JP2009202444A - Composite molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite molded article which has both of design properties and rigidity, is enhanced in the adhesiveness of respective layers constituting the composite molded article, is excellent in moldability and is effectively prevented from the occurrence of sink or warpage. <P>SOLUTION: The composite molded article comprises a laminate of an artificial marble layer and a reinforcing layer formed through a norbornene resin layer. Preferably, the norbornene resin layer is a layer comprising a norbornene resin molded object produced by subjecting a norbornene monomer to bulk polymerization in a mold. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composite molded body having an artificial marble layer and a reinforcing layer. More specifically, the composite molded body combines design and rigidity, and has high adhesiveness to each layer constituting the composite molded body, excellent moldability, and The present invention also relates to a composite molded body in which occurrence of sink marks and warpage is effectively prevented.

  In the field of housing equipment materials such as ceilings and wall panels, waterproof pans, bathtubs, bathroom counters, wash bowls, wash counters, kitchen counters, kitchen sinks, etc., there is a demand for resin molded articles with excellent design. As such a resin molded body, for example, an artificial marble obtained by adding various fillers to a thermosetting resin such as a vinyl ester resin, an unsaturated polyester resin, or an acrylic resin is used.

  On the other hand, since such an artificial marble has insufficient rigidity, a layer made of fiber reinforced plastic (FRP) is provided on the surface opposite to the design surface by interposing steel, wood, or the like. Improvement of rigidity is achieved by spray-up molding (see, for example, Patent Document 1). However, although the rigidity can be improved by forming the fiber reinforced plastic layer as in Patent Document 1, when the fiber reinforced plastic layer is formed by spray-up molding, generation of volatile organic gas (VOC) is generated. Therefore, there are concerns about the environmental impact of volatile organic gases. Moreover, in the case of spray-up molding, there is also a problem that the production cycle is bad.

  On the other hand, for example, a solid molding material that constitutes an artificial marble layer and a solid molding material that constitutes a fiber-reinforced plastic layer are directly laminated by hot pressing, and each layer is formed. A method of obtaining a laminated molded body composed of an artificial marble layer and a fiber reinforced plastic layer by curing the molding material to be constituted is also conceivable. However, when a laminated molded body is manufactured by such a method, the component constituting the artificial marble layer and the component constituting the fiber reinforced plastic layer are mixed at the interface, and the layered composite molding having good appearance is obtained. There is a problem that the body cannot be obtained. In addition, such a molded body is likely to warp, and further has a problem of poor adhesion between the artificial marble layer and the fiber-reinforced plastic layer.

JP-A-6-305038

  The present invention is made in view of such a situation, has an artificial marble layer and a reinforcing layer, combines design and rigidity, has high adhesion of each layer constituting the composite molded body, and has excellent moldability, And it aims at providing the composite molded object which generation | occurrence | production of sink and curvature was prevented effectively.

  As a result of earnest research to solve the above problems, the present inventors have found that the above object can be achieved by interposing a norbornene-based resin layer between an artificial marble layer and a reinforcing layer and laminating them. The present invention has been completed.

  That is, according to the present invention, there is provided a composite molded body in which an artificial marble layer and a reinforcing layer are laminated via a norbornene resin layer.

Preferably, the norbornene-based resin layer is a layer made of a norbornene-based resin molded body obtained by bulk polymerization of a norbornene-based monomer in a mold.
The artificial marble layer is preferably formed by molding a bulk molding compound comprising a thermosetting resin composition, and one or more resins selected from vinyl ester resins, unsaturated polyester resins and acrylic resins. It is more preferable to form a bulk molding compound comprising a composition containing
Preferably, the reinforcing layer is formed by molding a sheet molding compound made of an unsaturated polyester resin composition.

  According to the present invention, since the composite molded body is formed by laminating the artificial marble layer and the reinforcing layer via the norbornene-based resin layer, the composite molded body has both design and rigidity and constitutes the composite molded body. It is possible to provide a composite molded body having high adhesion of each layer, excellent moldability, and effectively preventing warpage.

The composite molded article of the present invention is a molded article obtained by laminating an artificial marble layer and a reinforcing layer via a norbornene-based resin layer.
Such a composite molded body of the present invention includes, for example, a molding material that constitutes an artificial marble layer, a norbornene resin molded body that constitutes a norbornene resin layer, and a molding that constitutes a reinforcing layer. It is possible to manufacture by laminating the materials in this order and integrally molding them.

Norbornene-based resin layer The norbornene-based resin layer constituting the composite molded body of the present invention is composed of a norbornene-based resin molded body.
In particular, in the present invention, the norbornene-based resin molded body for forming the norbornene-based resin layer is preferably a bulk polymer obtained by bulk polymerization of a norbornene-based monomer in a mold. Such a bulk polymer is prepared by dividing a norbornene monomer, a metathesis catalyst and an optional component into two or more liquids to prepare a reaction stock solution, and a reaction solution obtained by mixing the reaction stock solution is injected into a mold. It is manufactured by doing.

