JP2001287313A - Composite material and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite material having improved surface properties hard to generate a crack or the like even if a thermosetting resin molded object being a base material is a profile product or an uneven part is present on a surface while well keeping surface capacity such as design effect, antistaining properties, durability or the like. SOLUTION: A composite material, which is obtained by laminating a thermosetting resin layer 15 with a light transmissivity of 85% or more and an elongation of 5-<10% on the surface of the thermosetting resin molded object 13, and a film, which is obtained by preforming the thermosetting resin layer 15 into a film, are set in molds 11, 12 and the thermosetting resin molded object 13 is subsequently set in the molds and, if necessary, a fibrous base material 16 is placed on the molded object 13 to integrally mold the film and the thermosetting resin molded object 13.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin molded article having improved surface properties and a method for producing the same. More specifically, the present invention relates to a thermosetting resin molded article having a transparent and stretchable thermosetting resin layer on the surface and a method for producing the same.

[0002]

2. Description of the Related Art Thermosetting resin moldings are easy to compound with inorganic substances, have excellent moldability, have high heat resistance,
It is widely used in various fields such as architecture, furniture, electrical product housing, vehicles, and everyday products because of its excellent characteristics such as excellent durability and fire resistance. In order to impart or improve surface performance such as design properties, antifouling properties, and durability, these thermosetting resin molded articles are generally used by coating, glossing, patterning or laminating the surface. Is being done. The resin used for coating is generally a thermosetting resin, but the thermosetting resin molded body of the base material is a deformed product, or even a flat plate has a textured surface or other uneven surface. In some cases, the coating process is not only technically difficult but also disadvantageous in cost. Also, since this thermosetting resin coating film is a material that does not originally elongate, when a thick film having a certain thickness or more is formed, cracks are inevitable due to internal stress due to curing shrinkage, and heat of the base material is inevitable. Cracks occur because they cannot follow deformation and mechanical deformation. These cracks sometimes exert a wedge effect and can even destroy the substrate itself. In order to impart high gloss and surface smoothness to a molded product, a compression molding method, for example, a highly productive in-molding coating method (I
MC method) and high pressure coating method (HPC
Molding). However, in these methods, it is difficult to inject the coating agent from the viewpoint of adhesiveness to the base material of the molded article, and furthermore, the temperature is high (140 to 150).
° C), and cracks are likely to occur for the above reasons. Further, since the work is performed at a high temperature, troubles such as gelation of the resin injection line are observed, and there is a problem in terms of maintenance. As a complement to the above difficulties in coating technology, it is widely used to laminate a thermoplastic resin film typified by polyvinyl chloride, but since it is a thermoplastic resin, it is originally heat resistant. In addition to having inherent deficiencies in water resistance, solvent resistance, etc., recently, the contained halogens and plasticizers are starting to spark new debate in terms of environmental issues.

Next, a molded product having a design property, that is, a decorative molded product will be considered. At present, the following two methods are roughly divided. The first is a method of providing a sheet, mat, or film on which a pattern is printed on the surface of a molded article. This method uses printed sheets, mats,
Since the film is used, there is no design problem, but the manufacturing problem has not been overcome. That is, during molding, many occurrences of elongation, shrinkage, wrinkles, cuts and the like of the pattern layer are observed. In addition, the surface of the molded product is uneven,
Or, in reality, it has poor followability with a curved surface. Further, when a product having extremely high transparency and gloss is required, it is difficult to cope with this method. The second method is to use a molding material containing some decorative component. Decorating components include natural stones, artificial stones, glass, porcelain, metals, inorganic materials, colored thermoplastic resins, cured products of colored thermosetting resins, etc., colored staple fiber materials, printing or coloring. A strip of plastic film is used. in this way,
It is difficult to uniformly mix and disperse the above-mentioned material and the thermosetting matrix for molding, and it is easy to settle and separate from the relationship of the specific gravity difference. Generally difficult. Further, the pulverized product as described above is likely to be aggregated into a spherical shape, and as a result, a molded product to which these are added may cause variation or reduction in mechanical strength. Further, a method of appropriately kneading an uncured product of a coloring agent or a colored thermosetting resin into a molding material and producing a flow pattern is also performed.However, in this method, it is difficult to control the mixing time during production, Only the flow pattern is displayed, and it is impossible to display a large pattern.

[0004]

Under the circumstances described above, it is desired to establish a more effective method for further improving the performance of the surface layer of the thermosetting resin molded article. Further, it is desired to establish a more effective method for further improving the decorating performance of the thermosetting resin molded body. Therefore, an object of the present invention is to improve the surface properties such as design properties, antifouling properties, and durability, while the thermosetting resin molded product of the base material is a deformed product, or the surface has irregularities. It is an object of the present invention to provide a composite material having improved surface properties, in which cracks and the like are less likely to occur even when it is used, and a method for producing the same. Another object of the present invention is to provide a method for producing a composite material, which can further enhance the decoration performance.

