JP2002067229A - Composite molded item and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a composite molded item showing not only improved adhesion between a base material and a laminate but enhanced strength. SOLUTION: A composite molded item is manufactured by supplying a molding material 30 composed of a bulk molding material or a sheet molding material containing an unsaturated polyester resin to a cavity of a mold apparatus 20 in which a base material made of a polynorbornene-based resin is disposed followed by compression molding or injection molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molding in which a laminated material made of a thermosetting polyester resin is formed on a base material made of a polynorbornene resin, which is preferably applied to, for example, a bathtub or a washbasin ball. The present invention relates to a body and a method for producing the same.

[0002]

2. Description of the Related Art Polynorbornene resins are known to be excellent in heat resistance and chemical resistance, light and tough, and can be molded into large and complex shapes. Is difficult, and it is common to apply a paint or the like to the surface and use it in the form of a composite molded article. However, in a two-stage method in which a polynorbornene-based resin is molded and then coated, the complexity of the application and drying steps of the paint leads to an increase in the cost of the obtained molded body, and the painted surface is easily damaged. There was a case where durability was a problem.

On the other hand, FRP is widely used for molding external parts such as bathtubs. In this type of bath, a surface layer is usually formed by a BMC method, and a backup layer (backing layer) is formed by a hand lay-up method. However, after forming the surface layer, the backup layer is formed.
Since it is a stepwise method, as in the case of the above-mentioned polynorbornene-based resin, the operation becomes complicated, the cost is increased, and there are also problems in occupational health such as odor and dust.

In view of the above, various proposals have heretofore been made regarding a composite molded article having a layer (laminated material) formed of a specific resin on a substrate formed of a ring-opened polymer of a norbornene-based monomer. ing.

For example, in Japanese Patent Application Laid-Open No. 62-122718, a reaction stock solution containing a norbornene-based monomer is injected between bulk materials such as a hard plastic plate reinforced with unsaturated polyester or the like with glass fibers or the like to perform bulk polymerization. Thus, a method of manufacturing a plastic sandwich plate having a base material made of a polynorbornene resin between the laminated materials is disclosed.

In Japanese Patent Application Laid-Open No. 1-316262, a bulk polymerization is carried out by supplying a reaction solution containing a specific norbornene-based monomer to a mold in which a laminate made of an olefin-based polymer or the like is previously disposed. This discloses a method for producing a composite material having a laminated material made of an olefin-based polymer or the like on at least one surface of a substrate made of a polynorbornene-based resin.

In Japanese Patent Application Laid-Open No. 3-65319,
After a sheet made of an olefin-based polymer or the like is closely adhered to the inside of the mold by vacuum molding or the like to form a laminated material having a predetermined shape, a reaction solution containing a specific norbornene-based monomer is supplied to the voids in the mold. There is disclosed a method for producing a composite material having a laminated material made of an olefin-based polymer or the like on at least one surface of a substrate made of a polynorbornene-based resin by performing bulk polymerization.

Further, in JP-A-3-69356 and JP-A-3-69357, the outer periphery of a hollow body made of an olefin polymer or the like is surrounded by a mold, and the outer peripheral surface of the hollow body and the inner surface of the mold are defined. A reaction solution containing a specific norbornene-based monomer is supplied to the gaps between the layers to perform bulk polymerization, whereby a layer (base material) made of a polynorbornene-based resin is formed around a hollow body (laminated material) made of an olefin-based polymer or the like. A method for producing a hollow composite having

Furthermore, in Japanese Patent Application Laid-Open No. 3-69322, a light-resistant polymer film made of an ester polymer such as polyvinyl acetate, polymethyl methacrylate, and polyhexyl methacrylate is formed inside a mold. A method is disclosed in which a reaction stock solution containing a norbornene-based monomer is supplied into the mold to perform bulk polymerization, thereby producing a composite molded article in which the coating is integrated with a substrate made of a polynorbornene-based resin. .

[0010]

The composite molded article obtained by the production method described in the above-mentioned publication has excellent properties such as the ability to color the laminated material, improved weather resistance, and no sink marks. However, the adhesive strength of the laminated material to the base material tends to be insufficient, and further improvement in such adhesiveness has been demanded.

An object of the present invention is to provide a composite molded article having improved adhesion between a substrate and a laminated material and improved strength, and a method for producing the same.

