producing a molded article according to the present invention is characterized in that the compression molding sheet and the thermosetting molding material are placed on top of each other in a mold and heat compression molding is performed. is there.

The present invention will be described in detail below.

The high temperature curing type organic peroxide used in the present invention belongs to a high temperature type initiator, and preferably has a 10-hour half-life temperature (T _10h ) in the range of 80 to 110 ° C. When T _10h is lower than 80 ° C., when the compression molding sheet is semi-cured by light irradiation, the high temperature curable organic peroxide may be decomposed and the sheet may be completely cured.
On the other hand, when T _10h is higher than 110 ° C., the molding temperature becomes high, which may cause yellowing during molding.

Therefore, what is called a medium temperature curing type organic peroxide (initiator) having a T _10h of 30 to 70 ° C., such as 2,4,4-trimethylpentyl peroxydicarbonate and 2,4-dichlorobenzoyl peroxide. It is used by distinctly distinguishing.

The addition amount of the above high temperature curable organic peroxide is
It is preferably in the range of 0.05 to 4 parts by weight, more preferably 0.1 to 4 parts by weight based on 100 parts by weight of the total amount of the thermosetting resin, the copolymerizable monomer, and the low-shrinking agent resin added as necessary. 3 parts by weight, more preferably 0.3 to
It is in the range of 1.5 parts by weight. If the addition amount is less than 0.05 parts by weight, it takes a considerably long time to complete the curing,
The productivity of molded products deteriorates. On the contrary, if the addition amount is more than 4 parts by weight, the cost is high and it is disadvantageous.

Examples of the above-mentioned high temperature curable organic peroxide include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane,
1,1-di-t-butylperoxycyclohexane,
2,2-di-t-butylperoxybutane, t-butylperoxy-3,5,5-trimethylhexanoate,
t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, 1,6-bis (t-butylperoxycarboxy) hexane, diethylethylene glycol bis (t-butylperoxycarbonate), Methyl isobutyl ketone peroxide, t-butyl peroxymaleic acid, t-butyl peroxylaurylate,
2,5-Dimethyl-2,5-di (benzoylperoxy) hexane, 2,2-bis (t-butylperoxy)
Octane and di-t-butylperoxyisophthalate may be mentioned.

These high temperature curable organic peroxides may be used alone or as a mixture of plural kinds.

In the present invention, the radical cleavage type photoinitiator is used because the hydrogen abstraction type photoinitiator (for example, benzophenone, diethylthioxanthone, etc.) or the ion reaction type photoinitiator has a large extinction coefficient and an effective wavelength up to the inside. Since it is hard to penetrate, the curing inside the sheet is much less than that on the surface, and the thermosetting molding material exudes or is impregnated on the surface of the compression molding sheet during heat compression molding. This is because problems such as the mixture flowing out occur.

The addition amount of the radical-cleaving photoinitiator is preferably 0.05 based on 100 parts by weight of the total amount of the thermosetting resin, the copolymerizable monomer, and the low-shrinking agent resin which is optionally added. To 4 parts by weight, more preferably 0.1
To 2 parts by weight, more preferably 0.2 to 1 part by weight. If the addition amount is less than 0.05 parts by weight, it takes a considerably long time for the compression molding sheet to be semi-cured by irradiation with preliminary light, resulting in poor productivity. On the contrary, if the addition amount is more than 4 parts by weight, the cost becomes high and disadvantageous.
Since there are many initiators on the surface, the internal penetration of the effective wavelength becomes extremely weak, only the sheet surface is cured, and the thermosetting molding material oozes out to the compression molding sheet surface during heat compression molding, Alternatively, there arises a problem that the impregnated resin mixture flows out.

Examples of the radical-cleaving photoinitiator include benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, benzyl dimethyl ketal, hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-. Phenylpropane, acylphosphine oxide, 1- (4-dodecylphenyl) -2-
Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- {4- ( Methylthio) phenyl} -2-morpholinopropanone-1. These radical-cleaving photoinitiators may be used alone or in combination of two or more.

As the thermosetting resin in the compression molding sheet of the present invention, at least one kind of unsaturated polyester resin, epoxy acrylate resin and urethane acrylate resin is used. These resins may be used alone or as a mixture of plural kinds.

