JPH0940794A - Resin particles for FRP and FRP composition - Google Patents

Abstract

(57) Abstract: The resin particle for FRP of the present invention comprises a polymer particle core material and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material. Further, in the FRP composition of the present invention, resin particles composed of a polymer particle core material and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material are dispersed in a resin matrix. . [Effect] By blending the resin particles for FRP of the present invention, a molded article having excellent properties such as colorability, transparency and surface gloss can be produced. Of course, without reducing the boiling resistance of the molded body,
The shrinkage rate at the time of molding can be reduced, the generation of cracks can be prevented, and the dimensional accuracy is excellent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an FR having a novel structure.
The present invention relates to resin particles for P and an FRP composition containing the resin particles. More specifically, the present invention relates to resin particles to be blended with a resin in the production of FRP, particularly FRP called SMC and BMC, and particularly FR called artificial marble.
The present invention relates to a resin composition that can be preferably used for forming P and a resin composition that can produce a molded article containing the particles and having a marble-like appearance. Further, the present invention relates to resin particles capable of forming a molded product having low shrinkage and having little decrease in boiling resistance, transparency, colorability, mechanical strength, etc., and a resin composition containing the resin particles. .

[0002]

2. Description of the Related Art In recent years, FRP molded articles have been used in a wide variety of applications in terms of mechanical strength, chemical resistance, productivity, etc., and many studies have been conducted to improve the performance required for each application. Has been done.

For example, a method of molding at a high temperature is adopted in order to shorten the curing time and improve the productivity when manufacturing an FRP molded body. By increasing the molding temperature to such a high temperature, the curing time can be shortened, but on the other hand, the internal stress generated by the volume contraction of the composition accompanying the curing causes cracks in the molded body or the volume contraction causes the dimensional accuracy of the molded body to decrease. Is reduced. Further, since the surface smoothness of the molded body is likely to be impaired, there is a problem that the surface gloss of the molded body decreases.

As a method for solving such a problem, F
A method of incorporating an additive called a low-shrinking agent or a non-shrinking agent into the RP composition is adopted. However, the addition of this additive causes a new problem that the coloring property and transparency of the FRP molded product are deteriorated. Further, when a molded product containing such an additive is observed with time, the properties called water resistance, boiling resistance, hot water resistance, etc. also deteriorate.

By the way, one field of FRP molded products is artificial marble, and among them, BMC artificial marble is excellent in productivity. This artificial marble is an FRP molded body which is made by mixing a resin with inorganic powder or the like, and is colored to resemble marble, and is used as a countertop or a bathtub in a kitchen or a wash basin. Due to the use of such artificial marble, this FRP has transparency, uniform coloring,
The characteristics that make up the appearance of the molded product such as surface gloss are emphasized,
It is necessary to select the additive so that the coloring property and the transparency of the molded product are not deteriorated by the addition of the additive.

Further, the bathtub, which is a molded product of this FRP, is exposed to warm water of about 40 ° C., so that the deterioration of the molded product due to the addition of additives (usually such a characteristic is called “boiling resistance”). It's a big problem. In particular, recently, a bath system called a 24-hour bath, which can always take a bath, has become widespread. In such a system, the artificial marble bathtub is constantly in contact with hot water of about 40 ° C. More than a bathtub,
The boiling resistance has become an important characteristic. That is, when a conventional BMC artificial marble bathtub is used, deterioration of the bathtub is remarkably accelerated under the use condition, and the appearance of the bathtub becomes unaesthetic in a short time.

Various improved methods have been proposed for the problem of boiling resistance of a bathtub formed of such artificial marble. For example, as a filler used in an FRP composition,
A method using an inorganic material treated with a coupling agent such as an alkylsilane compound or a silane coupling agent, or a coupling agent such as a silane coupling agent and another FRP composition when preparing an FRP composition. Methods such as addition and kneading to the constituent materials are known (for example, JP-A-58-173114 and JP-A-63).
-235358, JP-A-02-99509, JP-A-03-50257, JP-A-05-170971, JP-A-62-259837, JP-A-03-45542 and JP-A-05-229860. reference).

Although the boiling resistance of the bathtub which is an FRP molded product is improved to some extent by such an improvement, it is still unusable for use in a harsh condition such as a 24-hour bath. This is because these improvements are intended to improve the state of the interface between the resin for FRP and the inorganic filler to improve the boiling resistance of the molded product as a whole. Alternatively, the crack preventive agent cannot solve the problem that the boiling resistance of the molded body is lowered.

[0009]

OBJECT OF THE INVENTION It is an object of the present invention to provide new resin particles to be added to FRP molded products.

The present invention also provides resin particles for FRP which, when added to a resin, are capable of forming a resin molding excellent in transparency, colorability, mechanical properties, surface gloss, boiling resistance and low shrinkage. Is intended to provide.