[0012]

Means for Solving the Problems The present inventors have made intensive studies on forming a thermosetting polyester resin and a polynorbornene-based resin into a composite with good interfacial adhesiveness. The present inventors have found that a composite material made of a thermosetting polyester resin having good interfacial adhesiveness can be formed on a substrate made of a polynorbornene-based resin by performing the compounding, and the present invention has been completed.

That is, in the composite molded article according to the first aspect, a laminate made of a thermosetting polyester resin is formed on at least a part of a substrate made of a polynorbornene-based resin, and at a measurement temperature of 23 ° C. JIS-K691
The flexural strength and flexural strain according to 1.
0 kgf / mm ² or more and bending strain: 50% or more.

The composite molded article according to the second aspect comprises a bulk molding compound having an unsaturated polyester resin (hereinafter sometimes abbreviated as BMC) or a sheet molding compound (hereinafter sometimes abbreviated as SMC). A laminate made of a thermosetting polyester resin obtained by compression molding or injection molding of a molding material is formed on at least a part of a substrate made of a polynorbornene-based resin.

The method for producing a composite molded article according to the present invention is directed to a bulk molding compound or sheet molding having an unsaturated polyester resin in a cavity of a mold apparatus in which a base made of a polynorbornene resin is disposed. A molding material comprising a compound is supplied, and compression molding or injection molding is performed.

[0016]

The present inventors have found that when a composite of a polynorbornene-based resin and a thermosetting polyester resin is formed by an ordinary method, the adhesion between the two interfaces is insufficient. ing.

On the other hand, in the method of manufacturing a composite molded article according to the present invention, a bulk molding compound or a sheet molding compound having an unsaturated polyester resin in a cavity of a mold to which a substrate made of a polynorbornene resin is attached. Is supplied, and compression molding or injection molding is performed. That is, in the present invention, the interfacial adhesiveness between the polynorbornene-based resin and the thermosetting polyester resin is extremely improved by performing the compounding of the polynorbornene-based resin and the thermosetting polyester resin using the molding material of a specific form. Good, in other words, a thermosetting polyester resin can be more firmly bonded to a polynorbornene-based resin, and a composite molded article having improved strength can be produced.

As described above, the reason why the polynorbornene-based resin and the thermosetting polyester resin are firmly adhered to each other by the method of the present invention is not necessarily clear. Polynorbornene resin and BM by the anchor effect due to micro unevenness or radical curing reaction of BMC or SMC
It is considered that either C is graft-polymerized or not.

The composite molded article obtained by the present invention is a laminated material whose outer surface is made of a thermosetting polyester resin,
Since the back surface is a substrate made of polynorbornene-based resin, it has excellent design while being relatively lightweight,
It has a high hardness appearance, and the base material on the back side has an advantage that it can cope with complicated built-in shapes such as a rib structure for reinforcement and integral molding of nuts for mounting components.

The composite molded article according to the present invention can be used for a wide variety of applications such as a bathtub, a washbasin, a washbasin, and a washing pan.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on an embodiment shown in the drawings. 1A to 1C are schematic views showing a method for manufacturing a composite molded article according to one embodiment of the present invention, and FIG. 2 is a cross-sectional view showing a composite molded article according to one embodiment of the present invention.

In the present embodiment, a composite molded body will be described with reference to FIG. 2, and then a method of manufacturing the composite molded body will be described with reference to FIGS. 1 (A) to 1 (C).

As shown in FIG. 2, the composite molded body 2 according to the present embodiment
Has a laminate 4 made of a thermosetting polyester resin formed on a base material 4 made of a polynorbornene-based resin.
Hereinafter, each component will be described in detail.

Substrate 4 The polynorbornene-based resin constituting the substrate 4 is obtained by subjecting a norbornene-based monomer to bulk polymerization in a mold cavity in the presence of a metathesis catalyst. In the bulk polymerization, an activator may be used if necessary.

The norbornene-based monomer which can be used in the present invention may be any one having a norbornene ring, and specific examples thereof include bicyclics such as norbornene and norbornadiene, and dicyclopentadiene (cyclopentadiene dimer). , Tricyclics such as dihydrodicyclopentadiene, tetracyclics such as tetracyclododecene, pentacyclics such as cyclopentadiene trimers, heptacyclics such as cyclopentadiene tetramers, and bicyclic to heptacyclic Alkyl, such as cyclic methyl, ethyl, propyl and butyl,
Substitutes such as alkenyl such as vinyl, alkylidene such as ethylidene, and aryl such as phenyl, tolyl and naphthyl; and further, polar groups such as ester groups, ether groups, cyano groups, and halogen atoms of these bicyclic to heptacyclic bodies. And the like. Among them, tricyclic or higher polycyclic norbornene monomers are preferable because they are easily available and excellent in reactivity, and more preferably tricyclic, tetracyclic or pentacyclic norbornene monomers. These norbornene monomers can be used alone or in combination of two or more.