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

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

As the urethane acrylate resin,
A conventionally known and conventional one is used. For example, 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.

The thermosetting resin used in the compression-molding sheet of the present invention may contain styrene, α-methylstyrene, divinylbenzene, vinyltoluene, diallylphthalate, various acrylate monomers, various methacrylate monomers, etc., if necessary. The copolymerizable monomer can be added in an amount of 0 to 80 parts by weight based on 100 parts by weight of the thermosetting resin. Usually, in the case of unsaturated polyester resin, 30 to 60% by weight of the monomer is contained in the total amount of the resin and the copolymerizable monomer.

The thermosetting resin liquid (thermosetting resin plus copolymerizable monomer) used in the compression-molding sheet of the present invention contains polyvinyl acetate as a low-shrinking agent,
Thermoplastic resins such as polymethyl (meth) acrylate, polyethylene, ethylene vinyl acetate copolymers, vinyl acetate-styrene copolymers, polybutadiene, saturated polyesters, saturated polyethers, etc. Total amount of polymerizable resin and copolymerizable monomer) 10
0 to 10 parts by weight can be added to 0 parts by weight.

The thermosetting resin used in the compression-molding sheet of the present invention contains glass powder, aluminum hydroxide, calcium carbonate, etc. as a filler in an amount of 0 to 150 relative to 100 parts by weight of the resin liquid. Parts by weight can be added.

Further, the thermosetting resin composition used in the compression molding sheet of the present invention includes dimethylaniline,
Known curing accelerators such as cobalt naphthenate, polymerization inhibitors such as parabenzoquinone, metal soaps such as zinc stearate, release agents such as aliphatic phosphates and lecithin, phosphite compounds, phenol compounds, etc. A stabilizer or the like can be added in an appropriate amount depending on the intended use and purpose.

As a reinforcing material for impregnating these thermosetting resin compositions, chopped strands such as glass fiber, polyester, polypropylene and rayon fiber,
Or glass fiber, polyester, polypropylene,
There are woven and non-woven fabrics made of rayon fibers and the like. Chopped strands can also be used as long as they are formed into a sheet with the thermosetting resin composition. Specific examples of woven and non-woven fabrics include glass roving cloth, glass chopped strand mat, filament mat,
Examples thereof include glass continuous mat, surface mat, polyester non-woven fabric, polypropylene non-woven fabric and the like. The woven or non-woven fabric may be printed with a stone pattern, a geometric frame pattern, a floral pattern, or the like. The weight per unit area of the above woven and non-woven fabric is 100 to 500 g / in the case of inorganic fiber
m ^2, whereas in the case of organic fibers 20 to 200 g / m ² is typical. The woven cloth and the non-woven cloth may be used as a single layer, or may be laminated as two or more layers.

The proportion of the reinforcing material in the total amount of the resin composition and the reinforcing material in the compression molding sheet is generally 5 to 50% by weight. If the proportion of the reinforcing material decreases, the flow of resin cannot be suppressed. On the contrary, if this ratio is too large, the reinforcing material is not sufficiently impregnated with the resin mixture, and air bubbles are easily mixed in the sheet.

The case where the compression-molding sheet of the present invention is used for decoration will be described below.

When the compression-molding sheet of the present invention is used for decoration, a method for imparting a pattern is to print a stone pattern, a geometric frame pattern, a floral pattern, etc. on the surface of the sheet-like reinforcing material. Is used to impart a pattern to the sheet. A pattern material, a pigment, etc. are mixed into the thermosetting resin composition to give a sheet a grain pattern or the like. Examples thereof include a method in which the refractive index of the thermosetting resin liquid, the reinforcing material, and the filling material are substantially matched to give an artificial marble-like pattern having a transparent feeling and a deep feeling to the sheet.

The pattern material of the present invention includes granules obtained by crushing thermosetting resin moldings such as unsaturated polyester resin, phenol resin or melamine resin, natural mica, colored mica, cold water stone, natural stone, shells, Metal powder can be used.
The shape of the pattern material is not particularly limited, and for example, a granular or scale-like material is used, and the size is usually 0.1 to 10 mm, preferably 0.5 to 5 mm, more preferably 1 to 3 mm. The blending amount of the above-mentioned pattern material varies depending on the manufacturing method and the required pattern, and is appropriately selected.