[0005]

According to the present invention, there is provided a thermosetting resin layer having a light transmittance of 85% or more and an elongation of 5% or more and less than 100% on the surface of the thermosetting resin molded article. And a composite material obtained by laminating the above. Further, the present invention provides a thermosetting resin constituting the thermosetting resin molded article, wherein the thermosetting resin is one or two selected from unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, phenol resin, epoxy resin, amino resin and polyurethane. The present invention provides a composite material as described above, which is at least one species. Further, in the present invention, the thermosetting resin layer comprises (A) a vinyl ester resin, (B) an alkyl (meth) acrylate,
A resin composition comprising a vinyl compound containing at least one monomer selected from alkoxyalkyl (meth) acrylate and alkoxypolyalkylene glycol (meth) acrylate as essential components, and (C) a polymerization initiator, The present invention provides the above-mentioned composite material, which is obtained by heat-curing or light-curing. Further, the present invention is characterized in that the vinyl ester resin of the component (A) is a vinyl ester resin obtained by reacting a bisphenol type or alicyclic epoxy compound with (meth) acrylic acid. Materials. In the present invention, the alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, and alkoxypolyalkylene glycol (meth) acrylate of the component (B) each have 6 carbon atoms in the alkyl, alkoxyalkyl, and alkoxypolyalkylene glycol portions. ~ 12,
The present invention provides a composite material as described above. Further, the present invention is characterized in that the thermosetting resin layer is a colored or printed pattern while substantially maintaining transparency,
The present invention provides a composite material as described above. Further, the present invention provides the above-mentioned composite material, wherein the composite material is a plate having a smooth or uneven surface or is a deformed product. The present invention also provides a method of forming the thermosetting resin layer into a film shape in advance, and using the uncured material of the thermosetting resin layer as an adhesive to form the obtained film on the surface of a thermosetting resin molded body. The present invention provides a method for producing a composite material, wherein the composite material is cured by adhering. Further, the present invention, the thermosetting resin layer is formed into a film in advance, the resulting film is set in a mold,
Subsequently, a thermosetting resin molded body is set in a mold, and the film and the thermosetting resin molded body are integrally formed. The present invention also provides a decorative component layer having a design property laminated on a thermosetting resin molded product, and the thermosetting resin layer laminated on the decorative component layer. It is intended to provide a method for producing a composite material, which is set in a mold and integrally molded. Further, the present invention, the thermosetting resin layer, a colored printed fibrous base material is adhered, and the fibrous base material and the thermosetting resin molded product are formed on the thermosetting resin molded product. It is intended to provide a method for producing a composite material, comprising laminating so as to be in contact with each other, setting the obtained laminate in a mold, and integrally forming the same. The present invention also provides
The method for producing a composite material, wherein the fibrous base material is impregnated with a second resin composition containing an uncured thermosetting resin and a polymerization initiator used in the thermosetting resin molded article. To provide. The present invention also provides a light transmittance of 8
A thermosetting resin having an elongation of 5% or more and an elongation of 5% or more and less than 100% is impregnated and / or applied to a colored printed fibrous base material and cured into a sheet. A method for manufacturing a composite material, comprising setting a curable resin molded body in a mold and integrally molding the same. The present invention also provides a method of applying a second resin composition containing an uncured thermosetting resin used for a thermosetting resin molded article and a polymerization initiator on a sheet, and applying the second resin composition to the sheet. An object of the present invention is to provide the above-described manufacturing method in which the mold is set in a mold so as to be in contact with a body and is integrally molded.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The thermosetting resin molded article of the substrate used in the present invention is not particularly limited, and can be appropriately selected. For example, a resin such as an unsaturated polyester resin, a vinyl ester resin, a diallyl phthalate resin, a phenol resin, an epoxy resin, an amino resin, or a polyurethane is molded into a deformed product or a plate by a known method such as press molding, injection molding, or roll molding. Things. The thermosetting resin molded article may be obtained by combining a plurality of the above resins. The raw material resin composition constituting these thermosetting resin molded articles is compounded with a reinforcing material, a filler, a flame retardant, a curing shrinkage reducing agent, a polymerization initiator, a polymerization accelerator, an ultraviolet absorber, an antioxidant and the like. It is also possible to use it.

In the present invention, the thermosetting resin layer used as the surface layer of the thermosetting resin molded article preferably has a light transmittance of 85% or more and an elongation of 5% or more and less than 100%. When the light transmittance is less than 85%, the expression of design, which is one of the important objects of the present invention, becomes unsatisfactory. If the elongation is less than 5%, the ability to follow the thermal and mechanical movements of the substrate becomes insufficient as in the case of the conventional thermosetting paint,
The risk of cracking and peeling increases. On the other hand, if the elongation percentage is 100% or more, the performance such as surface hardness and stain resistance is lower than the target level of the present invention, which is inappropriate. In the present invention, “transparent” refers to JIS K-7.
105 “Light transmittance” specified by “Testing method for optical properties of plastic” means 85% or more (sample thickness is 200 μm), and elongation is JIS K-69.
11 means a measured value.

In the present invention, the thermosetting resin layer comprises
(A) vinyl ester resin and (B) alkyl (meth)
Acrylate, alkoxyalkyl (meth) acrylate and alkoxypolyalkylene glycol (meth)
A resin composition obtained by curing a resin composition obtained by blending a vinyl compound containing at least one monomer selected from acrylates as an essential component and a polymerization initiator (C) is preferable. Component (A) is a vinyl ester resin. In a narrow sense, for example, as described in Polyester Resin Handbook by Eiichiro Takiyama (Nikkan Kogyo Shimbun, 1988, p. 336), a ring-opening reaction of an epoxy group is performed. A series of oligoacrylates sharing a secondary hydroxyl group and a (meth) acryloyl group generated in the same molecule in the same molecule is defined as a vinyl ester, and when a monomer is contained, the series is defined as a vinyl ester resin. However, in the present invention, a broader definition including a reaction product of an alcohol compound and (meth) acrylic acid as described below is assumed.