The resulting ring-opening polymer is preferably of a thermosetting type. For this purpose, among the norbornene-based monomers, a cross-linked polymer having two or more reactive double bonds such as cyclopentadiene trimer is preferred. Those containing at least a reactive monomer are used. The proportion of the crosslinkable monomer in all the norbornene monomers is preferably from 2 to 30% by weight.

A monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene and cyclododecene, which can be ring-opening copolymerized with a norbornene monomer, can also be used as a comonomer.

The metathesis catalyst that can be used in the present invention is not particularly limited as long as it is capable of ring-opening polymerization of a norbornene monomer by a reaction injection molding (RIM) method, and may be a known one. For example, any metathesis catalyst known as a catalyst for bulk polymerization of norbornene-based monomers such as tungsten hexachloride, or organic ammonium molybdate such as tridodecyl ammonium molybdate or tri (tridecyl) ammonium molybdate may be used. However, organic ammonium molybdate is preferred. In addition, as a metathesis catalyst, a known ruthenium carbene complex (WO97 / 06185, JP-T-10-50891, JP-A-11-329553) can be used.
No. publication) can also be applied.

The amount of the metathesis catalyst to be used is generally 0.01 mmol or more, preferably 0.1 mmol or more, and 50 mmol or less, preferably 20 mmol or less, per 1 mol of the monomer used in the whole reaction solution. If the amount of the metathesis catalyst used is too small, the polymerization activity is too low and the reaction takes a long time, so the production efficiency is poor.If the amount is too large, the reaction is too vigorous and the resin hardens before being sufficiently filled in the mold. Or the catalyst is likely to precipitate, making it difficult to store homogeneously.

The metathesis catalyst is usually used by dissolving it in a monomer. However, as long as the properties of the obtained molded article are not substantially impaired, the catalyst is suspended and dissolved in a small amount of a solvent, and then the monomer is mixed with the monomer. By mixing, precipitation may be suppressed, or solubility may be enhanced before use.

As the activator (cocatalyst), JP-A-58-1983
127728, JP-A-4-226124,
JP-A-58-129003, JP-A-4-1452
There is no particular limitation as long as it is a known activator as disclosed in JP-A-47-47, for example, alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride, organoaluminum compounds such as alkoxyalkylaluminum halide, and organotin. And the like. When a ruthenium carbene complex is used as a metathesis catalyst, an activator may or may not be used.

The use amount of the activator is not particularly limited,
Usually, it is 0.1 mol or more, preferably 1 mol or more, and 100 mol or less, preferably 10 mol or less, based on 1 mol of the metathesis catalyst used in the whole reaction stock solution. If no activator is used or the amount of the activator used is too small, the polymerization activity is too low and the reaction takes a long time, resulting in poor production efficiency. Conversely, if the amount is too large, the reaction may be too vigorous and may be cured before the mold is sufficiently filled.

The activator is used by dissolving it in a monomer.
As long as the properties of the obtained molded body are not substantially impaired, they may be suspended in a small amount of solvent and then mixed with a monomer to make it difficult to precipitate or may be used with increased solubility. .

In the present invention, an activity regulator may be used in combination with the above-mentioned active agent. The combined use of an activity regulator can change the reaction rate, the time from mixing of the reaction solutions to the start of the reaction, and the reaction activity.

The activity regulator usable in the present invention includes:
A compound having an action of reducing the metathesis catalyst is used, and examples of the activity regulator include alcohols, halo alcohols, esters, ethers, and nitriles. Among them, 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 halo alcohols As for 1,3-
Dichloro-2-propanol, 2-chloroethanol,
1-chlorobutanol and the like. The amount of the activity modifier varies depending on the compound used and is not uniform.

If necessary, the base material 4 may be made of, for example, a reinforcing material, an antioxidant, a filler, a pigment, a coloring agent, a foaming agent, a sliding agent, an elastomer, a dicyclopentadiene-based thermopolymerized resin, and the like. Various additives such as hydrogenated products may be blended. For the purpose of obtaining a molded article having particularly high mechanical strength, a reinforcing material may be filled in a mold in advance, and then a norbornene-based monomer may be injected into the mold and cured.

The thickness of the substrate 4 is not particularly limited, but is preferably 1 to 20 mm, more preferably 3 to 10 mm.