Further, glass powder, aluminum hydroxide, calcium carbonate or the like can be added as a filler to the thermosetting resin composition used in the compression molding sheet of the present invention. Glass powder, aluminum hydroxide and the like are suitable for imparting transparency and a sense of depth to the sheet, and calcium carbonate and the like are suitable for imparting concealing properties. The blending amount of the filler is a manufacturing method,
Since it depends on the required pattern, it is appropriately selected.

The thermosetting resin composition used in the compression molding sheet of the present invention includes carbon black, titanium oxide, iron oxide, cyanine pigment, aluminum flakes, nickel powder, gold powder, silver powder, titanium yellow, etc. Pigments, azo dyes, anthraquinones, indigoids,
A dye such as a stilbene-based dye can be added. The blending amount of the above-mentioned pigment varies depending on the required pattern and is appropriately selected.

An example of a method for producing the compression-molding sheet of the present invention will be given.

When the reinforcing material is chopped strands, first, a thermosetting resin, a radical cleavage type photoinitiator, a high temperature curing type organic peroxide, chopped strands and various additives to be added as necessary are blended, and then blended. The materials are well mixed with a mixer or the like to prepare a thermosetting resin composition. Next, the thermosetting resin composition is applied onto a protective film such as a polyethylene film or a polyethylene terephthalate film (hereinafter abbreviated as PET) to produce an uncured sheet.

When the reinforcing material is a woven fabric or a non-woven fabric, for example, a thermosetting resin, a radical cleavage type photoinitiator, a high temperature curing type organic peroxide and various additives to be added as necessary are blended. The mixture is thoroughly mixed with a mixer or the like to prepare a thermosetting resin composition. Next, for example, by laminating a woven fabric or a non-woven fabric on a protective film such as a polyethylene film or a PET film, the other side of the woven fabric or the non-woven fabric,
That is, the resin composition is applied and impregnated on the surface without the film, and a protective film is laminated on this surface as well to produce an uncured sheet. Alternatively, first, a thermosetting resin composition is applied to a protective film, and a chopped strand mat, a woven fabric, or a non-woven fabric is laminated on the applied layer to impregnate the resin composition into the mat, etc. A protective film is laminated on one surface to produce an uncured sheet.

Then, this uncured sheet is semi-cured by irradiation with preliminary light to produce a compression molding sheet. Specifically, a sterilizing lamp, an ultraviolet fluorescent lamp, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, etc., whose irradiation amount is 0.2 to 10
The sheet is semi-cured by irradiating light from both sides or one side of the uncured sheet so that the sheet has J / cm ² . A more preferable range of the irradiation amount is 1.0 to 8.0 J / cm ² .
If the irradiation dose is less than 0.2 J / cm ^2, the radical-cleavable photoinitiator in an amount sufficient to semi-cure the uncured sheet by pre-light irradiation will not be decomposed, and the sheet for compression molding of the sheet for heat-pressing will be formed. Resin may flow out. On the other hand, the irradiation dose is 10
If it is stronger than J / cm ² , the radical cleavage type photoinitiator is almost completely decomposed, and the compression molding sheet becomes too hard and cracks are generated at the time of heat and pressure molding.

The above semi-cured state means that the sheet retains its shape, the surface does not become sticky, and the sheet has strength and flexibility to the extent that resin does not flow out and cracks do not occur during heat / pressure molding. The range of curing degree of 5 to 60% is general, and the range of 15 to 45% is more preferable. Examples of the method of measuring the degree of curing include a method of quantifying the residual monomer.

The thickness of the compression molding sheet generally used is 0.3 to 3.0 mm. If the sheet is thin, the color of the molding material can be seen through. On the other hand, if the thickness of the sheet is thick, it will be difficult for the effective wavelength to penetrate into the inside of the sheet, so curing inside the sheet will be insufficient, and the thermosetting molding material will exude to the surface of the compression molding sheet during heat compression molding. Or, there arises a problem that the impregnated resin mixture flows out. Further, in the thermosetting molding material used in the present invention, unsaturated polyester resin, vinyl ester resin, urethane acrylate resin or the like is used as the thermosetting resin, and various copolymerizable monomers, low-shrinking agents, various Fillers, colorants, initiators, reinforcements, additives and the like can be added.