Further, according to the present invention, by adding to the resin, the appearance of the molded product such as coloring property, transparency and surface gloss,
And, of course, not only the mechanical strength of the molded product, but also the resin particles capable of reducing the shrinkage during molding of the molded product without lowering the boiling resistance of the molded product and the resin particles as described above. The object of the present invention is to provide a FRP composition capable of producing a molded product having the above-mentioned characteristics.

[0012]

SUMMARY OF THE INVENTION The FRP resin particles of the present invention are characterized by comprising a polymer particle core material and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material.

In the FRP composition of the present invention, resin particles composed of a polymer particle core material and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material are dispersed in a resin matrix. It is characterized by being.

The FRP resin particles of the present invention are particles in which one or both of the alkylsilane compound and the coupling agent are bonded to the surface of the polymer particles serving as the core material (that is, the core). By adding the resin particles for use in the FRP molding, it is possible to manufacture a molding having excellent characteristics such as colorability, transparency and surface gloss. Further, by using such resin particles, not only the strength of the molded body, but also the boiling resistance of the molded body is not reduced, the shrinkage rate at the time of molding the molded body is reduced, and the formation of cracks Can be prevented, and a molded product having excellent dimensional accuracy can be manufactured.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Next, the FRP resin particles of the present invention and the FRP composition containing the resin particles will be specifically described.

The resin particles of the present invention are composed of polymer particles forming a core material, and an alkylsilane compound and / or a coupling agent bonded to the surface of the core material. In the present invention, the polymer particles forming the core material can be formed by using various resins. In particular, in the present invention, the resin used for forming the FRP molded body and such resin are It is preferably formed of a resin that is not dissolved in the polymerizable monomer used as the solvent of the contained FRP composition and has a swelling property with respect to any of the components constituting the FRP composition.

Here, "the polymer particles swell into the polymerizable monomer" is a characteristic determined by measuring the swelling degree of the polymer according to the measuring method described below.

The method for measuring the degree of swelling of polymer particles in the present invention is as follows. Inner diameter 14 mm, height 135 mm,
Accurately weigh 0.5 g of a sample into a graduated cylinder of 20 ml of colorless glass and 20 ml of graduation, and tap several times. Then, 20 g of styrene monomer was gently poured along the wall surface, and the height of the swollen polymer particle phase when left standing for 24 hours at room temperature was read in ml, and the value calculated by the following formula from this measured value was calculated. It is defined as the degree of swelling. Swelling degree = (reading value (ml) × 0.5) / mass of sampling material (g) In the present invention, the polymer particles are styrene, α-
Styrene derivatives such as styrene, vinyltoluene and pt-butylstyrene; methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate,
Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, ( Glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, propoxylethyl (meth) acrylate,
Butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, phenoxy (meth) acrylate Ethyl, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, benzyl (meth) acrylate,
Cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylic acid-2-hydroxy (Meth) acrylic acid ester monomers such as ethyl, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; vinyl-based monomers having one vinyl group in one molecule such as vinylpyridine. It can be produced by (co) polymerization alone or in combination.

In the present invention, the above-mentioned monomers (co) are used.
It is preferable that a crosslinked structure is formed in the polymer particles produced by polymerization. That is, the degree of swelling of the above-mentioned polymer particles can be adjusted by forming a cross-linking structure in the polymer particles, and this cross-linked structure has a mixed amount of a bifunctional monomer or a polyfunctional monomer. Can be adjusted and controlled. The formation of the crosslinked structure allows the polymer particles to exhibit a suitable degree of swelling without exhibiting solubility in the polymerizable monomer constituting the FRP composition. Examples of the bifunctional monomer or the polyfunctional monomer used to form the crosslinked structure in the polymer particles include ethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate and trimethylol. Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
1,1,1-trishydroxymethylethane diacrylate,
Mention may be made of 1,1,1-trishydroxymethylpropane triacrylate and divinylbenzene.

The above-mentioned bifunctional reactive monomer or polyfunctional reactive monomer varies depending on the kind, but it is a monofunctional monomer 1 used when forming polymer particles.
It is usually used in an amount of 0.005 to 2.0 parts by weight, preferably 0.1 to 1.0 parts by weight, based on 00 parts by weight.

The method for producing such polymer particles is not particularly limited, and for example, it is produced by employing a polymerization method such as solution polymerization, bulk polymerization, casting polymerization, emulsion polymerization, multistage seed polymerization and suspension polymerization. be able to. For example, in order to produce polymer particles by a method such as bulk polymerization and casting polymerization, after the completion of polymerization, the polymer is pulverized to a desired particle size,
After classifying the pulverized product, the obtained particles are spheroidized.
Further, it is possible to produce polymer particles having a predetermined particle diameter by employing a polymerization method such as emulsion polymerization, multi-step seed polymerization, suspension polymerization. Among these polymerization methods, the suspension polymerization method is a preferable method in the present invention because the particle size can be easily controlled.