Although the size and shape of the substrate 4 are not particularly limited, a bathtub is exemplified in this embodiment as described later.

Laminate 6 The laminate 6 constituting the composite molded body 2 contains a thermosetting polyester resin.

As described later, the thermosetting polyester resin may be a BMC or SMC having an unsaturated polyester resin.
It is manufactured by compression molding or injection molding using a molding material composed of MC.

The laminate 6 may contain various additives such as a reinforcing material, an inorganic filler, a release agent, and a coloring agent, if necessary. In this case, the amount is usually about 5 to 100 parts by weight based on 100 parts by weight of the thermosetting polyester resin.

Although the thickness of the laminated material 6 is not particularly limited,
Preferably it is 1 to 10 mm, more preferably 2 to 6 mm.

The area occupied by the laminated material 6 with respect to the substrate 4 may be the same as or different from the area of the substrate 4 and may be appropriately determined according to the purpose of use.

The composite molded body 2 according to this embodiment having such a configuration is preferably manufactured, for example, as follows.

Production Method of Composite Molded Product (1) First, a stock solution containing at least a norbornene-based monomer and a metathesis catalyst is supplied into a cavity formed inside a mold (not shown) to allow bulk polymerization to proceed. In this way, a cured product (corresponding to the base material 4 in FIG. 1A) made of a polynorbornene-based resin as a female mold described below is formed.

The above-mentioned various additives may be added to the reaction stock solution used in the present invention, if necessary. For the purpose of obtaining a substrate having particularly high mechanical strength, a reinforcing material can be filled in the cavity in advance, and then the reaction solution can be injected and cured.

In the present invention, the norbornene-based monomer is
It is used by dividing into two or more reaction stock solutions. Specifically, at least two reaction stock solutions, a stock solution of a norbornene-based monomer containing a metathesis catalyst (solution B) and a stock solution of a norbornene-based monomer containing an activator (solution A), are prepared. The optional components described above are accordingly contained in at least one of these reaction stock solutions. It is preferable that each of the liquid A and the liquid B is placed in a separate tank. Each of the reaction stock solutions alone does not cause polymerization of the norbornene-based monomer, but when each of the reaction stock solutions is mixed, bulk polymerization occurs. The sum of the components contained in each reaction stock solution corresponds to the amount of the components required for the bulk polymerization of the present invention. In addition, when the above-mentioned additive is added, it is preferable that the additive is previously mixed with one or both of the reaction stock solutions, or placed in a cavity of a mold (not shown). . When performing bulk polymerization, two or more reaction stock solutions are instantaneously mixed using a mixing head or the like, and the mixed solution is immediately injected into a cavity of a mold (not shown) to start polymerization. Then, when the bulk polymerization (reaction injection molding) in the cavity of the mold apparatus is completed and the molded body is solidified, the mold is opened, so that the molded body (the base material 4 in FIG. Corresponding) is obtained. The material and size of the mold to be used, the polymerization time during molding, the mold temperature, and other conditions may be the same as those of ordinary molding by bulk polymerization of polynorbornene-based resin.

(2) Next, as shown in FIG. 1 (A), the cured product made of the polynorbornene resin thus obtained is set in, for example, a mold apparatus 20 shown below.

As shown in FIG. 1A, a mold device 20 according to the present embodiment comprises a male mold 24 which can be divided along a division surface 22 and a base material 4 which is a female mold. Has a mold mold 26 arranged on a mold mold body 26a,
A cavity (not shown) is formed inside the core mold 24 and the mold cavity 26 by clamping the mold with the dividing surface 22. In the present embodiment, the core type 2
4 and the mold-type main body 26a are made of, for example, synthetic resin or metal. In the present embodiment, the convex mold is called a core mold, and the concave mold is called a mold mold.However, a mold in contact with a product surface side is called a mold mold, and a mold in contact with a non-product surface side is called a core mold. There is also.

The mold main body 26 constituting the mold 26
The shape and size of the substrate 4 arranged in a are not particularly limited, but in the present embodiment, a bathtub is illustrated as an example of the substrate. If strength or the like is required, a rib can be provided on the back surface of the base material 4 (the side in contact with the mold-type main body 26a).

(3) Next, after the above-described mold apparatus 20 is opened, the BMC 30 as a molding material is supplied onto the base material 4 arranged on the mold body 26a.