As a particularly general-purpose example of such a molding material, for example, an unsaturated polyester resin is dissolved in styrene, a low-shrinking agent made of a thermoplastic resin is added, and an organic peroxide or the like as an initiator is added. In addition, various fillers, reinforcing materials such as glass fibers, etc. are added to form SMC or BMC.

The materials for the compression-molding sheet of the present invention are as described above, and the method for producing a molded article according to the present invention using the same 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 form of the molding die, generally upper and lower dies 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 mold is attached to the above molding machine, and
After heating to ˜180 ° C., the compression molding sheet is placed at a required position on the lower mold.

Then, a thermosetting molding material such as SMC or BMC is overlaid, the mold is clamped, pressure molding is carried out at a pressure of 10 to 120 kg / cm ² for 30 seconds to 15 minutes, and after curing, the mold is opened. When the product is demolded, a molded product made of a laminated material and optionally decorated is obtained.

Here, when a decorated sheet is used as the compression molding sheet, the direction in which it is placed on the lower mold is as follows.
The product surface side is usually the surface that is printed or decorated with a pattern material or the like, but if necessary, the molding material side such as SMC or BMC may be the surface that is decorated.

Here, the size of the decorative molding sheet may be large so as to decorate the entire surface of the molded product, or small so that only a part of the surface of the molded product is decorated. It can be one. That is, the size of the decorative forming sheet may be any size and shape depending on the desired design.

[0045]

The radical cleaving photoinitiator used in the present invention has a small extinction coefficient, so that the effective wavelength easily penetrates into the interior of the sheet, and therefore the preliminary light irradiation causes
It is possible to easily obtain a compression molding sheet in a substantially homogeneous semi-cured state. Then, even if the thermosetting molding material is overlaid on the compression molding sheet in the mold and subjected to heat compression molding, the resin mixture of the compression molding sheet flows out into the molding material layer or is thermoset. Does not exude on the surface of the compression molding sheet. Moreover, since the compression molding sheet has not been completely cured, the sheet has flexibility,
The sheet does not crack during heat compression molding.

According to the method for producing a molded article of the present invention, since the compression molding sheet is in a semi-cured state, the workability in placing it on the mold is good, and it is not completely cured. In combination with the good affinity with the thermosetting molding material and the very good adhesiveness at the interface, a molded product can be efficiently obtained.

[0047]

EXAMPLES Examples of the present invention and some comparative examples to be compared with them will be shown below. All parts are by weight.

<Preparation of SMC> ・ Unsaturated polyester resin liquid (about 60 wt% of isophthalic acid-based unsaturated polyester resin and about 4 parts of styrene monomer)
70 parts by weight dissolved in 0% by weight-Polystyrene low-shrinking agent resin (polystyrene resin approx. 3)
30 parts of 0% by weight dissolved in about 70 parts of styrene monomer) -Calcium carbonate powder (NS-100: Nitto Koka Kogyo Co., Ltd.) 120 parts-Curing agent (Kayabutyl B: Kayaku Akzo Co., tertiary Butyl peroxybenzoate content: 98 wt% 1 part ・ Thickener (magnesium oxide powder, Kyowamag 15)
0: manufactured by Kyowa Chemical Industry Co., Ltd.) 1 part Internal release agent (zinc stearate: manufactured by Sakai Chemical Industry Co., Ltd.) 3 parts After mixing the above materials and thoroughly stirring, the resulting mixture was impregnated with SMC. Depending on the device, glass fiber (Roving made by Asahi Fiber Glass Co., Ltd .: ER4630LBD1
Sixty parts (66 W cut into a length of 25 mm) were impregnated and aged at 40 ° C. for 24 hours to obtain SMC.