The polymer particles are usually 10-100.
It has an average particle diameter of 40 to 60 μm, especially when the resin particles of the present invention are used as particles for producing artificial marble. Is preferred. Furthermore, it is preferable that the polymer particles have uniform particle diameters, and that the polymer particles are true spherical monodisperse particles having a relative standard deviation of 30% or less.

The FRP resin particles of the present invention are particles in which the alkylsilane compound and / or the coupling agent are bonded to the surface of the polymer particles as described above.
The alkylsilane compound used in the present invention has the formula: R _n
SiY _4-n (wherein R represents an alkyl group, Y represents a hydrolyzable group, and n is an integer of 1 to 3).

Here, the alkyl group may be linear,
Alternatively, they may be branched, and when n is 2 or 3, these alkyl groups may be the same or different. Particularly in the present invention, the alkyl group represented by R preferably has 3 to 10 carbon atoms, and further preferably has 3 to 10 carbon atoms and has a linear structure. . That is, when an alkylsilane compound having an alkyl group as described above is mixed with a resin to produce, for example, an FRP composition, the alkyl groups derived from the alkylsilane compound are physically entangled in the FRP resin at the molecular level. The FRP resin particles of the present invention can be stabilized in the resin (resin composition) forming the FRP. When the alkyl group has less than 3 carbon atoms, the lipophilicity of the alkyl group portion does not become so high, so the dispersibility of the resin particles of the present invention in the FRP composition may not be sufficiently improved. Also, FR
The stability of the FRP resin particles of the present invention in the P composition may not be improved. Conversely, the alkyl group has 1 carbon atom
When it exceeds 0, the lipophilicity of the alkylsilane becomes excessively high, and thus the treatment efficiency at the time of treating the resin particles with the alkylsilane may decrease. Further, the one having a straight-chain alkyl group has a longer molecular chain length than the alkyl group having a branched structure, and more effectively penetrates into the FRP resin in the FRP molded product to obtain good particle dispersion stability. Show.

The hydrolyzable group of the alkylsilane compound used in the present invention is hydrolyzed to form a silanol group, which is dehydrated and condensed with the surface of polymer particles. Examples of the hydrolyzable group include an alkoxy group and an acetoxy group. Among them, an alkoxy group having a good reactivity with the surface of polymer particles is preferable, and an ethoxy group and / or a methoxy group is particularly preferable. preferable.

Further, in the above formula, n is not particularly limited as long as it is an integer of 1 to 3, but it is particularly preferable that n is 1. This is because in the resin particles of the present invention, the smaller the number of n is, the stronger the bond of the alkylsilane compound to the layer due to the surface of the polymer particles is. By reducing the number, it is possible to prevent adverse effects due to steric hindrance between alkyl groups.

Among such alkylsilane compounds,
Preferable examples include normal propyl trimethoxysilane, normal hexyl trimethoxy silane, normal decyl trimethoxy silane, normal propyl triethoxy silane, normal hexyl triethoxy silane, and normal decyl triethoxy silane.

Two or more kinds of this alkylsilane compound can be used in combination as long as the performance thereof is not affected. In the present invention, the coupling agent, which is used separately or together with the alkylsilane compound, is a compound which causes a coupling reaction between an inorganic substance and an organic substance, or a polymer particle surface and an FRP composition. A compound that causes a coupling reaction between the two, specifically, examples of the coupling agent used in the present invention include a silane coupling agent, an organotitanium coupling agent, a chromium coupling agent, and a silyl coupling agent. Examples thereof include peroxides, organic phosphorus-based coupling agents, and aluminum-based coupling agents.

Here, the silane coupling agent is represented by the formula (X
R) _n is a compound represented by SiY _4-n . Here, X is a functional group having reactivity with a resin constituting the FRP resin or a polymerizable monomer blended as a solvent for this resin, R is an organic group, and Y is a hydrolyzable group. Meaning,
n is an integer of 1 to 3.

Examples of the functional group reactive with the resin constituting the FRP resin represented by "X" in the above formula or the polymerizable monomer added as a solvent for the resin include a vinyl group and a methacryloxy group. , Glycidoxy group, amino group and the like. In the present invention, a methacryloxy group is particularly preferred.

The organic group represented by "R" in the above formula is usually a hydrocarbon group such as an alkyl group or a group in which an atom such as oxygen, nitrogen or sulfur is bonded to the hydrocarbon group. The organic group may be linear or branched. In the FRP molded product, the functional group having reactivity with the FRP resin and the polymerizable monomer added as the solvent of the resin in the molecule of the silane coupling agent is added as the FRP resin or the solvent of the resin. It is considered that it is reacting with the polymerizable monomer that is present.