  The norbornene-based monomer is a compound having a norbornene ring structure, and any compound may be used as long as it is such a compound. Especially, since the molded object excellent in heat resistance is obtained, it is preferable to use the polycyclic norbornene-type monomer more than tricyclic.

  Specific examples of norbornene-based monomers include bicyclic compounds such as norbornene and norbornadiene; tricyclic compounds such as dicyclopentadiene (cyclopentadiene dimer) and dihydrodicyclopentadiene; tetracyclic compounds such as tetracyclododecene; Pentacycles such as pentadiene trimer; heptacycles such as cyclopentadiene tetramer; alkyl such as methyl, ethyl, propyl and butyl, alkenyl such as vinyl, alkylidene such as ethylidene, phenyl, tolyl, naphthyl, etc. And substituted groups having polar groups such as ester groups, ether groups, cyano groups, and halogen atoms. These monomers may be used in combination of two or more. Among these, a tricyclic, tetracyclic or pentacyclic monomer is preferable, and dicyclopentadiene is particularly preferable because it is easily available, has excellent reactivity, and has excellent heat resistance of the obtained molded body. preferable.

  In addition, it is preferable that the ring-opening polymer to be produced is a thermosetting type. For this purpose, among the norbornene-based monomers, two or more reactive double bonds such as a symmetric cyclopentadiene trimer are used. It is preferable to use at least a crosslinkable monomer. The ratio of such a crosslinkable monomer (excluding dicyclopentadiene) in all norbornene monomers is preferably 2 to 30% by weight.

  In addition, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene, which can be ring-opening copolymerized with a norbornene-based monomer, may be used as a comonomer within a range not impairing the object of the present invention.

The metathesis catalyst is not particularly limited as long as it can ring-open polymerization a norbornene monomer in the reaction injection molding method (RIM method), and may be a known one.
Examples of such a metathesis catalyst include compounds of transition metals belonging to Group 5 or Group 6 of the periodic table, metal carbene complexes having a metal atom of Group 8 of the periodic table as a central metal, and the like.

Examples of transition metal compounds of Group 5 or Group 6 of the periodic table include halides, oxyhalides, oxides, organic ammonium salts, oxyacid salts, and heteropolyacid salts of these transition metals. Among these, halides, oxyhalides and organic ammonium salts are preferable, and organic ammonium salts are more preferable. Moreover, as a transition metal, molybdenum, tungsten, and tantalum are preferable, and molybdenum and tungsten are more preferable.
Particularly preferred embodiments of the metathesis catalyst include tridodecyl ammonium molybdate and tungstate, methyl tricapryl ammonium molybdate and tungstate, tri (tridecyl) ammonium molybdate and tungstate, and Examples include trioctylammonium molybdate and tungstate.

  When the compound of transition metal belonging to Group 5 or Group 6 of the periodic table is used as a metathesis catalyst, the amount used is usually 0.01 to 50 mmol, preferably 0, per 1 mol of norbornene monomer in the reaction solution. .1-20 mmol.

  When the amount of the metathesis catalyst used is too small, the polymerization activity is too low and the reaction takes time, and the production efficiency tends to be lowered. On the other hand, if the amount used is too large, the reaction becomes too violent, and bulk polymerization proceeds before the reaction solution is sufficiently filled in the mold, and the catalyst tends to precipitate, making it difficult to store homogeneously. Tend to be.

  The metathesis catalyst may be used by dissolving or dispersing in a small amount of an inert solvent. Examples of such inert solvents include chain aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic carbonization such as cyclopentane, cyclohexane, methylcyclohexane, decahydronaphthalene, tricyclodecane, and cyclooctane. Hydrogen solvents; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ether solvents such as diethyl ether and tetrahydrofuran. Further, a liquid anti-aging agent, a plasticizer or an elastomer may be used as a solvent as long as the activity as a catalyst is not lowered. Among these solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and alicyclic hydrocarbon solvents that are widely used industrially are preferable.

  Moreover, in this invention, it is preferable to use a filler as an arbitrary component and to make a norbornene-type resin molded object contain a filler. The filler is not particularly limited as long as it is a solid material insoluble in the norbornene-based monomer, but it is preferable to use a fibrous filler and a particulate filler. By using such two kinds of fillers, fibrous and particulate, the rigidity and dimensional stability of the resulting composite molded body can be improved.