(Example 1) 100 parts of unsaturated polyester resin liquid (product number 9305Z, styrene content 50% by weight: manufactured by Takeda Pharmaceutical Co., Ltd.) and t-butyl peroxybenzoate (T _10h 105 ° C .: Kayaku Akzo Co., Ltd.) 1 part), 2-hydroxy-2-methyl-1-phenylpropane (manufactured by Merck Ltd.) 0.5 part, colored mica (black) 3 parts with a particle size of about 3 mm, and coloring with a particle size of about 3 mm. 0.5 part of mica (white), 0.5 part of colored mica having a particle size of about 3 mm (gray) (manufactured by Ito Sangyo Co., Ltd.), and 75 parts of glass powder (particle size 5.7 μm: manufactured by Nitto Boseki Co., Ltd.) When,
A resin composition comprising 25 parts of aluminum hydroxide was kneaded with a mixer, the resulting kneaded product was applied to a PET film, and a chopped strand mat (weight per unit area: 450 g / m ² ) was laminated on the applied layer to form a mat. Was impregnated with the resin composition, and a PET film was laminated on the other side of the mat. The resin composition layer side of this laminate was irradiated with a sterilizing lamp at 0.54 J / cm ² (180 seconds), and the opposite side of the same layer was irradiated with a sterilizing lamp at 2.7 J / cm ² (900 seconds) and compressed. A molding sheet was produced.

The structure of this decorative compression molding sheet is shown in FIG. In FIG. 1, (1) is PE first coated with the resin composition.
A chopped strand mat is laminated on the T film, and the mat is impregnated with the resin composition.
(1 ') is a PET film laminated on the other side of the mat, (2) is a decorative compression molding sheet obtained by impregnating the mat with a resin composition, and (2') is a resin composition of the sheet Physical layer,
(3) is a colored mica contained as a pattern material in the same composition.

In FIG. 2, an upper die (4) of a 300 mm × 300 mm square flat plate die is placed at 115 ° C. and a lower die (5).
After heating to 135 ° C., the PET film (1) (1 ′) laminated on both sides of the decorative compression molding sheet (2) cut into 200 mm × 200 mm is peeled off, and the resin composition layer
The sheet (2) was placed with the side (2 ') facing the mold surface of the lower mold (5). Decorative compression molding sheet with 400g of SMC (6) above
The upper mold (4) and the lower mold (5) were clamped with a 300-ton press in this state, and heat compression molding was performed at a pressure of 70 kg / cm ² for 400 seconds. The obtained molded product is
The decorative surface layer and the molding material layer were integrated, and there was no flow of the resin mixture, seepage of SMC, and cracks in the decorative sheet.

(Example 2) A resin composition comprising the same unsaturated polyester resin liquid as in Example 1 was kneaded in a mixer, except that glass powder and aluminum hydroxide were not blended. The resulting kneaded product is applied to a PET film, and a chopped strand mat (weight per unit: 450 g / cm ² : manufactured by Nitto Boseki Co., Ltd.) is laminated on the applied layer to impregnate the resin composition into the mat, and the other side of the mat is used. The PET film was also laminated on the side of. Both sides of this laminate were exposed to 2.4 J / cm ² (30
Second) for irradiation to produce a compression molding sheet.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the decorative surface layer and the molding material were integrated, and there was no flow of the resin mixture, no SMC seepage, and no cracks in the decorative sheet.

(Example 3) 100 parts of unsaturated polyester resin liquid (same as in Example 1), 1 part of t-butylperoxyisopropyl carbonate (T _10h 97 ° C), and 2 parts
-Hydroxy-2-methyl-1-phenylpropane 2.
0 part, 100 parts of glass powder (5.7 μm), 3 parts of colored mica (black) having a particle size of about 3 mm, 0.5 part of colored mica (white) having a particle size of about 3 mm, and a particle size of about 3 mm A resin composition consisting of 0.5 part of colored mica (gray) was kneaded with a mixer, and the obtained kneaded product was applied to a PET film,
Chopped strand mat (Meshsuke 3
50 g / m ² ) was laminated to impregnate the mat with the resin composition, and the PET film was laminated on the other side of the mat. Both sides of this laminate are 1.6 J / c with an ultra-high pressure mercury lamp.
Irradiation with m ² (20 seconds) was performed to produce a compression molding sheet.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the decorative surface layer and the molding material were integrated, and there was no flow of the resin mixture, no SMC seepage, and no cracks in the decorative sheet.