A compound having a terminal epoxy group: a reaction product of bisphenol A and epichlorohydrin, a reaction product of hydrogenated bisphenol A and epichlorohydrin, a reaction product of cyclohexanedimethanol and epichlorohydrin, a reaction product of norbornanedialcohol and epichlorohydrin, Reaction product of tetrabromobisphenol with epichlorohydrin, reaction product of tricyclodecane dimethanol with epichlorohydrin, alicyclic diepoxy adipate, alicyclic diepoxy carbonate, alicyclic diepoxy acetal, alicyclic diepoxy carboxylate , Novolak epoxy compounds, cresol novolak epoxy compounds. Terminal hydroxyl group compound: bisphenol A, hydrogenated bisphenol A, cyclohexane dimethanol, norbornane dialcohol, tetrabromobisphenol A, tricyclodecane dimethanol. Compounds obtained by adding ethylene oxide and / or propylene oxide to terminal hydroxyl groups: bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, cyclohexane dimethanol ethylene oxide adduct, cyclohexane dimethanol propylene oxide adduct, hydrogenated bisphenol A Ethylene oxide adducts, hydrogenated bisphenol A propylene oxide adducts, diphenylethylene oxide adducts, diphenylpropylene oxide adducts, tetrabromobisphenol A ethylene oxide adducts. In this case, although the number of moles of ethylene oxide and propylene oxide added is relatively small, an average of about 4 to 5 moles of the adduct is preferable in terms of heat resistance, weather resistance, moisture resistance and the like. Usually, vinyl ester resins are synthesized in oxygen-containing air with a retarding effect in order to avoid the risk of gelling during production, in which case the product may be significantly colored. In such a case, the synthesis of the vinyl ester resin is preferably performed in an inert gas atmosphere. The reaction between an epoxy compound and an unsaturated acid in such an inert gas atmosphere is commonly considered to be gelling and dangerous, but it can be dealt with by precisely controlling the stirring conditions, temperature, and reaction time. sell. Examples of the inert gas here include helium, argon, and the like in addition to nitrogen, but nitrogen is practical. Among these vinyl ester resins, in the present invention, bisphenol A type and / or alicyclic vinyl ester resins are particularly suitable, and these are bisphenol A type or alicyclic epoxy compounds or hydroxyl group-containing compounds. Alternatively, it can be synthesized relatively easily by reacting methacrylic acid. It is sometimes consistent with the object of the present invention that the vinyl ester resin synthesized in this way has little coloring.

Also, the alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate and alkoxypolyalkylene glycol (meth) acrylate of the component (B) have carbon atoms in the alkyl, alkoxyalkyl and alkoxypolyalkylene glycol portions, respectively. Is preferably 6 to 12. If the number of carbon atoms is less than 6, elasticity and elongation at break tend to be small, and if it exceeds 12, the compatibility with the vinyl ester resin (A) becomes insufficient, and phase separation is likely to occur. (B)
Examples of the component include the following (meth) acrylic acid esters. Heptyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, lauryl (meth) acrylate, butoxyethyl (meth) Acrylate, propoxyethyl (meth) acrylate, ethoxybutyl (meth)
Acrylate, ethoxydiethylene glycol (meth)
Acrylates, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, and halogen-substituted compounds such as bromo and chloro of the exemplified monomers.

The component (B) includes the above-mentioned alkyl (meth)
Acrylate, alkoxyalkyl (meth) acrylate or alkoxypolyalkylene glycol (meth)
In addition to acrylates, acrylate monomers,
One or a plurality of monomers selected from the group of methacrylate monomers and other vinyl monomers can be used in combination, and specific examples include the following. These halogen-substituted compounds can also be used for flame retardation. Acrylic acid ester monomer, methacrylic acid ester monomer: phenoxyethyl methacrylate, isobornyl methacrylate, benzyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylol Propane triacrylate,
Trimethylolpropane trimethacrylate, trimethylolpropane tris-oxyethylene acrylate,
Trimethylolpropane tris-oxyethylene methacrylate, pentaerythritol tetraacrylate,
Pentaerythritol tetramethacrylate, glycerin diacrylate, glycerin dimethacrylate, 1,
6-hexanediol diacrylate, methyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, EO adduct dimethacrylate of bisphenol A, EO adduct diacrylate of bisphenol A, polyethylene glycol dimethacrylate, polyethylene Glycol diacrylate, other vinyl monomers: vinyl monomers such as styrene, α-methylstyrene, acrylonitrile, and vinyl acetate.

The proportion of the component (B) in the total of the components (A) and (B) is preferably from 10 to 60% by weight, and more preferably from 20 to 50% by weight. When the proportion of the component (B) is less than 10% by weight, the elongation of the thermosetting resin layer may be insufficient. On the other hand, the proportion of the component (B) is 60% by weight.
If it exceeds, the tensile strength tends to be poor. For the same reason, the proportion of the alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate or alkoxypolyalkylene glycol (meth) acrylate in the component (B) is 20 to 100% by weight, more preferably 30 to 100% by weight. is there.