  The fibrous filler has an aspect ratio of preferably 5 to 100, more preferably 10 to 50, particularly preferably 15 to 35, and a 50% volume cumulative diameter, preferably 0.1 to 50 μm, more preferably 1 to 50 μm. 30 μm. The aspect ratio of the filler is a ratio between the average major axis diameter of the filler and the 50% volume cumulative diameter. Here, the average major axis diameter is a number average major axis diameter calculated as an arithmetic average value obtained by measuring the major axis diameters of 100 fillers randomly selected from an optical micrograph. The 50% volume cumulative diameter is a value obtained by measuring the particle size distribution by the X-ray transmission method.

  Specific examples of the fibrous filler include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapot type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, acicular carbonate Calcium, acicular boehmite and the like can be mentioned. Especially, since the intensity | strength of the molded object obtained with a small usage-amount can be raised and a block polymerization reaction is not inhibited, wollastonite is preferable.

  The particulate filler has an aspect ratio of preferably 1 to 2, more preferably 1 to 1.5, and a 50% volume cumulative diameter is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. .

  Specific examples of the particulate filler include calcium carbonate, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, carbon black, graphite, antimony oxide, Examples thereof include red phosphorus, various metal powders, clay, various ferrites, and hydrotalcite. These particulate fillers may be hollow bodies. Of these, calcium carbonate is preferable because it does not inhibit the bulk polymerization reaction.

  In the case of using a fibrous filler and a particulate filler, these ratios are preferably in a weight ratio of fibrous filler: particulate filler = 95: 5 to 5:95, 95: 5 The range of ˜50: 50 is more preferable, and the range of 80:20 to 60:40 is particularly preferable. By setting the ratio of the fibrous filler to the particulate filler within the above range, the rigidity and dimensional stability of the obtained molded body can be made uniform, and the anisotropy of the obtained composite molded body can be improved. Can be small.

  These fibrous fillers and particulate fillers preferably have a hydrophobic surface. By using a hydrophobized filler, the filler can be uniformly dispersed in the norbornene-based resin layer, the rigidity and dimensional stability of the resulting composite molded body can be made uniform, and further anisotropic Can be reduced. Examples of the treating agent used for the hydrophobizing treatment include silane coupling agents, titanate coupling agents, aluminum coupling agents, fatty acids, fats and oils, surfactants, waxes, and other polymers.

  Moreover, in this invention, when making a norbornene-type resin molding contain a fibrous filler and a particle | grain filler, it is preferable to use these as a hybrid filler by stirring these at high speed at high speed.

  The hybrid filler only needs to be obtained by high-speed stirring of the fibrous filler and the particulate filler at high speed, and the stirring conditions for high-speed stirring are not particularly limited. Can be obtained by stirring so that the peripheral speed (blade tip speed) of the rotary blade is usually 10 to 60 m / s, preferably 15 to 55 m / s. By dispersing these fibrous fillers and particulate fillers at high speed to form a hybrid filler, the dispersibility in the norbornene-based monomer can be enhanced, and the effect of adding these fillers can be enhanced.

  In addition, it is preferable to hydrophobize the surface of the fibrous filler and the particulate filler when dry-stirring at high speed to form a hybrid filler.

  Moreover, in this invention, you may use arbitrary components other than the filler mentioned above. Such optional ingredients include activators, activity modifiers, elastomers, and antioxidants.

  Examples of the activator include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides obtained by substituting a part of the alkyl groups of these alkylaluminum halides with alkoxy groups; organotin compounds; Although the usage-amount of an activator is not specifically limited, Usually, it is 0.1-100 mol with respect to 1 mol of metathesis catalysts used with the whole reaction liquid, Preferably it is 1-10 mol.

The activity regulator can change the reaction rate, the time from the mixing of the reaction solution to the start of the reaction, the reaction activity, and the like.
In the case of using a transition metal compound of Group 5 or Group 6 of the periodic table as the metathesis catalyst, examples of the activity regulator include compounds having an action of reducing the metathesis catalyst. Alcohols, haloalcohols, esters , Ethers, nitriles, and the like can be used. Of these, alcohols and haloalcohols are preferable, and haloalcohols are particularly preferable.
Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol and the like. Specific examples of haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol and the like.

  A Lewis base compound is mentioned as an activity regulator in the case of using a metal carbene complex as a metathesis catalyst. Lewis base compounds include Lewis base compounds containing phosphorus atoms such as tricyclopentylphosphine, tricyclohexylhexylphosphine, triphenylphosphine, triphenylphosphite, n-butylphosphine; n-butylamine, pyridine, 4-vinylpyridine, acetonitrile , Lewis base compounds containing nitrogen atoms such as ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, imidazole, and the like. In addition, norbornene substituted with an alkenyl group such as vinyl norbornene, propenyl norbornene and isopropenyl norbornene is the norbornene-based monomer and also serves as an activity regulator. The amount of these activity regulators used varies depending on the compound used and is not uniform.

  Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and ethylene. -Propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), hydrides thereof and the like. The viscosity of the reaction solution can be adjusted by dissolving the elastomer in the reaction solution. Moreover, the impact resistance of the norbornene-based resin molded body and composite molded body obtained can be improved by adding an elastomer. The usage-amount of an elastomer is 0.5-20 weight part normally with respect to 100 weight part of norbornene-type monomers in a reaction liquid, Preferably it is 2-10 weight part.

  Examples of the antioxidant include various antioxidants for plastics and rubbers such as phenol, phosphorus and amine.

  And the norbornene-type resin molding which forms the norbornene-type resin layer of this invention divides each above-mentioned component into two or more liquids as a reaction stock solution, and injects the reaction stock solution into the mold, and the norbornene in this mold It is produced by bulk polymerization of a system monomer.

Examples of the combination of two or more reaction stock solutions include the following two types (a) and (b) depending on the type of metathesis catalyst used.
That is, (a) as a metathesis catalyst, it does not have a polymerization reaction activity alone, but when a catalyst that exhibits a polymerization reaction activity by using an activator in combination is used, a reaction stock solution containing a norbornene monomer and an activator ( A reaction stock solution is prepared by dividing into a1) and a reaction stock solution (a2) containing a norbornene monomer and a metathesis catalyst. And these reaction stock solutions are used, and these can be mixed and the above-mentioned reaction solution can be obtained. In this case, a reaction stock solution (a3) containing a norbornene-based monomer and containing neither a metathesis catalyst nor an activator may be used in combination.
Moreover, when using what has a polymerization reaction activity alone as (b) metathesis catalyst, it reacts by dividing into reaction stock solution (b1) containing a norbornene-type monomer, and reaction stock solution (b2) containing a metathesis catalyst. Prepare stock solution. And these reaction stock solutions are used, and these can be mixed and the above-mentioned reaction solution can be obtained. At this time, as the reaction stock solution (b2), a solution obtained by dissolving or dispersing a metathesis catalyst in a small amount of an inert solvent is usually used.

  In the case of using the fibrous filler and the particulate filler, in any of the above (a) and (b), these fillers may be contained in any reaction stock solution, but the norbornene monomer It is preferable that it is contained in the reaction stock solution containing. That is, in the case of the above (a), it may be contained in one or more of the reaction stock solutions (a1), (a2) and (a3), but from the viewpoint of easy reaction control, (a2 ) Or (a3) preferably contains a filler. In the case of (b), it is preferably contained in the reaction stock solution (b1).

  In the present invention, a collision mixing apparatus conventionally known as a reaction injection (RIM) molding apparatus can be used for mixing the reaction stock solution during bulk polymerization. Then, two or more reaction stock solutions are instantaneously mixed with a mixing head of a RIM machine to form a reaction solution, this reaction solution is poured into a mold, and a norbornene monomer is polymerized in this mold. In addition to the collision mixing device, a low-pressure injector such as a dynamic mixer or a static mixer can also be used.

  The mold used for the reaction injection molding does not necessarily need to be a high-rigid and expensive mold, and is not limited to a metal mold, and a resin mold or a simple mold can be used. This is because reaction injection molding can be performed at a relatively low temperature and low pressure using a low-viscosity reaction stock solution. Further, it is preferable to replace the inside of the mold with an inert gas such as nitrogen gas before injecting the reaction solution.

  The mold temperature is preferably 10 to 150 ° C, more preferably 30 to 120 ° C, still more preferably 50 to 100 ° C. The mold clamping pressure is usually in the range of 0.01 to 10 MPa. The bulk polymerization time may be appropriately selected, but is usually 20 seconds to 20 minutes, preferably 20 seconds to 5 minutes after the injection of the reaction stock solution.

Artificial marble layer The artificial marble layer is formed by molding a molding material that constitutes the artificial marble layer, and exhibits a natural stone-like appearance. In the present invention, the artificial marble layer is preferably formed by reaction-curing bulk molding (BMC) made of a thermosetting resin composition as a molding material.

  The thermosetting resin composition constituting the BMC contains a thermosetting resin, a polymerizable compound, a filler, and a curing agent.

  As a thermosetting resin which comprises a thermosetting resin composition, 1 type, or 2 or more types chosen from a vinyl ester resin, an unsaturated polyester resin, and an acrylic resin is mentioned.