In this embodiment, the BMC 30 comprises an unsaturated polyester resin (A), a liquid polymerizable monomer (B),
It contains a curing agent (C) and a thickener (D). As described above, by performing the compression molding described below using the BMC 30 which is a molding material of a specific form, the laminated material 6 having excellent adhesion to the substrate 4 made of a polynorbornene-based resin can be formed.

The unsaturated polyester resin (A) which can be used in the present invention is not particularly limited, and may be a known unsaturated polyester resin which is conventionally used in general unsaturated polyester resin molded articles. Unsaturated polyester resins of this kind can be obtained from α, β-unsaturated carboxylic acids or α, β-unsaturated carboxylic acids, optionally containing saturated carboxylic acids, and alcohols.

Examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid,
Alternatively, dimethyl esters thereof may be mentioned. These α, β-unsaturated carboxylic acids may be used alone or in combination of two or more.

As the saturated carboxylic acid, for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexic acid, hexahydrophthalic anhydride, adipic acid, sebacic acid, azelaic acid and the like can be mentioned. These saturated carboxylic acids may be used alone or in combination of two or more.

Examples of the alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,6- Hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, glycerin monoallyl ether, hydrogenated bisphenol A, 2,2-bis (4-hydroxypropoxyphenyl) propane, Examples thereof include diols such as 2,2-bis (4-hydroxyethoxyphenyl) propane, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These alcohols may be used alone or in combination of two or more.

A part of the above unsaturated polyester resin may be replaced with an epoxy acrylate resin for improving chemical resistance or a urethane acrylate resin for improving adhesion by insert processing or the like. it can.

Examples of the epoxy acrylate resin in this case include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolak type epoxy resin and the like to which acrylic acid or methacrylic acid is added. Can be

Examples of urethane acrylate resins include, for example, JP-B-55-30527 and JP-B-60-2.
No. 6,132, and JP-B-60-26133, toluene diisocyanate is added to both ends of ethylene glycol, and further, 2-hydroxyethyl methacrylate is added to both ends.

The liquid polymerizable monomer (B) which can be used in the present invention is a liquid polymer which is usually used also as a solvent for an unsaturated polyester resin and is liquid at normal temperature and normal pressure. , Methacrylate,
Examples thereof include an aromatic vinyl compound and an aromatic allyl compound. This liquid polymerizable monomer causes a crosslinking reaction with the above-mentioned unsaturated polyester resin during molding.

As the acrylate, for example,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-
Examples include ethylhexyl acrylate and n-octyl acrylate.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate,
Examples include diethylene glycol dimethacrylate and trimethylolpropane trimethacrylate.

As the aromatic vinyl compound, for example,
Styrene, α-methylstyrene, vinyltoluene, t-
Butylstyrene, α-chlorostyrene, dichlorostyrene, divinylbenzene, and the like.

As the aromatic allyl compound, for example,
Diallyl phthalate, diallyl isophthalate, triallyl trimellitate and the like. Of these liquid polymerizable monomers, styrene is particularly preferred. Each of these liquid polymerizable monomers may be used alone,
Two or more kinds may be used in combination.

The amount of the liquid polymerizable monomer is usually 10 to 1 based on 100 parts by weight of the unsaturated polyester resin.
00 parts by weight, preferably 15 to 80 parts by weight. If the compounding amount is less than 10 parts by weight, the fluidity of the composition becomes poor, and the water resistance of the finally obtained laminated material decreases, and
When the amount exceeds the weight part, the finally obtained laminated material tends to be brittle.

The curing agent (C) which can be used in the present invention is decomposed by heating to generate radicals, and the liquid polymerizable monomer is crosslinked and polymerized on the unsaturated polyester resin, whereby the entire composition is cured. It has a curing effect. Such materials include, for example, t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, cyclyl peroxide, t-butyl peroxy-2-ethylhexanoate, di-t-butyl hydroperoxide, Lauroyl peroxide, 1,
1-di-t-butylperoxy-3,5,5-trimethylcyclohexane, t-butylperoxyisopropyl carbonate, bis (4-t-butylcyclohexyl)
Organic peroxides such as peroxycarbonate are exemplified. If necessary, hydroquinone, naphthoquinone,
A curing stabilizer such as t-butyl catechol may be used in combination with the curing agent. These curing agents may be used alone or in combination of two or more.

The amount of the curing agent is usually 0.5 to 2.0 parts by weight, preferably 0.7 to 1.8 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. If the amount is less than 0.5 part by weight, curing during molding may be insufficient, and if it exceeds 2.0 parts by weight, the storage stability of the composition may be reduced.