In the present invention, when the transparent and stretchable thermosetting resin layer is cured by photocuring, it is preferable to use a large number of acrylate monomers, but it is also possible to use other monomers in combination. . When a transparent and stretchable thermosetting resin layer is formed by heat curing, there is no particular designation.

In the present invention, as a method for curing the thermosetting resin layer, either a method of heat curing or a method of light curing or a combination of both methods can be used. In the case of curing by heating, it is convenient to use an organic peroxide as the polymerization initiator (C). Known organic peroxides such as dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, and peroxyesters can be used, and specific examples thereof include the following. Benzoyl peroxide, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t-butylperoxybenzoate, t-butylhydroper Oxide, cumene hydroperoxide, dicumyl peroxide,
Di-t-butyl peroxide, 1,1,3,3-trimethylbutylperoxy-2-ethylhexanate,
2,5-dimethyl-2,5-dibutylperoxyhexane.

For photo-curing, a general-purpose photopolymerization initiator as exemplified below is added as the component (C), and irradiation with active energy rays such as light may be performed. 2,2-
Dimethoxy-1,2-diphenylethan-1-one, 1
-Vidoxy-cyclohexyl-phenyl-ketone, benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-monforinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,2-hydroxy-2-methyl-
1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide. The component (C) can be used in combination of two or more, and the use amount thereof is preferably in the range of about 0.5 to 4% by weight based on the components (A) and (B).

The composite material of the present invention can employ a general method in which a thermosetting resin layer is coated on the surface of a thermosetting resin molded article which has been formed in advance and cured, for example. If a suitable molding method is adopted, a composite material that further meets the object of the present invention can be molded. One is a method in which a thermosetting resin layer previously formed into a film is adhered and fixed to the surface of a molded thermosetting resin molded body, and is thermoset to be integrated. At this time, it is preferable to use an uncured material of the thermosetting resin layer as the adhesive in terms of both adhesiveness and refractive index. Another method is a method in which a thermosetting resin layer previously formed into a film is set in a mold when forming a thermosetting resin molded body and integrally molded. There is an advantage that the step can be omitted. Further, in this method, the thermosetting resin layer is controlled to have the same thickness even on the uneven surface, so that an excellent sense of depth, which cannot be realized by the conventional coating method, is realized. The reason why high adhesiveness is obtained for the film by this molding method is that the film is chemically bonded at the molecular level when the thermosetting resin molded article is cured. If the surface irregularities are about the grain pattern, the elongation percentage of the film of the thermosetting resin layer is 5
About 10 to 10% is sufficient, and when the surface has severe irregularities, it is preferable to use a film with a little more elongation. The processing temperature of the thermosetting resin molded body is higher than the glass transition temperature of the film, and the film is more easily stretched at room temperature, which is also advantageous to the above processing method. In this molding method, the printed titanium oxide-containing paper impregnated with the resin can be cured and integrated between the thermosetting resin molded body and the thermosetting resin layer.

In the case of manufacturing a decorative molded product, it is desirable to adopt the following method. FIG. 1 shows that a decorative component layer having a design property is laminated on a thermosetting resin molded product, the thermosetting resin layer is laminated on the decorative component layer, and the obtained laminate is molded into a mold. It is a figure for explaining a method of setting inside and performing integral molding. A decorative component layer 14 having a design property is formed on the thermosetting resin molded body 13 in the pair of molds 11 and 12.
And the thermosetting resin layer 15 are laminated and integrally formed. The decorative component layer is not particularly limited, but for example, a fibrous base material that is colored and printed is preferable. As the fibrous base material, various known forms and materials can be used, but those such as nonwoven fabric, paper, woven fabric, mat, and net are particularly preferable. The fiber material can be arbitrarily selected from natural fibers and synthetic fibers. In addition to organic fibers, inorganic fibers can be used. When a fibrous base material is used, as shown in FIG. 2, a fibrous base material 16 is adhered to a thermosetting resin layer 15, and the fibrous base material It is desirable to laminate the thermosetting resin molded body 13 so as to be in contact therewith, set the obtained laminated body in a mold, and integrally mold. At this time, if the fibrous base material is impregnated with the second resin composition containing the uncured resin of the resin used for the thermosetting resin molded product and the polymerization initiator, the thermosetting resin molded product and the fibrous base material are impregnated. Strong integration of the material is achieved. The adhesive for adhering the fibrous base material to the thermosetting resin layer is not particularly limited, but is preferably one that does not melt by heating and pressing during compression molding with a mold. Usually, the molding temperature is 140-150
° C, it is preferable to use an adhesive having a heat-resistant temperature of 160 to 170 ° C.

As another method, an uncured thermosetting resin used for the thermosetting resin layer is impregnated and / or coated on a colored printed fibrous base material and cured into a sheet to obtain a thermosetting resin. A method in which the sheet and the thermosetting resin molded body are set in a mold and integrally molded. For example,
As shown in FIG. 3, a fibrous base material 16 ′ impregnated with the uncured thermosetting resin is placed on a thermosetting resin molded body 13 in a pair of molds 11 and 12, and integrated. Molding. At this time, as shown in FIG.
On the 6 ′, a second resin composition 17 containing an uncured thermosetting resin used for the thermosetting resin layer and a polymerization initiator is applied, and the applied side is in contact with the thermosetting resin molded body 13. If the thermosetting resin molded body 13 and the fibrous base material 16 are firmly integrated, they are set in a mold and integrally molded. In the case where the thermosetting resin and the fibrous base material are integrated, the light transmittance naturally decreases. Therefore, in the present specification, when a fibrous base material is used,
The light transmittance of the thermosetting resin before integrating the fibrous base material may be 85% or more.