  Examples of the vinyl ester resin include an epoxy acrylate resin obtained by esterifying an unsaturated acid with a terminal hydroxyl group of an epoxy resin. Such an epoxy acrylate resin can have various structures depending on the epoxy resin and unsaturated acid used. Epoxy resins include bifunctional vinyl ester resins such as bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, and polyphenylene ether type epoxy resins; multifunctional types such as modified bisphenol A type epoxy resins and novolac type epoxy resins. Vinyl ester resin; and the like. Moreover, as a monomer which comprises epoxy acrylate resin, a (meth) acrylic-type monomer is mentioned, Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other (meth) acrylates having one acryloyl group in the molecule; ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate having two acryloyl groups in the molecule such as (meth) acrylate; (meth) acrylate having three acryloyl groups in the molecule such as trimethylolpropane tri (meth) acrylate; and the like.

  The unsaturated polyester resin is synthesized by addition reaction or dehydration condensation reaction of α, β-olefin type unsaturated dicarboxylic acid or its anhydride and glycol. In addition to these, saturated dicarboxylic acids and aromatic dicarboxylic acids, or anhydrides thereof, dicyclopentadiene that reacts with carboxylic acids, and the like can also be used in combination.

Examples of the α, β-olefinic unsaturated dicarboxylic acid constituting the unsaturated polyester resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of these dicarboxylic acids.
Moreover, as a saturated dicarboxylic acid (dicarboxylic acid having no carbon-to-carbon unsaturated bond other than an aromatic ring) used in combination with an α, β-olefinic unsaturated dicarboxylic acid, for example, adipic acid, sebacic acid, succinic acid Phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid and the like.
Among these, it is preferable to use fumaric acid as the α, β-olefin unsaturated dicarboxylic acid, and to use phthalic acid as the saturated dicarboxylic acid in combination.

Examples of the glycol constituting the unsaturated polyester resin include the following.
That is, examples of the diol include alkanediol, polyalkylene glycol, hydrogenated bisphenol A, diol obtained by adding ethylene oxide or propylene oxide to bisphenol A, and hydrogenated products thereof.
Moreover, as alkanediol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol and cyclohexanediol.
Examples of the polyalkylene glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
In addition to these glycols, monools such as octyl alcohol and oleyl alcohol; triols such as trimethylolpropane;
Among these, it is preferable to use hydrogenated bisphenol A, neopentyl glycol, and 1,6-hexanediol in combination.

  Examples of the acrylic resin include those obtained by radical polymerization of a monomer mixture containing one or more of the above-described (meth) acrylic monomers as a main component.

  Further, as the thermosetting resin, urethane (meth) acrylate having a urethane bond in the molecule may be used in addition to the above-described resins or in addition to the above-described resins.

  Examples of the polymerizable compound include styrene, divinylbenzene, chlorostyrene, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclohexane. Pentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, bisphenol A alkylene oxide Examples include di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

  The content of the polymerizable compound is preferably 10 to 100 parts by weight, more preferably 25 to 85 parts by weight with respect to 100 parts by weight of the thermosetting resin. When there is too little content of a polymeric compound, the fluidity | liquidity of a thermosetting resin composition may worsen, or the water resistance of the composite molding obtained may fall. On the other hand, if the amount is too large, the resulting composite molded body may become brittle.

  As the filler, crushed stones such as olivine, nepheline, feldspar, wollastonite, apatite, calcite, rhodolite, barite, etc .; mica, glass, aluminum hydroxide, alumina, kaolin, etc. are preferred, and crushed stones Particularly preferred. These fillers may be used alone or in combination of two or more.

  The filler is preferably treated with a coupling agent in order to improve the adhesion at the interface with the resin. Although it does not specifically limit as a coupling agent, A silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc. are mentioned. A coupling agent may be used independently and may be combined two or more types.

  The content of the filler is preferably 50 to 400 parts by weight, more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the thermosetting resin. When there is too little content of a filler, the designability of the composite molding obtained may fall. On the other hand, if the amount is too large, workability may be reduced.

Examples of the curing agent include organic peroxide polymerization initiators and metal soaps, and these may be used in combination.
Examples of the organic peroxide polymerization initiator include bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, t-butylperoxyneodecanoate, and t-butylperoxyneohexanoate. Ate, t-butylperoxyneoheptanoate, t-hexylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxyneodecanoate, t-butylperoxypivalate, Lauroyl peroxide, 2,4,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate Eate.
Examples of the metal soap include cobalt salts such as cobalt naphthenate and cobalt octylate, manganese naphthenate, potassium naphthenate, potassium octylate, calcium naphthenate, and calcium octylate.

The content of the curing agent is preferably 0.01 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the thermosetting resin. When there is too little content of a hardening | curing agent, hardening of an artificial marble layer may become inadequate. On the other hand, when too much, the storage stability of a thermosetting resin composition may fall.
These curing agents may be used alone or in combination of two or more.