Further, the hydrolyzable group in the above formula representing the silane coupling agent is a group which undergoes hydrolysis to become a silanol group, which is dehydrated and condensed with the surface of the polymer particles. Examples of the hydrolyzable group include a general alkoxy group and an acetoxy group. Among them, an alkoxy group having good reactivity with the surface of the polymer particles is preferable,
Further, an ethoxy group and a methoxy group are particularly preferable.

Further, in the above formula, n is usually 1
Is an integer of 3 and preferably n is 1. This is because, in the resin particle of the present invention, the smaller the number of n, the stronger the bond of the silane coupling agent to the surface of the polymer particle, and at the same time, the functional group in the silane coupling agent is added. By reducing the number of the organic groups, it is possible to prevent adverse effects due to steric hindrance between the organic groups.

Examples of such silane coupling agents are vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ.
-Glycidoxypropyltriethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
Examples thereof include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

Examples of organic titanium coupling agents include tripropyltriisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphite) titanate, tetraoctyl bis (dioctyl phosphite) titanate, Tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphophosphate) oxyacetate titanate, bis (dioctyl pyro) Phosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dioctyl phosphite) Over G) titanate, diisopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, it may be mentioned dicumyl phenyloxy acetate titanate, and diisostearoyl ethylene titanate.

As the chromium-based coupling agent,
Chromium methacrylate complex compound and palchrome 5015
(Product name: Vakcarome5015, manufactured by Valchem).

Further, examples of the silyl peroxide include pentyl trimethyl silyl peroxide, butyl trimethyl silyl peroxide, tert-butyl dimethyl silyl peroxide, tert-butyl dimethyl phenoxy silyl peroxide, bis (tert-butyl dimethyl silyl) peroxide, and dimethyl phenyl silyl peroxide. Can be mentioned.

Further, as an example of the organic phosphoric acid type coupling agent, the following formula: RO-PO (OH) ₂ (wherein R represents an ethyl group, a butyl group, an isoamyl group), the following formula: RO -PO (OR) ₂
(In the formula, R is each independently a methyl group, an ethyl group,
Butyl group, 2-ethylhexyl group, phenyl group),
A substance represented by the following formula: HO-PO (OR) ₂ (wherein each R independently represents a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group or a phenyl group) can be mentioned. .

Further, as an example of the aluminum-based coupling agent, acetoalkoxyaluminum diisopropionate can be mentioned. In the present invention, as the coupling agent, any of the above-mentioned coupling agents can be used, but a silane coupling agent is preferably used from the viewpoint of coupling performance, easiness of handling and the like.

The above coupling agents can be used alone or in combination. Further, it can be used in combination with the above-mentioned alkylsilane compound. The amount of the alkylsilane compound and / or the coupling agent used in the present invention is preferably such that a uniform layer can be formed on the surface of the core polymer particles. That is, it is usually 0.01 to 5 parts by weight, preferably 0.0 to 100 parts by weight of the polymer particles.
Used in an amount in the range of 5 to 2.0 parts by weight.

By using the alkylsilane compound and / or the coupling agent in the above amount, the boiling resistance of the FRP molded product containing the additive particles becomes very good. Incidentally, even if used in a large amount outside the above range, the characteristics of the obtained molded article hardly show the improvement of the characteristics corresponding to the compounding amount, but the characteristics are not deteriorated and the cost is disadvantageous. It just becomes.

The amount of the above-mentioned alkylsilane compound and / or the coupling agent used is a standard amount, and in the present invention, the average particle size, particle size distribution and surface of the polymer particles as the core material are used. The usage amount can be appropriately set according to the state, the minimum clothing area depending on the type of the alkylsilane compound or the coupling agent used, and the like.

As a method of reacting the alkylsilane compound and / or the coupling agent with the surface of the polymer particles, the alkylsilane compound and / or the coupling agent may be added to the polymer particles as they are or under stirring. Examples thereof include a method of dissolving in a solvent and spraying, and a method of mixing an alkylsilane compound and / or a coupling agent dissolved in a suitable solvent with polymer particles to form a slurry and then dehydrating and drying. When the resin particles are produced by this method, it is necessary to treat the surface of the polymer particles with the alkylsilane compound and / or the coupling agent sufficiently at a suitable temperature for a sufficient time even after drying. desirable. However,
The heating temperature in this case is a temperature at which the resin forming the polymer particles does not undergo thermal denaturation.

When the alkylsilane compound or the coupling agent is dissolved in the solvent, it is preferable to add an acidic compound such as acetic acid to the solvent to adjust the pH value of the solvent to about 3-4. By adding the acidic compound in this manner, the solubility of the alkylsilane compound or the coupling agent in the solvent is improved, the hydrolysis of the alkoxy group is promoted by the presence of the acidic compound, and the silanol group formed is Stabilization is also improved.