The thickener (D) usable in the present invention includes, for example, oxides or hydroxides of alkaline earth metals such as magnesium oxide, magnesium hydroxide and calcium oxide. The amount of the thickener is
It is usually 0.5 to 2.0 parts by weight, preferably 0.7 to 1.8 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. If the amount is less than 0.5 part by weight, the thickening effect is poor, and if it exceeds 2.0 parts by weight, the handleability tends to be poor.

The BMC 30 used in the present embodiment may optionally contain additives such as a reinforcing material, a low-shrinking agent, an inorganic filler (a bulking agent), and a release agent. .

As the reinforcing material, for example, glass fiber,
FR such as polyester fiber, phenol fiber, polyvinyl alcohol fiber, aromatic polyamide fiber (Kevlar fiber, trade name of DuPont), nylon fiber, carbon fiber, etc.
P (Fiber Reinforced Plasti
and those commonly used in the production of cs). Examples of the form of these reinforcing materials include chopped strands, chopped strand mats, rovings, and woven fabrics. These reinforcing materials are appropriately selected in consideration of the viscosity of the composition, the strength of the obtained molded article, and the like. By adding such a reinforcing material, the obtained laminated material can be given sufficient mechanical strength. In addition,
Chopped strand length is typically 2-8 for BMC
mm, but 5 to 60 mm for SMC. When the shorter is heated, the molding material tends to flow when heated, but the mechanical strength of the molded article is reduced.

Examples of the low shrinkage agent include thermoplastic resins such as polystyrene, polyethylene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polycaprolactam, saturated polyester, styrene-acrylonitrile copolymer, polybutadiene, and polybutadiene. Isoprene,
Rubbery polymers such as styrene-butadiene copolymer and acrylonitrile-butadiene copolymer are exemplified. The amount of addition of the low shrinkage agent is as follows:
It is usually about 5 to 20 parts by weight with respect to 00 parts by weight.

Examples of the inorganic filler (bulking agent) include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barlite, baryta, silica, silica sand, dolomite limestone, and gypsum. , Aluminum fine powder, hollow balloon, alumina, glass powder, aluminum hydroxide, fluorite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide and the like. These inorganic fillers are appropriately selected in consideration of workability and the strength, appearance, economy, and the like of the obtained molded product, and usually, calcium carbonate or aluminum hydroxide is used. The amount of the inorganic filler is usually about 50 to 300 parts by weight based on 100 parts by weight of the unsaturated polyester resin.

Examples of the releasing agent include higher fatty acids such as stearic acid, salts of higher fatty acids such as zinc stearate, and alkyl phosphates. The compounding amount of the release agent is usually about 3 to 7 parts by weight based on 100 parts by weight of the unsaturated polyester resin.

In addition to these, a curing accelerator, a coloring agent, a defoaming agent, a viscosity reducing agent and the like can be used as required.

The BMC 30 used in this embodiment is prepared by, for example, dissolving an unsaturated polyester resin in all or a part of a liquid polymerizable monomer in advance, and adding it to a known material such as a planetary mixer, a kneader, and a disper. Using a mixer, a predetermined amount of each of the remaining components is stirred and mixed at once,
It can be obtained by taking it out of the mixer, forming it into a predetermined size and shape, and aging it.

Aging is usually carried out for half a day to two days at 30 to 60 ° C.
By placing the material under the following temperature conditions.

The amount of the BMC 30 used in the present embodiment is appropriately selected according to the size of the finally formed laminated material.

The BMC 30 used in this embodiment can be in various shapes and sizes such as pellets, pebbles, bricks, etc., and usually has a diameter or a side of 0.5 to 50 cm. Usually, one side or short side is about 10 cm or more cubic, rectangular parallelepiped, or a sphere whose diameter or small diameter is about 10 cm or more,
Bulks such as ellipsoids are stored covered with a release film.

(4) Next, as shown in FIG. 1B, the mold is clamped, and the BMC 30 is compression-molded.
The molding conditions are such that the mold temperature of the core mold 24 in contact with the product surface is preferably 80 to 140 ° C., and the temperature of the substrate 4 (mold mold 26) in contact with the product back surface is preferably 40 ° C.
１００100 ° C. The molding time is preferably 2 to
The molding pressure is preferably about 2 to 20 MPa for about 10 minutes.

(5) Then, as shown in FIG. 1 (C), after a predetermined time has elapsed, the mold is opened and the mold is released, so that a thermosetting resin is formed on the substrate 4 made of polynorbornene resin. A laminated material 6 made of a polyester resin is formed,
The composite molded article (bath) 2 according to the present embodiment is obtained.