In the thermosetting resin composition, if necessary, thickener, metal powder, mold release agent other than the above, curing accelerator, polymerization inhibitor, ultraviolet absorber, light stabilizer, color pigment, An extender pigment, a conductive pigment, a modified resin, a surface preparation agent, and the like can be blended.
Examples of the thickener include oxides or hydroxides of alkaline earth metals such as magnesium oxide, magnesium hydroxide, and calcium oxide.

The reinforcing layer reinforcing layer is formed by molding a molding material that constitutes the reinforcing layer, and imparts rigidity to the composite molded body. In the present invention, it is preferable that the reinforcing layer is formed by using a sheet molding compound (SMC) made of the unsaturated polyester resin composition for reinforcing layer as a molding material, and reaction-curing it.

  The unsaturated polyester resin composition for reinforcing layer constituting SMC contains an unsaturated polyester, a polymerizable compound, a reinforcing fiber material, and a curing agent.

  As unsaturated polyester resin which comprises the unsaturated polyester resin composition for reinforcement layers, the thing similar to the unsaturated polyester resin used for the thermosetting resin composition mentioned above can be used.

  Or what introduce | transduced dicyclopentadiene frame | skeleton into the unsaturated polyester resin used for the thermosetting resin composition mentioned above may be used. The dicyclopentadiene skeleton includes, for example, a method using an adduct obtained by adding dicyclopentadiene to the α, β-olefin unsaturated dicarboxylic acid described above, or an α, β-olefin unsaturated dicarboxylic acid or its Examples include a method of copolymerizing dicyclopentadiene at the time of polymerization of an anhydride and glycol.

  As a polymeric compound, the thing similar to the thermosetting resin composition mentioned above can be used, and the content should just be the same as that of a thermosetting resin composition.

  Examples of the reinforcing fiber material include those used for conventionally known fiber reinforced plastics, such as inorganic fibers such as glass fiber, carbon fiber, metal fiber, and ceramic fiber, vinylon, phenol, nylon, polytetrafluoroethylene, and aramid. And organic fibers such as polyester. Examples of the shape include mats such as cloth, chop strand mat, preformable mat, continuous strand mat, and surfacing mat, chop, roving, and non-woven fabric.

  The content of the reinforcing fiber material is preferably 15 to 150 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the unsaturated polyester. If the content of the reinforcing fiber material is too small, the mechanical strength of the reinforcing layer may be insufficient. On the other hand, if the amount is too large, workability may be reduced.

  As a hardening | curing agent, the thing similar to the thermosetting resin composition mentioned above can be used, and the content should just be the same as that of a thermosetting resin composition.

  Further, in the unsaturated polyester resin composition for the reinforcing layer, if necessary, thickener, metal powder, mold release agent other than the above, curing accelerator, polymerization inhibitor, ultraviolet absorber, light stabilizer, Coloring pigments, extender pigments, conductive pigments, modified resins, surface preparation agents, and the like can be blended.

Composite molded body The composite molded body of the present invention is a molded body obtained by laminating the above-described artificial marble layer and the reinforcing layer via the above-described norbornene-based resin layer.
Such a composite molded body of the present invention includes, for example, BMC composed of the above-described thermosetting resin composition, norbornene-based resin molded body, and SMC composed of the unsaturated polyester resin composition for reinforcing layer, It can be manufactured by integral molding such as compression molding or injection molding.

  For example, when the composite molded body of the present invention is manufactured by compression molding, BMC, norbornene-based resin molded body, and SMC are laminated in this order, hot-pressed, and BMC and SMC are respectively reaction-cured. Thus, the composite molded body of the present invention can be produced.

  Lamination and hot pressing of BMC, norbornene-based resin molded body and SMC can be performed using a press machine that can be heated, such as an electric heat press machine, and a mold made of a female mold and a male mold. Specifically, first, SMC, norbornene-based resin molded body and BMC are arranged in this order on the female mold, and the female mold and the male mold are heated by the electric heat press machine in a state where the female mold and the male mold are heated. It can be performed by pressing the laminate.

  In addition, the temperature of the female mold or the mold on the SMC side during the hot pressing is preferably 60 to 160 ° C, more preferably 70 to 150 ° C. The temperature of the male mold or the mold on the BMC side is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. If the heating temperature is too low, the curing of SMC and BMC will be insufficient, and the resulting composite molded article will be inferior in mechanical strength. On the other hand, when too high, reaction will become quick and the fluidity | liquidity and filling property of a thermosetting resin will worsen.

Moreover, definitive during hot pressing, the mold clamping force is preferably 50 to 200 kg / cm ^2, more preferably 100~150kg / cm ^2.