The average particle diameter of the resin particles of the present invention in which the alkylsilane compound and / or the coupling agent are bonded to the surface of the polymer particles as described above is usually 10 to 10.
It is in the range of 100 μm, preferably 30 to 70 μm. In the present invention, the average particle size of the particles is measured by a laser diffraction type particle size distribution measuring device (MALVERN MASTER SI
Volume-based integration of particle groups measured using ZER) 50%
Is the diameter. When the average particle size of the FRP resin particles is less than 10 μm, the resin particles added to the FRP composition are
Since the number per unit weight is relatively large, FRP
The transparency of the molded body tends to decrease. The average particle size is 1
When it is larger than 00 μm, the number of resin particles added to the FRP composition is relatively small per unit weight, so that the shrinkability of the FRP molded article is not sufficiently reduced, and the resin particles are removed from the surface of the molded article. Since it tends to protrude, the surface smoothness and surface gloss of the molded product may deteriorate.

The resin particles for FRP of the present invention may further contain an antiaging agent, an antistatic agent, a plasticizer and the like. Further, the compound or the like used in the step of producing polymer particles may remain in the FRP resin particles of the present invention.

The FRP composition of the present invention contains the above-mentioned FRP.
Resin particles for RP are dispersed in the resin forming FRP. Here, as an example of the resin forming the FRP composition, a thermosetting resin such as an unsaturated polyester resin, an epoxy resin, a vinyl ester (epoxy acrylate) resin, a phenol resin, a silicone resin, or a thermosetting acrylic resin is preferably used. You can do it. Among these, it is particularly preferable to use unsaturated polyester or vinyl ester (epoxy acrylate) resin.

As these resins, generally commercially available resin compositions can be used. In the case of an unsaturated polyester resin, for example, a commercially available resin composition is sold in a state in which the unsaturated polyester resin is dissolved in a vinyl monomer. Then, a small amount of a polymerization inhibitor is contained in the vinyl monomer that serves as a solvent here. Therefore, commercially available unsaturated polyester resin compositions are often vinyl monomer solutions of unsaturated polyester resins.

Examples of the unsaturated dibasic acid used as a raw material for such an unsaturated polyester resin include maleic anhydride and fumaric acid. Examples of the saturated dibasic acid include phthalic acid, isophthalic acid, terephthalic acid, adipic acid, tetrabromophthalic anhydride,
Himic acid etc. can be mentioned.

Examples of glycols used as raw materials for the unsaturated polyester resin include polypropylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A and propylene oxide-added bisphenol A. You can

Further, examples of vinyl monomers used as a solvent for such unsaturated polyester resins include:
Styrene, methyl methacrylate, monochlorostyrene,
Examples thereof include diallyl phthalate and triallyl cyanuphthalate.

Of the commercially available resin compositions, the vinyl ester resin composition is obtained by reacting an oligomer obtained by ring-opening addition polymerization of an epoxy resin and an unsaturated monobasic acid such as methyl methacrylate with a reaction such as styrene. Many of them are sold in a state of being dissolved in a polymerizable vinyl monomer.

Examples of the epoxy resin used as the raw material of the vinyl ester resin composition are bisphenol A type, novolac phenol type, and bisphenol F type.
Examples thereof include resins such as resins, brominated epoxy resins, cycloaliphatic resins, glycidyl ester resins, and glycidyl amine heterocyclic epoxy resins.

The amount of resin contained in 100 parts by weight of this resin composition is usually 60 to 80 parts by weight. When a molded product is produced from an FRP composition using these resin compositions, the molded product can be cured to form a molded product having good aesthetics and boiling resistance. However, due to volume contraction during curing, a molded product having a desired size cannot be obtained, or a molded product that is cracked during curing may be broken. In order to prevent this phenomenon, a low-shrinking agent has been conventionally added, but the dimensional accuracy of the molded product is improved by this, but the transparency, coloring property and boiling resistance of the molded product are reduced.

In the FRP composition of the present invention, the above-mentioned FRP resin particles are usually 0.1 to 10 parts by weight, preferably 2 to 100 parts by weight of the FRP resin composition forming the molded article. It is compounded in an amount of 5 parts by weight. By blending the resin particles for FRP in the above amount, F
The volume shrinkage at the time of molding using the FRP composition can be sufficiently reduced without lowering the aesthetics and boiling resistance of the resin composition for RP, and cracks due to volume shrinkage in the molded product. This can be prevented from occurring, and a molded product having a desired size can be obtained.