Example 4 100 parts of unsaturated polyester resin liquid (product number 7682, styrene content 33% by weight: manufactured by Nippon Yupica Co., Ltd.) and t-butylperoxyisopropyl carbonate (T _10h 97 ° C .: Kayaku Akzo Co., Ltd.) (Made by the company) 1 part, 2-hydroxy-2-methyl-1-phenylpropane 0.2 part, colored mica with a particle size of about 3 mm (black) 3 parts, colored mica with a particle size of about 3 mm (white) 0 .5
Part and 0.5 part of colored mica (gray) having a particle size of about 3 mm are kneaded with a mixer, the obtained kneaded product is applied to a PET film, and a polyester nonwoven fabric ( Sontara # 8100: Basis weight 136g / m
² : DuPont Japan Co., Ltd.) was laminated to impregnate the nonwoven fabric with the resin composition, and the PET film was laminated on the other side of the polyester nonwoven fabric. Both sides of this laminate were irradiated with an ultra-high pressure mercury lamp at 4.0 J / cm ² (50 seconds) to produce a compression molding sheet.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the decorative surface layer and the molding material were integrated, and there was no flow of the resin mixture, no SMC seepage, and no cracks in the decorative sheet.

Example 5 100 parts of unsaturated polyester resin liquid (same as in Example 1), 0.5 part of methyl isobutyl ketone peroxide (T _10h 88 ° C.), and 2-hydroxy-2-methyl-1. -0.5 parts of phenylpropane, 0.5 parts of colored mica (black) of about 3 mm, and particle size of about 3
mm of a colored mica (white), 2 parts of a colored mica having a particle size of about 3 mm (gray), and 0.05 part of carbon black were kneaded with a mixer, and the resulting kneaded product was PET. It was applied to a film, a chopped strand mat (weight per unit area: 350 g / m ² ) was laminated on the applied layer to impregnate the resin composition into the mat, and a PET film was laminated on the other side of the mat. The resin composition layer side of this laminate was exposed to 1.6 J / cm ² (20
Second), and the other side of the layer is 3.2 J / cm with an ultra-high pressure mercury lamp.
² (40 seconds) was irradiated to produce a compression molding sheet.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the decorative surface layer and the molding material were integrated, and there was no flow of the resin mixture, no SMC seepage, and no cracks in the decorative sheet.

Example 6 Unsaturated polyester resin liquid
100 parts (same as Example 4) and methyl isobutyl keto
Peroxide (T_10h88 ° C) 0.5 part and bend
Le dimethyl ketal (manufactured by Nippon Ciba Geigy Co., Ltd.)
0.5 part and 25 parts of glass powder (5.7 μm),
3 parts of colored mica (black) with a particle size of about 3 mm, and a particle size of about 3 mm
0.5 parts of colored mica (white) and a colored mica with a particle size of about 3 mm
Mix the resin composition consisting of 0.5 part of squid (gray) with a mixer.
Kneading with a kneader and applying the resulting kneaded product to a PET film
Then, add chopped strand mat (eye
With 350g / cm²: Nitto Boseki Co., Ltd.)
Impregnate the resin composition on the mat and
A PET film was also laminated on one side. This laminated tree
0.54 J / cm on the side of the fat composition layer with a germicidal lamp²(180
Sec), and 2.16 J / cm on the other side of the same layer with a germicidal lamp ²
Irradiation (720 seconds) was performed to produce a compression molding sheet.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the decorative surface layer and the molding material were integrated, and there was no flow of the resin mixture, no SMC seepage, and no cracks in the decorative sheet.

Example 7 100 parts of an unsaturated polyester resin liquid (same as in Example 4), 1 part of t-butylperoxyisopropyl carbonate (T _10h 97 ° C.), and 0.5 part of hydroxycyclohexyl phenyl ketone. , 6 parts of colored mica (black) with a particle size of about 3 mm, 1 part of colored mica with a particle size of about 3 mm (white), 1 part of colored mica with a particle size of about 3 mm (gray), and 0.05 part of carbon black The resin composition consisting of the above is kneaded with a mixer, the obtained kneaded product is applied to a PET film, and a chopped strand mat (basis weight 450 g / cm ² : manufactured by Nitto Boseki Co., Ltd.) is laminated on the applied layer to form a mat. The resin composition was impregnated therein and a PET film was laminated on the other side of the mat. The resin composition layer side of this laminated body was 0.54 with a germicidal lamp.
A sheet for compression molding was produced by irradiating J / cm ² (180 seconds) and the other side of the same layer with a germicidal lamp at 2.7 J / cm ² (900 seconds).