The thickness of the thermosetting resin layer used in the present invention is, for example, 10 to 500 μm. The thermosetting resin layer can be colored or printed by a conventional method, whereby the design of the composite material of the present invention can be further enhanced.

In order to improve the hardness, durability, weather resistance, water resistance, corrosion resistance, etc., the thermosetting resin layer used in the present invention contains a light scattering agent, an ultraviolet absorber, a light stabilizer, Additives such as a light diffusing agent, an antioxidant, an antifoaming agent, a leveling agent, a thixotropy-imparting agent, and an internal mold release agent can be added to further improve the performance. When flame retardancy is required for the composite material of the present invention, a compound containing a halogen among the components (A) and / or (B) described above is used, and if necessary, flame retardancy is used. The required characteristics can be realized by using the additives in combination. The composite material of the present invention is excellent in design, antifouling property, surface performance such as durability, construction, furniture,
It can be widely used in various fields such as electric product housings, vehicles, and daily necessities.

[0021]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention. Example 1 A resin composition was prepared by uniformly dissolving and mixing each component in a mixing ratio shown in Table 1 below.

[0022]

Table 1 Bisphenol A type vinyl ester resin 100 parts by weight (manufactured by Showa Polymer Co., Ltd., trade name: lipoxy resin RF-312, containing 40% by weight of styrene) isononyl acrylate 20 parts by weight ethoxydiethylene glycol acrylate 10 parts by weight t -Butyl peroxybenzoate 1.5 parts by weight

The mixed air bubbles did not disappear easily.
Then, the mixture was heated to 50 ° C., and the pressure was slightly reduced at about 20 Torr. As a result, bubbles could be removed quickly. This resin composition is referred to as composition P-1. This resin composition P-1 is coated to a thickness of 50 μm on each surface of a cured glass fiber reinforced epoxy resin plate and a cured glass fiber reinforced phenol resin plate whose surfaces are cleaned, and cured by heating at 130 ° C. for 10 minutes. I let it. The light transmittance of the resin composition P-1 was 93%, and the elongation was 9%. The appearance of the molded product was glossy and deep, and the adhesion was 00/100 in the cross-cut peeling test.

Example 2 The resin composition P-1 of Example 1 was sandwiched between polyethylene terephthalate (PET) films, passed between rolls having a constant gap, and then heated at 130 ° C. for 5 minutes to a thickness of 200 μm.
Was obtained. This film is designated as Q-1.
Table 2 below shows the physical properties of the Q-1 film.

[0025]

Table 2 Tensile strength 43 MPa Tensile modulus 760 MPa Elongation 9% Light transmittance 93%

With the single-sided PET film of this Q-1 film still attached, the PET film was set in a mold for forming an unsaturated polyester SMC plate so as to contact the mold,
Place an unsaturated polyester resin composition impregnated (70 g / m ² ) printed titanium paper and then apply SMC material to 70% of the total area.
And press (pressure 1MPa) and 1
Heat curing was performed at 40 ° C. for 5 minutes. The molded plate has a grain pattern with a height difference of about 1.8 mm.
The -1 film followed these irregularities well and had good adhesion. In particular, the transparency was very good, and a characteristic was seen in a unique depth feeling that has never been seen before. In addition, as a test for heat resistance and contamination resistance, a test was conducted in which a lit cigarette was pressed and extinguished. No abnormalities were observed, and this test was a weak point for the surface material of thermoplastic resin such as polyvinyl chloride. It is clear that there is a great difference from the above.

Example 3 In a 1-liter flask equipped with a thermometer, a stirrer, a fractionating condenser and a gas inlet tube, 480 g (1.20 mol) of alicyclic diepoxy adipate and 172.8 g of acrylic acid (2. 4 mol), 1.5 g of chromium octylate, 0.15 g of phosphorous acid, 0.2 g of hydroquinone
Was added, and the mixture was reacted at 120 to 125 ° C. for 2 hours while blowing nitrogen gas. At the stage when the acid value reached 11.0, the resin in the flask was poured into a metal vat and cooled, whereby a colorless and transparent resin was obtained. This resin is designated as A-1.
Next, the components shown in Table 3 below were uniformly dissolved and mixed in a flask to prepare a base resin composition P-2.

[0028]

Table 3 A-1 resin 50 parts by weight Butoxyethyl acrylate 30 parts by weight Phenoxyethyl acrylate 20 parts by weight 2-hydroxy-2-methyl-1-phenyl-propan-1-one 1.5 parts by weight (manufactured by Ciba-Geigy Co., Ltd.) Product name Darocure 1173)

The surface of the molded product having a different shape using a soft polyurethane resin is cleaned, spray-coated with a resin composition P-2 to a thickness of 40 μm, and irradiated with ultraviolet rays (high-pressure mercury lamp 8 KW) for 5 seconds while rotating. Hardened. The light transmittance of the resin composition P-2 was 92%.
And the elongation was 48%. The surface showed excellent luster, and a test in which 100 cycles of a warming / cooling cycle of -10 to 100 ° C were performed was performed, and it was confirmed that there was no problem in adhesion.