The composite molded body 2 thus obtained is
The interfacial adhesion and strength between the base material 4 and the laminated material 6 are extremely excellent. Specifically, the flexural strength at a measurement temperature of 23 ° C. according to JIS-K6911 is 7.0 kgf
/ Mm ² or more, preferably 8.0 kgf / mm ² or more. In addition, JIS-K6 at a measurement temperature of 23 ° C.
The flexural modulus according to 911 is 200 kgf / mm ²
Above, preferably 300 kgf / mm ² or more.
Further, the bending strain at a measurement temperature of 23 ° C. according to JIS-K6911 is 50% or more, preferably 100% or more.

The size and shape of the composite molded article according to the present invention are not particularly limited, and the composite molded article can have a desired size and shape according to the purpose and the like.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and can be implemented in various modes without departing from the gist of the present invention. Of course.

For example, in the above-described embodiment, the BMC
Although the composite molded body 2 is manufactured by compression-molding the composite body 30, the composite molded body 2 may be manufactured by injection molding. The molding conditions in this case may be performed under ordinary conditions.

The form of the material used for molding is not limited to BMC, but may be SMC (sheet molding compound) material. When an SMC material is used, it can be formed into a sheet by a known method.

Further, in the above-described embodiment, after the base material 4 made of the polynorbornene resin is formed, the base material 4 is set in another mold apparatus 20 and compression-molded.
After molding a base material made of polynorbornene-based resin using one mold apparatus, the mold is slightly opened, and the BM is inserted into this gap.
A molding material such as C may be supplied and compression molded.

[0087]

EXAMPLES The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these examples. In the following examples, parts and percentages are by weight unless otherwise specified.

Reference Example 1 (Preparation of DCP Polymer Molded Product) 100 parts of dicyclopentadiene (DCP), 7 parts of a styrene-isoprene-styrene block copolymer (Quintac 3530, manufactured by Zeon Corporation) and phenol-based oxidation 2 parts of an inhibitor (Irganox 1010, manufactured by Ciba Specialty Chemicals) was dissolved and placed in two containers. In one container, 53 mmol of diethylaluminum chloride (DEAC) and 53 mass of 1,3-dichloro-2-propanol were added to DCP.
A millimolar concentration of silicon tetrachloride was added to a concentration of 20 mmol (Solution A). In the other container, 1 (tri (todecyl) ammonium molybdate) was added to DCP.
It was added to a concentration of 1 mmol (solution B).

The thus-prepared unreacted A and B reaction solutions were mixed at a ratio of 1: 1 using a two-liquid collision mixing injection device, and then heated to 85 ° C. on the cavity surface / 55 ° C. on the core surface. It was poured into a mold (500 mm × 500 mm × 3 mm). After the injection, a polymerization reaction was performed for about 3 minutes to obtain a DCP polymer plate-like molded product. Using the obtained molded body, JIS-
Table 1 shows the results of measuring the flexural strength, flexural modulus and flexural strain according to the test method of K-6911 (measuring temperature 23 ° C.).

Example 1 (Preparation of Composite Molded Body) The upper and lower stools of the electric heating press were heated to 125 ° C., and the DCP polymer plate-like molded product prepared in Reference Example 1 described above was placed on the lower stool. Placed on the previous day), and a stainless steel square spacer (200 mm × 300
mm × 4 mmt). At the center of the spacer, 30 parts of a liquid polymerizable monomer (styrene), 1 part of a curing agent (benzoyl peroxide), and a thickener (magnesium oxide) based on 100 parts of an orthophthalic unsaturated polyester resin. BMC500 containing 1.5 parts
After placing g, the upper and lower platens are clamped by 100 tons / cm.
² and hot press formed for 6 minutes. Table 1 shows the results of the same evaluation as in Reference Example 1 performed using the plate-shaped composite molded body composed of the DCP polymer (thickness 3 mm) and the polyester resin (thickness 4 mm) thus obtained.

Example 2 (Preparation of Composite Molded Product) The height of the stainless steel square spacer of Example 1 was 2 m.
mt and the amount of BMC was changed to 250 g, followed by hot press molding in the same manner as in Example 1 to obtain a plate-shaped composite molded body composed of DCP polymer (thickness 3 mm) and polyester resin (thickness 2 mm). . Table 1 shows the results of the same evaluation as in Reference Example 1 for this composite molded article.