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the decorative surface layer and the molding material were integrated, and there was no flow of the resin mixture, no SMC seepage, and no cracks in the decorative sheet.

(Example 8) 100 parts of unsaturated polyester resin liquid (same as in Example 1), 1 part of t-butylperoxyisopropyl carbonate (T _10h 97 ° C), and 2 parts
-Hydroxy-2-methyl-1-phenylpropane 0.
03 parts, 3 parts of colored mica (black) having a particle size of about 3 mm, 0.5 part of colored mica (white) having a particle size of about 3 mm, and a particle size of about 3 m
m of a colored mica (gray) of 0.5 m was kneaded with a mixer, the resulting kneaded product was applied to a PET film, and a chopped strand mat (weight per unit area: 450 g / m ² 2) was laminated to impregnate the mat with the resin composition, and the PET film was laminated on the other side of the mat. Both sides of this laminate were irradiated with an ultra-high pressure mercury lamp at 6.0 J / cm ² (75 seconds) to produce a compression molding sheet.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, only a slight flow of the pattern layer was observed on the surface.

(Example 9) 100 parts of unsaturated polyester resin liquid (same as in Example 1), 1 part of t-butylperoxyisopropyl carbonate (T _10h 97 ° C), and 2 parts
5 parts of hydroxy-2-methyl-1-phenylpropane, 3 parts of colored mica (black) having a particle size of about 3 mm, and a particle size of about 3
mm of colored mica (white) and 0.5 part of colored mica having a particle size of about 3 mm (gray) were kneaded with a mixer, and the resulting kneaded product was applied to a PET film. Then, a chopped strand mat (basis weight: 450 g / m ² ) was laminated on the coated layer to impregnate the resin composition into the mat, and a PET film was laminated on the other side of the mat. Irradiate the resin composition layer side of this laminate with an ultra-high pressure mercury lamp at 0.8 J / cm ² (10 seconds), and irradiate the opposite side of the same layer with an ultra-high pressure mercury lamp at 2.4 J / cm ² (30 seconds). , A compression molding sheet was produced.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. This molded product had only a few cracks on the surface.

(Comparative Example 1) A decorative sheet was manufactured according to the method described in JP-A-2-279313. Specifically, an unsaturated polyester resin liquid (same as in Example 4),
t-Butyl peroxybenzoate (T _10h 105 ° C)
1 part, 100 parts of glass powder, 8 parts of mica having a particle diameter of about 3 mm (made by Ito Sangyo Co., Ltd.), 0.1 part of iron oxide (black), and 1 part of titanium oxide (white) were mixed to obtain The resulting mixture was applied on a PET film, and a polyester non-woven fabric (Sontara # 8100: basis weight 136 g) was applied on this coating layer.
/ M ² : DuPont Japan Co., Ltd.)
A PET film was also laminated on the other side of the non-woven fabric.
Thus, a decorative compression molding sheet was manufactured.

The PET film on the opposite side of the resin coating layer was peeled from the decorative compression molding sheet cut into 200 mm × 200 mm, and the sheet was placed with the coating layer of the resin composition facing the lower mold surface. Others were molded in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the decorative surface layer and the molding material were integrated, but SMC exuded on the surface of the decorative sheet.

Comparative Example 2 Unsaturated polyester resin liquid
100 parts (same as Example 1), medium temperature curing type organic peroxide
2,4,4-trimethylpentylperoxy
Dicarbonate (T _10h41 ° C: Kayaku Akzo Co., Ltd.
1 part) and 2-hydroxy-2-methyl-1-phenyl
0.5 parts of propane and glass powder (5.7 μm)
25 parts, 3 parts of colored mica (black) having a particle size of about 3 mm, and particles
0.5 parts of colored mica (white) with a diameter of about 3 mm and a particle size of about 3 m
Resin composition consisting of 0.5 parts of mica (gray)
Knead the product with a mixer, and put the resulting kneaded product in PET fill
Applied to a chord and place the chopped strand marker on top of this coating layer.
Unit (weight per unit 450 g / m²) Is laminated and the resin is placed in the mat.
Impregnate the composition with PET on the other side of the mat.
The film was laminated. Both sides of this stack are super high pressure mercury lamps
2.4 J / cm²(30 seconds) Irradiate and compress for molding
Manufactured.