Example 4 The same operation as in Example 2 was carried out using the resin composition P-2 of Example 3 to obtain a transparent film Q-2 having a good transparency and a thickness of 200 μm. Its physical properties were as follows.

[0031]

Table 4 Tensile strength 21 MPa Tensile modulus 65 MPa Elongation 48% Light transmittance 92%

When a helmet is formed into a bag using a glass fiber reinforced vinyl ester resin sheet, the transparent film Q-2 is preliminarily heated and set so as to be approximately in a mold. The mixture was pressed and heated and cured at 140 ° C. for 3 minutes. A product in which a transparent film having an unprecedented soft feel was compounded was obtained, and the adhesion was 100/100 in a crosscut peel test, which was confirmed to be good.

Example 5 Unsaturated polyester-based SMC (trade name: Rigolac MC-314, manufactured by Showa Polymer Co., Ltd.) was placed in a mold for flat plate molding at a ratio of 70% of the total area. On this SMC, a stone-grain-printed polyester nonwoven fabric impregnated with a terephthalic acid-based unsaturated polyester resin (trade name: Rigolac M-505, manufactured by Showa Polymer Co., Ltd., containing 1% by weight of t-butylperoxybenzoate) Further, a single-sided PET film of the Q-1 film of Example 2 was stuck on this resin-impregnated nonwoven fabric, and the PET film side was set up.
In this state, compression molding was performed at a molding pressure of 3 MPa and a molding temperature of 140 ° C. for 5 minutes. The molded flat plate M-1 has a surface gloss and an unprecedented stone pattern depth.
No peeling of one film was observed. Table 5 shows the main physical properties of M-1.

[0034]

[Table 5] Glossiness (60 degrees) 98 Adhesion (cross cut tape method) 10 points

The glossiness is a value measured as a glossiness in JIS K7105 “Testing method for optical properties of plastics”, and the adhesion is an adhesion-cross-cut tape in JIS K5400 “General paint test method”. Numerical values measured by the method are shown.

Example 6 Example 5 was repeated, except that the mold of Example 5 was replaced with a mold having a stone pattern. As a result, the flat plate M-
No. 2 was a molded article with a clear stone pattern and glossy design. Similarly, M-2 did not exhibit peeling of the Q-1 film. Table 6 shows the main physical properties of M-2.

[0037]

[Table 6] Glossiness (60 degrees) 95 Adhesion (cross cut tape method) 10 points

Example 7 Unsaturated polyester SMC (trade name: Rigolac MC-314, manufactured by Showa Polymer Co., Ltd.) was placed in a mold for flat plate molding at a ratio of 70% of the total area. On this SMC, an isophthalic unsaturated polyester resin (trade name: Rigolac M-414, manufactured by Showa Kobunsha Co., Ltd.) was used as an adhesive, and a nonwoven fabric on which a stone-like pattern was printed and the Q-1 film of Example 2 were used. The bonded decorative component layer was placed. In this case, the non-woven fabric side is SMC
On the side. In this state, a molding pressure of 3 MPa and a molding temperature of 1
Compression molding was performed at 40 ° C. for 5 minutes. Molded flat plate M
-3, in particular, had a surface gloss and an unprecedented stone pattern depth, and no peeling of the Q-1 film was observed. This M
Table 7 shows the main physical properties of -1.

[0039]

[Table 7] Glossiness (60 degrees) 95 Adhesion (cross cut tape method) 10 points

Example 8 Using the resin A-1 of Example 3, the compositions shown in Table 8 below were uniformly dissolved and mixed in a flask to prepare a resin composition P-3.

[0041]

[Table 8] A-1 resin 50 parts by weight Butoxyethyl acrylate 30 parts by weight Phenoxyethyl acrylate 20 parts by weight t-butyl peroxybenzoate 1.5 parts by weight

Using this resin composition P-3, a transparent film Q-2 ′ having a thickness of 200 μm was obtained in the same manner as in Example 2. Table 9 below shows the physical properties of Q-2 ′.

[0043]

[Table 9] Tensile strength 21 MPa Tensile modulus 65 MPa Elongation 48% Light transmittance 92%

Example 9 Example 7 was repeated except that the Q-2 'film was used, to obtain a flat plate M-4. Table 10 shows the results.

[0045]

[Table 10] Glossiness (60 degrees) 95 Adhesion (cross cut tape method) 10 points

Comparative Example 1 Resin B-1 was synthesized in Example 3 without performing the antioxidant method (indicating addition of phosphorous acid and introduction of nitrogen gas) used in the synthesis of resin A-1. This resin B-1 was a resin having a larger coloring and yellowing than the resin A-1. Table 11 below shows the difference in hue between Resins A-1 and B-1.

[0047]

[Table 11] Hue of resin A-1 Hazen 50 Hue of resin B-1 Gardner 6

Using the resin B-1, the compositions shown in Table 12 below were uniformly dissolved and mixed in a flask.
4 was produced.

[0049]

Table 12 B-1 resin 50 parts by weight Butoxyethyl acrylate 30 parts by weight Phenoxyethyl acrylate 20 parts by weight t-butyl peroxybenzoate 1.5 parts by weight

Using this resin composition P-4, a transparent film Q-3 having a thickness of 200 μm was obtained in the same steps as in Example 2.
Table 13 shows the physical properties of Q-3.