The FRP composition of the present invention may further contain a curing agent, a non-filling material, a fibrous filling material, a heat resistance stabilizer, a weather resistance stabilizer, a release agent, a coloring agent, an adhesive agent and the like. . Examples of curing agents include methyl ethyl ketone peroxide, tert-butyl (2-ethylhexanoate), 1,1-bis-tert-butylperoxy- (3,3,5-trimethylcyclohexane), cumylperoxy. Mention may be made of neodecanoate. The amount of such a curing agent is usually 0.5 to 100 parts by weight of the FRP composition.
2 parts by weight.

Examples of the inorganic filler include powders of alumina, silica, calcium carbonate, clay, glass, aluminum hydroxide and the like, or powders obtained by subjecting the surface of these powders to a functional treatment. Of these, powders of glass and aluminum hydroxide are preferably used. These inorganic fillers can be used alone or in combination. These inorganic fillers are FR
It is usually 200 to 400 parts by weight with respect to 100 parts by weight of the P composition.

Further, examples of the fibrous filler include glass fiber, carbon fiber, boron fiber and the like. These may be used alone or in combination. This amount is usually 1 to 50 parts by weight with respect to 100 parts by weight of the FRP composition.

Further, examples of the release agent include phosphoric acid esters and metal salts of stearic acid.
Zinc stearate is particularly preferable. The release agent as described above is used by being blended with the FRP composition. In addition to the release agent (internal release agent) blended with the FRP composition,
There is a release agent (external release agent) that is used by applying it to a mold at the time of molding the FRP composition, and in the present invention, for example, wax, polyvinyl alcohol or the like is used as such an external release agent. You can also

Further, as the thickener, hydroxides and oxides of alkaline earth metals and polyisocyanate compounds can be used, and magnesium oxide is particularly preferable.

Using the FRP composition as described above, generally used FRP molding methods such as hand lay-up molding method, spray-up molding method, resin injection molding method, injection molding method, filament winding molding method and pultrusion molding method. The FRP molded body having a desired shape can be manufactured with a desired size by the breath molding method.

Using the FRP composition of the present invention, a conventional FR
Although it is possible to manufacture a P molded body, it is particularly suitable for manufacturing a molded body called artificial marble. Since artificial marble is excellent in transparency and colorability, it is used for countertops such as kitchens and washstands, bathtubs, etc., and boiling resistance is required. The resin particles contained in the FRP composition of the present invention do not impair the appearance of the FRP molded product while imparting a sufficiently low shrinkage property to the FRP molded product, and do not lower the boiling resistance, so that an artificial marble is produced. Suitable for In particular, it is suitable for producing a molded product such as a BMC artificial marble bathtub that is in contact with hot water for a long time.

[0063]

The FRP resin particle of the present invention comprises an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle as the core material, and therefore, the FRP composition containing such resin particle. The molded product formed from shows good shrinkage resistance and crack resistance without lowering boiling resistance, transparency, colorability, mechanical strength and the like.

Further, the composition containing the FRP resin particles can produce an FRP molded article having excellent properties such as boiling resistance, transparency, colorability and mechanical strength. By blending resin particles, it is possible to manufacture a molded body known as an artificial marble having a marble-like appearance. The artificial marble produced from the composition containing the FRP resin particles of the present invention is particularly excellent in boiling resistance.

[0065]

EXAMPLES The present invention will now be described in more detail with reference to examples of the present invention, but the present invention is not limited thereto.

[0066]

Example 1 Methyl methacrylate 3 in a glass reaction vessel
9.5 parts by weight, 60 parts by weight of styrene, and 0.5 parts by weight of divinylbenzene were added and mixed, and then benzoyl peroxide 1 was added.
Part by weight was added and dissolved.

Separately, 2 parts by weight of polyvinyl alcohol was added and dissolved in 300 parts by weight of ion-exchanged water to prepare a solution, and this solution was added to the above glass reaction container and dispersed by vigorous stirring with a homomixer. A nitrogen gas introduction tube, a thermometer and a condenser were attached to this reaction vessel, nitrogen gas was introduced and purged, and then the dispersion liquid was heated to 80 ° C. while stirring.

After maintaining this temperature for 8 hours, the obtained suspension was cooled to room temperature and filtered to separate the polymer particles and the polyvinyl alcohol aqueous solution as the dispersion medium.

The obtained polymer particles were redispersed in 100 parts by weight of methyl alcohol, stirred for 1 hour, and then filtered to separate the polymer particles. 8 polymer particles obtained
It was crushed after being dried for 8 hours using a dryer kept at 0 ° C. The average particle size of the obtained polymer particles is 4
It was 5.1 μm.

A solution prepared by dissolving 0.1 part by weight of commercially available n-hexyltrimethoxysilane (manufactured by Chisso Corp., HTS-M) in 60 parts by weight of a 50% by weight methyl alcohol aqueous solution was added.
100 parts by weight of the polymer particles obtained above were added and stirred to form a slurry.