The thickness of the norbornene-based resin layer in the composite molded body of the present invention is preferably 1 to 8 mm, more preferably 2 to 5 mm, and particularly preferably 3 to 5 mm. The norbornene-based resin layer acts as a spacer for joining the artificial marble layer and the reinforcing layer. If the norbornene-based resin layer is too thin, the norbornene-based resin will be deformed when molding a composite molded body. Or may break. On the other hand, if it is too thick, the thermal conductivity of the mold may deteriorate.
The thickness of the SMC is preferably 1 to 8 mm, more preferably 2 to 5 mm, and particularly preferably 2 to 3 mm. The thickness of BMC is preferably 1 to 8 mm, more preferably 1 to 4 mm, and particularly preferably 2 to 3 mm.

  The composite molded body of the present invention thus obtained has both design and rigidity, has high adhesion of each layer constituting the composite molded body, is excellent in moldability, and is effective in occurrence of sink marks and warpage. It has been prevented. Therefore, the composite molded body of the present invention makes use of such characteristics and is suitable for the field of housing equipment materials such as ceilings and wall panels, waterproof pans, bathtubs, bathroom counters, wash bowls, wash counters, kitchen counters, kitchen sinks, etc. Can be used.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” are based on weight unless otherwise specified.
Moreover, each characteristic was measured by the method shown below.

Linear expansion coefficient The linear expansion coefficient of the norbornene-based resin molding was measured according to JIS K7197. A test piece having a length of 10 mm, a width of 5 mm, and a thickness of 4 mm was used.

Thermal deformation temperature The thermal deformation temperature of the norbornene-based resin molded product was measured according to JIS K7191 under the condition of a load of 1.8 MPa. Note that a test piece having a length of 120 mm, a width of 12.7 mm, and a thickness of 4 mm was used.

Interfacial state, presence / absence of warpage The interfacial state of the composite molded body (whether mixing of components of each layer constituting the composite molded body occurred) and the presence / absence of warpage were confirmed visually.

Adhesion test For composite molded bodies, it was visually confirmed whether or not the composite interface was peeled off when repeated testing was conducted for 10 cycles under the condition of 2 cycles at −20 ° C. and 2 hours at 60 ° C. As a result, the adhesiveness of each layer constituting the composite molded body was evaluated.

Example 1
Preparation of reaction stock solution 3 parts of styrene-isoprene-styrene block copolymer (Quintac 3421: manufactured by Nippon Zeon Co., Ltd.) was dissolved in a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene. Next, diethylaluminum chloride as an activator and 1,3-dichloro-2-propanol as an activity regulator were added to a concentration of 100 mmol / kg, and 0.1 part of silicon tetrachloride was further added. Then, these were uniformly mixed and dispersed to obtain a reaction stock solution (A solution). The specific gravity of the liquid A thus obtained was 0.98.

  Separately from the above, 3 parts of a styrene-isoprene-styrene block copolymer (Quintaq 3421) was dissolved in a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene. Next, 2 parts of a phenolic antioxidant (Irganox 1010: manufactured by Ciba Specialty Chemicals) is dissolved therein, and tri (tridecyl) ammonium molybdate as a polymerization catalyst is added to a concentration of 25 mmol / kg. Then, these were uniformly mixed and dispersed to obtain a reaction stock solution (B solution). The specific gravity of the B liquid thus obtained was 0.98.

Prepare a reaction injection mold having a space (cavity) of 300 mm in length × 300 mm in width × 4 mm in thickness inside the production of the composite molded body. One of the molds is heated to 90 ° C and the other is heated to 60 ° C. did. Then, 50 parts of the liquid A and 50 parts of the liquid B prepared above are fed into the mixing head, and then injected into the heated reaction injection mold at an injection pressure of 5 MPa or less to perform bulk polymerization. The reaction was carried out for 3 minutes after the start. At this time, the mixing ratio of liquid A and liquid B was 1: 1 by volume. After completion of the reaction, the norbornene resin molded product was taken out from the mold. The thickness of the obtained norbornene-based resin molded body is 4 mm.

Next, on the lower surface plate of the electric heating press heated to 125 ° C. on the upper surface plate and 145 ° C. on the lower surface plate, above 500 parts of sheet molding compound (SMC) for forming the reinforcing layer, the above The norbornene-based resin molded body manufactured in the above is installed, 500 parts of bulk molding compound (BMC) for forming an artificial marble layer is placed thereon, and the upper and lower surface plates are fastened with a clamping force of 100 kg / cm ² for 10 minutes. Hot press molding was performed, and then the obtained molded body was taken out from the mold to produce a composite molded body. The thickness of each component of the obtained composite molded body was SMC 2.5 mm, norbornene resin molded body 4 mm, and BMC 2.5 mm.
The SMC for forming the reinforcing layer includes 30 parts of an unsaturated polyester resin composition raw material comprising an orthophthalic acid unsaturated polyester resin and styrene as a polymerizable compound, 1 part of benzoyl peroxide as a curing agent, glass What contained 20 parts of fibers and 50 parts of calcium carbonate as a thickener was used. The BMC for forming an artificial marble layer includes 100 parts of an unsaturated polyester resin composition raw material comprising an orthophthalic unsaturated polyester resin and styrene as a liquid polymerization compound, 1 part of benzoyl peroxide as a curing agent, A material containing 1.5 parts of magnesium oxide as a sticking material and 150 parts of aluminum hydroxide as a filler was used.