[0051]

[Table 13] Tensile strength 19 MPa Tensile modulus 62 MPa Elongation 45% Light transmittance 58%

Next, except for using the Q-3 film,
Example 5 was repeated to obtain a flat plate M-5. Table 14 shows the results.
Shown in

[0053]

[Table 14] Glossiness (60 degrees) 75 Adhesion (cross cut tape method) 10 points

Example 10 The resin composition P-1 of Example 1 was impregnated into a stone-grain printed polyester nonwoven fabric, and was passed between rolls at regular intervals with a polyethylene terephthalate (PET) film sandwiched between the upper and lower parts, and then at 130 ° C. For 5 minutes to obtain a decorative sheet. This sheet is designated as Q-4. Unsaturated polyester SMC (trade name: Rigolac MC-31, manufactured by Showa Kogyo KK)
4) was placed in a mold for plate forming at a rate of 70% of the entire area. A single-sided PET film of a Q-4 sheet was stuck on this SMC and set with the PET film side up. In this state, compression molding was performed at a molding pressure of 3 MPa and a molding temperature of 140 ° C. for 5 minutes. The formed flat plate M-6 had a surface gloss, an unusual stone pattern depth, and no peeling of the Q-4 film was observed. Table 15 shows the main physical properties of M-6.

[0055]

[Table 15] Glossiness (60 degrees) 96 Adhesion (cross cut tape method) 10 points

Example 11 The resin composition P-1 of Example 1 was applied to both sides of a grain-printed polyester non-woven fabric, and the upper and lower portions were sandwiched between polyethylene terephthalate (PET) films and passed between rolls at regular intervals. Heating was performed at 130 ° C. for 5 minutes to obtain a decorative sheet. This sheet is designated as Q-5. Next, except for using the Q-5 sheet, the compression molding in Example 10 was performed to produce a flat plate M-7. M-7, in particular, had a surface gloss, an unprecedented stone pattern depth, and no peeling of the Q-5 film was observed. Table 16 shows the main physical properties of this M-7.
Shown in

[0057]

[Table 16] Glossiness (60 degrees) 95 Adhesion (cross cut tape method) 10 points

Example 12 The resin composition P-1 of Example 1 was impregnated into a stone-pattern printed polyester nonwoven fabric, and was passed between rolls at regular intervals with a polyethylene terephthalate (PET) film sandwiched between upper and lower sides. Thereafter, the PET film on one side was peeled off, and the resin composition P-1 was applied to this side. The PET film was covered again and heated at 130 ° C. for 5 minutes to obtain a decorative sheet. This sheet is designated as Q-6. Next, the compression molding in Example 10 was performed to produce a flat plate M-8, except that the resin composition P-1 coated side of the Q-6 sheet was placed on the SMC. M-8, in particular, had a surface gloss and an unprecedented stone pattern depth, and no peeling of the Q-6 sheet was observed. Table 17 shows the main physical properties of this M-8.

[0059]

[Table 17] Glossiness (60 degrees) 98 Adhesion (cross cut tape method) 10 points

Example 13 The resin composition P-3 of Example 8 was replaced with Q-
A Q-7 sheet was obtained in the same process as in the case where four sheets were produced. Next, except that the Q-7 sheet was used, the compression molding in Example 10 was performed to produce a flat plate M-9.
M-9, in particular, had a surface gloss and an unprecedented stone pattern depth, and no peeling of the Q-7 sheet was observed. This M
Table 18 shows the main physical properties of -9.

[0061]

[Table 18] Glossiness (60 degrees) 97 Adhesion (cross cut tape method) 10 points

Comparative Example 3 The resin composition P-4 of Comparative Example 1 was replaced with Q in Example 10.
A Q-8 sheet was obtained in the same process as in the case of producing a -4 sheet. Next, Example 10 was repeated except that the Q-8 sheet was used, to obtain a flat plate M-10. Flat plate M-10
Was a molded article having a dull stone pattern and poor surface gloss. The results are shown in Table 19.

[0063]

[Table 19] Glossiness (60 degrees) 75 Adhesion (cross cut tape method) 10 points

Comparative Example 4 Using the resin composition P-5 shown in Table 20 below, a sheet Q-9 was obtained in the same manner as in the preparation of the Q-4 sheet in Example 10.

[0065]

[Table 20] Terephthalic acid-based unsaturated polyester resin 100 parts by weight (manufactured by Showa Polymer Co., Ltd., trade name: Rigolac resin M-505, containing 34.5% by weight of styrene monomer) Neopentyl glycol diacrylate 20 parts by weight Styrene Monomer 10 parts by weight t-butyl peroxybenzoate 1.5 parts by weight

Next, a flat plate M-11 was obtained by repeating Example 10 except that the Q-9 sheet was used. Flat plate M-1
No. 1 was a molded article having a dull stone pattern and poor surface gloss. The results are shown in Table 21.

[0067]

[Table 21] Glossiness (60 degrees) 75 Adhesion (cross cut tape method) 0 points

[0068]

According to the present invention, while maintaining good surface properties such as designability, antifouling property and durability, the thermosetting resin molded product of the base material is irregularly shaped or has irregularities on the surface. Provided is a composite material having improved surface properties, in which cracks and the like are less likely to occur even if a part exists, and a method for producing the same. Further, according to the present invention, there is provided a method of manufacturing a composite material, which can further enhance the decoration performance.