Molding was performed in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. This molded product had many cracks on the surface of the decorative sheet.

Comparative Example 3 100 parts of unsaturated polyester resin liquid (same as in Example 1), 1 part of t-butylperoxyisopropyl carbonate (T _10h 97 ° C.), and benzophenone which is a hydrogen abstraction type photoinitiator. 0.5 parts (manufactured by Nippon Kayaku Co., Ltd.), 1 part 2-ethylaminoethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 3 parts colored mica (black) having a particle size of about 3 mm, and a particle size of about 3 mm. 0.5 parts of colored mica (white) and 0.5 part of colored mica (gray) having a particle diameter of about 3 mm are kneaded with a mixer, and the resulting kneaded product is applied to a PET film, On top of this coating layer, chopped strand mat
g / m ² ) was laminated to impregnate the mat with the resin composition, and the PET film was laminated on the other side of the mat. Irradiate the resin composition layer side of this laminate with an ultra-high pressure mercury lamp at 1.6 J / cm ² (20 seconds), and irradiate the opposite side of the layer with an ultra-high pressure mercury lamp at 3.2 J / cm ² (40 seconds). , A compression molding sheet was produced.

Molding was carried out in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the resin mixture of the compression molding sheet flowed except the decorated portion, and SMC exuded on the surface of the compression molding sheet.

Comparative Example 4 100 parts of an unsaturated polyester resin liquid (same as in Example 1), 1 part of t-butylperoxyisopropyl carbonate (T _10h 97 ° C.) and diethyl which is a hydrogen abstraction type photoinitiator. Thioxanthone 0.
5 parts (manufactured by Nippon Kayaku Co., Ltd.), colored mica with a particle size of about 3 mm (black), 3 parts, and colored mica with a particle size of about 3 mm (white)
0.5 parts and colored mica (gray) having a particle size of about 3 mm.
A resin composition consisting of 5 parts was kneaded with a mixer, the resulting kneaded product was applied to a PET film, and a chopped strand mat (weight per unit area: 450 g / m ² ) was applied on this coating layer.
Was laminated to impregnate the mat with the resin composition, and the PET film was laminated on the other side of the mat. The resin composition layer side of this laminate was 1.6 J / cm with an ultra-high pressure mercury lamp.
² (20 seconds), and the other side of the same layer with an ultra-high pressure mercury lamp.
Irradiation with ² J / cm ² (40 seconds) produced a compression molding sheet.

Molding was performed in the same manner as in Example 1. The PET film was peeled off from the obtained molded product. In this molded product, the resin mixture of the compression molding sheet flowed except the decorated portion, and SMC exuded on the surface of the compression molding sheet.

Tables 1 to 9 show Examples 1 to 9 for the composition of the thermosetting resin composition used in the production of the compression molding sheet, and the like.
Comparative Examples 1 to 4 are collectively shown in Table 2.

[0077]

[Table 1]

[Table 2]

[0078]

According to the present invention, the compression molding sheet is semi-cured by irradiation with preliminary light. Therefore, a thermosetting molding material is laminated on the sheet for heat and pressure molding. And, in the obtained molded product, in addition to the portion where the sheet is placed, the impregnated resin composition flows out, the thermosetting molding material exudes into the compression molding sheet, or the compression molding sheet cracks. It is possible to efficiently obtain a molded product having a desired appearance without causing the occurrence of.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a decorative compression molding sheet having PET films laminated on both sides.

FIG. 2 is a cross-sectional view showing a state where a compression molding sheet and a molding material are arranged on the compression molding sheet.

[Explanation of symbols]

 1, 1 ': PET film 2: Sheet for decorative compression molding 2': Resin composition layer 3: Colored mica 4: Upper mold 5: Lower mold

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08J 5/04 // B29K 101: 10 105: 20 B29L 9:00

Claims (2)

[Claims] 1. A thermosetting resin composition containing a thermosetting resin as a main component and containing a high temperature curable organic peroxide and a radical cleavage type photoinitiator is impregnated into a sheet-shaped reinforcing material, and preliminary light irradiation is performed. A sheet for compression molding obtained by semi-curing the same composition. 2. A method for producing a molded article, comprising placing the compression-molding sheet according to claim 1 and a thermosetting molding material on the compression-molding sheet in a mold, and performing heat compression molding. .