Then, according to the above-described method, each evaluation of the linear expansion coefficient and the thermal deformation temperature of the norbornene-based resin molded body manufactured above, and the interface state of the composite molded body manufactured above (each layer constituting the composite molded body) Whether or not mixing of these components occurred), the presence or absence of warpage, and adhesion were evaluated. The results are shown in Table 1. In Table 1, α _spx is a value measured for a test piece prepared such that the length direction of the test piece is parallel to the longitudinal direction of the mold. Further, α _spy is a value measured for a test piece prepared so that the length direction of the test piece is parallel to the lateral direction of the mold.

Example 2
First, a reaction stock solution (solution C) was prepared according to the following method.
That is, to 100 parts of a mixed monomer composed of 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene, wollastonite (SH-400, manufactured by Kinsei Matech, 50% volume cumulative diameter: 20 μm, aspect ratio: 18) 97.5 parts and 32.5 parts of heavy calcium carbonate (SCP-E # 2300, manufactured by Sankyo Seimitsu Co., Ltd., 50% volume cumulative diameter: 1.4 μm, aspect ratio: 1) are obtained by high-speed stirring treatment. 130 parts of the obtained hybrid filler was added to obtain a reaction stock solution (solution C). In the liquid C thus obtained, the ratio of the fibrous filler to the particulate filler was 75:25 by weight, and the specific gravity was 1.6.

  In Example 2, the reaction stock solution to be injected into the reaction injection mold is prepared from 50 parts of A liquid and 50 parts of B liquid, 26.8 parts of A liquid, 26.8 parts of B liquid, and the above. A norbornene-based resin molded body and a composite molded body were produced in the same manner as in Example 1 except that the amount was changed to 46.4 parts of the C1 solution, and each evaluation was performed in the same manner as in Example 1. At this time, the mixing ratio of liquid A, liquid B and liquid C1 is 1: 1: 1 by volume, the amount of fibrous filler is 18.75 parts, and the amount of particulate filler is 6.25. Was part. The results are shown in Table 1.

Example 3
Each evaluation was performed in the same manner as in Example 2 except that vinyl ester resin (Neopall 8355 manufactured by Nippon Iupika Co., Ltd.) was used as the BMC for forming the artificial marble layer. The results are shown in Table 1.

Example 4
Each evaluation was carried out in the same manner as in Example 2 except that an acrylic resin (manufactured by Iupika 8900, Japan) was used as the BMC for forming the artificial marble layer. The results are shown in Table 1.

Comparative Example 1
A composite molded body was produced in the same manner as in Example 1 except that the norbornene-based resin molded body was not used, and each evaluation was performed in the same manner as in Example 1. That is, in Comparative Example 1, a BMC for forming an artificial marble layer is directly placed on an SMC for forming a reinforcing layer, and hot press molding is performed under the same conditions as in Example 1 to obtain a composite molded body. Manufactured. The results are shown in Table 1.

As shown in Table 1, when an artificial marble layer and a reinforcing layer are laminated via a norbornene-based resin layer, mixing of components between the artificial marble layer and the reinforcing layer is effectively prevented. Further, the obtained composite molded body was effectively prevented from warping, and the adhesiveness of each layer constituting the composite molded body was high (Examples 1 to 4).
On the other hand, when the artificial marble layer and the reinforcing layer were directly laminated, the artificial marble layer component and the reinforcing layer component were mixed, resulting in poor appearance. Furthermore, the obtained composite molded body was warped (Comparative Example 1).

Claims (5)

  A composite molded body obtained by laminating an artificial marble layer and a reinforcing layer via a norbornene resin layer.   The composite molded body according to claim 1, wherein the norbornene-based resin layer is a layer made of a norbornene-based resin molded body obtained by bulk polymerization of a norbornene-based monomer in a mold.   The composite molded body according to claim 1 or 2, wherein the artificial marble layer is formed by molding a bulk molding compound made of a thermosetting resin composition.   The composite molded body according to claim 3, wherein the thermosetting resin composition is a composition containing one or more resins selected from vinyl ester resins, unsaturated polyester resins, and acrylic resins.   The composite molded body according to any one of claims 1 to 4, wherein the reinforcing layer is formed by molding a sheet molding compound made of an unsaturated polyester resin composition.