The resulting slurry was thoroughly dried with stirring in a vacuum dryer, and then normal hexyltrimethoxysilane was bound to the surface of the polymer particles in a dryer kept at 105 ° C. for 5 hours. , FRP of the present invention
Resin particles were produced.

When the average particle size of the FRP resin particles was measured by a laser diffraction type particle size distribution measuring device, the average particle size was 45.8 μm.

[0073]

Example 2 100 parts by weight of the polymer particles prepared in Example 1 was added to 0.2 parts by weight of 0.2 parts by weight of commercially available γ-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unica Co., Ltd., A-187).
FRP resin-added particles were prepared in the same manner except that the slurry was added to a solution dissolved in 60 parts by weight of a 0% by weight methyl alcohol aqueous solution and stirred to form a slurry.

[0074]

Example 3 100 parts by weight of the polymer particles prepared in Example 1 were mixed with commercially available γ-methacryloxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd., AZ-6167).
FRP resin-added particles were prepared in the same manner except that 3 parts by weight was added to a solution prepared by dissolving 60 parts by weight of a 50% by weight methyl alcohol aqueous solution and stirred to form a slurry, and this slurry was used.

[0075]

Example 4 99 parts by weight of styrene and 1 part by weight of vinylbenzene were placed in a glass container and mixed, and then 0.5 part by weight of benzoyl peroxide was added and dissolved.

Separately, 0.4 part by weight of sodium dodecylbenzenesulfonate was added to 190 parts by weight of ion-exchanged water, and then 10 parts by weight of hydroxyapatite (Supertite 10 manufactured by Nippon Kagaku Kogyo Co., Ltd.) (solid content: 10 parts by weight). Part, water content 90 parts by weight) was vigorously stirred and dispersed with a homomixer. This hydroxyapatite dispersion was added to a glass reaction vessel and further vigorously stirred with a homomixer to disperse. A nitrogen inlet tube, a thermometer and a condenser were attached to the glass reaction vessel, the glass reaction vessel was purged with nitrogen gas, and the dispersion was heated to 85 ° C. while stirring.

After maintaining this temperature for 8 hours, the obtained suspension was cooled to room temperature and filtered to separate the polymer particles from the dispersion medium sodium dodecylbenzenesulfonate aqueous solution.

100 parts by weight of the obtained polymer was added to 5% by weight.
Redisperse in 200 parts by weight of hydrochloric acid aqueous solution, stir for 8 hours,
After dissolving the hydroxyapatite, the polymer particles were separated by filtration.

The polymer particles from which the hydroxyapatite was removed in this manner were mixed with 0.2 part by weight of commercially available normal hexyl trimethoxysilane (manufactured by Chisso Corporation, HTS-M) in an amount of 0.2 part by weight.
The mixture was added to a solution prepared by dissolving 65 parts by weight of an aqueous isopropyl alcohol solution in weight% and stirred to form a slurry.

Resin particles for FRP were manufactured in the same manner as in Example 1 except that this slurry was used.

[0081]

Example 5 Methyl methacrylate 8 in a glass reaction vessel
After 9.9 parts by weight, 10 parts by weight of 2-ethyl acrylate and 0.1 parts by weight of ethylene glycol dimethylmethacrylate were added and mixed, 0.8 part by weight of lauryl peroxide was added and dissolved.

Separately, 2.5 parts by weight of a sodium salt of polyacrylic acid and 6 parts by weight of sodium sulfate were added to 290 parts by weight of ion-exchanged water to dissolve them, and the resulting mixture was added to the above-mentioned glass reaction vessel and further mixed with a homomixer. Stir vigorously to disperse. A nitrogen gas introducing tube, a thermometer and a condenser were attached to facilitate the reaction, nitrogen gas was introduced and purged, and then the dispersion was heated to 75 ° C. while stirring.

After maintaining this temperature for 8 hours, the resulting suspension was cooled to room temperature and filtered to separate the polymer particles from the dispersion medium of sodium salt of polyacrylic acid and aqueous sodium sulfate solution.

30 parts by weight of the obtained polymer particles were redispersed in 200 parts by weight of an isopropyl alcohol aqueous solution to prepare 1
After stirring for an hour, the polymer particles were separated by filtration.
While drying the obtained polymer particles (wet) in a fluidized bed drier at 80 ° C., 100 parts by weight of the polymer particles were mixed with commercially available tetra (2,2, -diallyloxymethyl-1-butyl) bis. (Dodecyl) sulfonate titanium (Ajinomoto Co., Inc.
A solution prepared by dissolving 1 part by weight of KR55 manufactured by K.K. in 99 parts by weight of water was sprayed.

Then, the surface of the polymer particles was reacted with the titanium coupling agent using a dryer heated to 105 ° C. for 5 hours to prepare FRP resin particles.
The average particle diameter of the resin particles for FRP was measured by a laser diffraction particle size distribution measuring device, and the average particle diameter was 54.
It was 1 μm.