Comparative Example 1 (Preparation of polyester molded article) Example 1 was repeated except that no DCP polymer molded article was used.
Hot press molding in the same manner as in
mm) in a plate-like shape.
Table 1 shows the results of the same evaluation as in Reference Example 1 performed on this molded body.

[0093]

[Table 1]

From the results shown in Table 1, the bending strain of the molded body of the DCP polymer alone as in Reference Example 1 was 350
%, But the flexural strength was 6.6 kgf / mm ² and the flexural modulus was 170 kgf / mm ² , showing relatively soft and sticky properties. Also, as in Comparative Example 1, the BM
The flexural modulus of the molded product of C alone is 1378 kgf / m.
Although higher and m ^2, bending strength 8.0 kgf / mm ² and low low bending strain of 28%, showed a relatively hard and brittle properties.

On the other hand, as in Examples 1 and 2, B
When compounding with a DCP polymer molded body was performed using a molding material composed of MC, the flexural modulus was 469 kgf.
/ Mm ² (Example 1) and 352 kgf / mm ²
(Example 2) Low, but bending strength is 8.3 kgf / mm
² (Example 1) and as high as 9.6 kgf / mm ² (Example 2), and the bending strain was as high as 138% (Example 1) and 183% (Example 2), showing tough properties. From this, in the composite molded articles of Examples 1 and 2, in addition to the fact that the base material and the laminated material were more firmly joined, a composite effect that the strength was improved from the average value of both materials could be confirmed. .

In the composite molded products of Examples 1 and 2, no interfacial peeling was observed in the bending test, and only the polyester resin was broken at the yield point. From this, it was confirmed that it was an integrally molded body that was firmly joined.

[0097]

As described above, according to the present invention, it is possible to provide a composite molded article in which the adhesion between the base material and the laminate is improved and the strength is improved, and a method for producing the same.

[Brief description of the drawings]

1 (A) to 1 (C) are schematic views showing a method for producing a composite molded article according to one embodiment of the present invention.

FIG. 2 is a sectional view showing a composite molded body according to one embodiment of the present invention.

[Explanation of symbols]

 2 ... Composite molded body 4 ... Substrate made of polynorbornene resin 6 ... Laminated material made of thermosetting polyester resin 20 ... Mold device 22 ... Splitting surface 24 ... Core mold 26 ... Cavity mold 26a ... Cavity mold main body 30 ... BMC

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C08F 283/01 C08F 283/01 B29K 67:00 B29K 67:00 105: 08 105: 08 B29L 31:00 B29L 31 : 00 (72) Inventor Koji Miyazaki 1-2-1, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Zeon Corporation General Development Center (72) Inventor Katsuo Suzuki 1-2-1, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Inside Zeon Corporation R & D Center (72) Inventor Toshio Miyake 505 Kamikusai, Yamato-cho, Kamo-gun, Hiroshima Prefecture Daikyo Co., Ltd. F term in the Yamato factory (reference) 2D032 AB02 4F100 AK02B AK44A BA02 BA15 DH01A EH112 EH312 EH36A EH362 EJ17A EJ172 EJ20 GB08 JB13A JK01 JK04 JK06 JL11 YY00 4F204 AA41 AD05 AD01 AG03 AB01 AB05 AB19 AB23 AB24 AB25 AB32 AC03 AC06 AE02 A E03 AE05 AG01 AJ08 AJ09 BA05 BA07 BA10 BA17 BA22 BA23 BA26 CA02 CA03 CA04 CA05 CA06 CA07 CA08 CA10 CA12 CA14 CA16 CA18 CA19 CA32 CA36 CA38 CB03 CC02 CD01 CD02

Claims (3)

[Claims] 1. A laminate made of a thermosetting polyester resin is formed on at least a part of a substrate made of a polynorbornene-based resin, and has a bending strength and a bending strain according to JIS-K6911 at a measurement temperature of 23 ° C. Has a bending strength of 7.0 kgf / m
m ² or more, bending strain: composite molding, characterized in that at least 50%. 2. A laminate comprising a thermosetting polyester resin obtained by compression molding or injection molding of a molding material comprising a bulk molding compound or a sheet molding compound having an unsaturated polyester resin, comprises a base comprising a polynorbornene resin. A composite molded article formed on at least a part of a material. 3. A molding material comprising a bulk molding compound or a sheet molding compound having an unsaturated polyester resin is supplied into a cavity of a mold apparatus in which a base material composed of a polynorbornene resin is disposed, and compressed. A method for producing a composite molded article, comprising molding or injection molding.