[Brief description of the drawings]

FIG. 1 A decorative component layer having a design property is laminated on a thermosetting resin molded product, and the thermosetting resin layer is laminated on the decorative component layer. It is a figure for explaining a method of setting inside and performing integral molding.

FIG. 2 is a view for explaining another embodiment of the manufacturing method of the present invention.

FIG. 3 is a diagram for explaining another embodiment of the manufacturing method of the present invention.

FIG. 4 is a diagram for explaining another embodiment of the manufacturing method of the present invention.

[Explanation of symbols]

 11, 12 Mold 13 Thermosetting resin molded article 14 Decorating component layer 15 Thermosetting resin layer 16, 16 'Fibrous base material 17 Second resin composition

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Minoura 5-3-23, Sakushindai, Hanamigawa-ku, Chiba-shi, Chiba (72) Inventor Junnosuke Suzuki 2-19-4, Osugi, Edogawa-ku, Tokyo (72) Invention Person Fumiaki Sano 779-8, Tamamura-cho, Sawa-gun, Gunma Prefecture (72) Inventor Nobuto Hagiwara 1441 Miyakocho, Isesaki-shi, Gunma 204 Sezon Kokuya 204 (72) Inventor Takeshi Noguchi 3-Hanazumisaka, Kyotanabe-shi, Kyoto 16-1 F-term (reference) 4F100 AK01A AK01B AK21A AK21B AK25B AK33A AK36A AK41A AK43A AK51A AK53A AR00C BA02 BA03 BA07 BA10A BA10C CA30B EJ37B GB33 HB00C JB13A JB01 JN00B06

Claims (14)

[Claims] 1. A thermosetting resin molded article having a light transmittance of 85% or more and an elongation of 5% or more and 100% or more on the surface thereof.
A composite material obtained by laminating a thermosetting resin layer of less than. 2. The thermosetting resin constituting the thermosetting resin molded product is one or two selected from unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, phenol resin, epoxy resin, amino resin and polyurethane. The composite of claim 1, which is at least one species. 3. The thermosetting resin layer is composed of (A) a vinyl ester resin and (B) one or more selected from alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates and alkoxypolyalkylene glycol (meth) acrylates. 3. A resin composition obtained by blending a vinyl compound containing a monomer as an essential component and (C) a polymerization initiator, and obtained by heat-curing or light-curing, wherein the resin composition is obtained. The composite material as described. 4. The vinyl ester resin (A) is a vinyl ester resin obtained by reacting a bisphenol type or alicyclic epoxy compound with (meth) acrylic acid. A composite material according to item 1. 5. The alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate and alkoxypolyalkylene glycol (meth) acrylate of the component (B) each having 6 carbon atoms in the alkyl, alkoxyalkyl and alkoxypolyalkylene glycol portions. The composite material according to claim 3, wherein 6. The thermosetting resin layer according to claim 1, wherein the thermosetting resin layer is colored or printed with a pattern while substantially maintaining transparency. Composite materials. 7. The composite material according to claim 1, wherein the composite material is in the form of a plate having a smooth or uneven surface, or is a deformed product. 8. The thermosetting resin layer according to claim 1, 3, 4, 5 or 6, wherein said thermosetting resin layer is formed into a film in advance, and said uncured thermosetting resin layer is used as an adhesive to obtain said thermosetting resin layer. A method for producing a composite material, comprising bonding the obtained film to the surface of a thermosetting resin molded article and curing the same. 9. The thermosetting resin layer according to claim 1, 3, 4, 5, or 6, is formed into a film in advance, and the obtained film is set in a mold. A method for producing a composite material, comprising setting a molded body in a mold and integrally molding the film and the thermosetting resin molded body. 10. A decorative component layer having a design property is laminated on a thermosetting resin molded article, and the decorative component layer is formed on the decorative component layer.
Laminating the thermosetting resin layer according to 3, 4, 5 or 6,
A method for producing a composite material, comprising setting the obtained laminate in a mold and integrally forming the same. 11. A fibrous base material, which is colored and printed, is adhered to the thermosetting resin layer according to claim 1, 3, 4, 5, or 6, and the fibrous base material is applied on a thermosetting resin molded body. A method for producing a composite material, comprising laminating a base material and the thermosetting resin molded body so as to be in contact with each other, setting the obtained laminated body in a mold, and integrally molding. 12. The fibrous base material is impregnated with a second resin composition containing an uncured thermosetting resin used for a thermosetting resin molded article and a polymerization initiator. 3. The method for producing a composite material according to item 1. 13. A thermosetting resin having a light transmittance of 85% or more and an elongation of 5% or more and less than 100%,
Impregnating and / or applying to the colored printed fibrous base material and curing it into a sheet form, setting the obtained sheet and thermosetting resin molded body in a mold, and integrally molding, Manufacturing method of composite material. 14. A second resin composition containing an uncured thermosetting resin used for a thermosetting resin molded article and a polymerization initiator is applied on a sheet, and the coated side is coated with the thermosetting resin molded article. 14. The method for producing a composite material according to claim 13, wherein the composite material is set in a mold so as to be in contact with a body and integrally molded.