[0086]

Example 6 The polymer particles before drying treatment prepared in Example 5 were dried for 8 hours by using a dryer kept at 80 ° C. and then crushed.

100 parts by weight of the obtained particles are added to commercially available γ-
Methacryloxypropyl methoxysilane (Nippon Unicar
(Manufactured by KK, AZ-6167) 0.2 parts by weight was dissolved in 60 parts by weight of a 50% by weight aqueous solution of methyl alcohol.
Add and stir to make a slurry.

Thereafter, the same operation as in Example 1 was carried out to prepare FRP resin particles.

[0089]

Comparative Example 1 The polymer particles prepared in Example 1 were used as FRP resin particles without treatment with a silane compound or a coupling agent.

[0090]

Comparative Example 2 The polymer particles prepared in Example 4 were used as FRP resin particles without treatment of the polymer particles obtained by dissolving and removing hydroxyapatite with an aqueous hydrochloric acid solution without using a silane compound or a coupling agent.

[0091]

Comparative Example 3 The polymer particles prepared in Example 5 were used as FRP resin particles without being treated with a silane compound or a coupling agent.

[0092]

Example 7 and Comparative Example 4 F obtained as described above
5 parts by weight of resin particles for RP, 100 parts by weight of unsaturated polyester resin composition for BMC (manufactured by Nippon Yupica Co., Ltd., Yupica 7685X-1, styrene solution of unsaturated polyerter resin), inorganic filler (Japan) Frit Co., Ltd., GF-2-10A) 300 parts by weight, polymerization initiator (NOF Corporation, Perbutyl I) 1 part by weight, silane coupling agent (Nippon Unicar Co., Ltd.,
A-174) 3 parts by weight, internal mold release agent (NOF Corporation, zinc stearate) 3 parts by weight, thickener (Kyowa Chemical Industry Co., Ltd., Kyowamag # 150) 4.5 parts by weight desktop type Biaxial kneader (PNV-1 manufactured by Irie Shokai Co., Ltd.)
Type) and kneaded at room temperature and aged at 40 ° C. for 2 to 4 days.

The FRP composition thus obtained was subjected to pressure heating to heat the BMC composition after aging using a backward-moving hydraulic molding machine in which a mold having a built-in heating device was set to a thickness of 8 m.
It was molded into a flat plate of m.

Using the obtained flat plate, the moldability and the molded product were evaluated.

[0095]

[Evaluation Method of Resin Particles] (1) Evaluation and Transparency of Molded Body The obtained BMC molded body was visually judged. Compared with a molded body (hereinafter referred to as a blank) in which the resin particles of the example of the present invention or a comparative example is not added (hereinafter referred to as a blank), the molded body has severe white turbidity and the transparency is remarkably deteriorated ×, slightly decreased. When it was done, it was evaluated as Δ, and when there was no difference from the blank, it was evaluated as ○.

Colorability The BMC molded body obtained was visually judged. Compared with the blank, the case where the unevenness of the color of the molded product was severe was evaluated as ×, the case where slight unevenness was observed was evaluated as Δ, and the case where the difference with the blank was not observed was evaluated as ○.

Mechanical Strength The surface hardness of the obtained BMC molded product was measured by a Barcol hardness meter and evaluated. Compared to the blank, the case where the barcol hardness was reduced by 10% or more was evaluated as ×, and the case where a decrease of 5% to less than 10% was observed, and the case where no difference from the blank was observed was evaluated as ◯.

-Boiling resistance The obtained BMC molded product was continuously boiled in hot water at 90 ° C for 500 hours, and the color change (whitening and yellowing) of the molded product was measured using a color difference meter. When the color change was significantly more severe than that of the blank, it was evaluated as ×, when the color change was slightly observed, it was evaluated as Δ, and when the difference with the blank was not observed, it was evaluated as ○.

Low shrinkage and crack prevention The dimensions of the obtained BMC molded product and the dimensions of the mold were measured using a caliper to calculate the shrinkage. Here, the shrinkage ratio is (dimension of mold-dimension of molded body) / (dimension of mold). Shrinkage of 0 to 0.01% is ◯, 0.011
˜0.02% was evaluated as Δ, and 0.021% or more was evaluated as ×.

Tables below. 1 shows the evaluation results of Examples of the FRP additive of the present invention and the evaluation results of Comparative Examples.

[0101]

[Table 1]

Claims (3)

[Claims] 1. FRP resin particles comprising a polymer particle core material and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material. 2. The average particle diameter of the polymer particle core material is 1
The resin particles for FRP according to claim 1, wherein the resin particles are in the range of 0 to 100 μm. 3. Resin particles comprising a polymer particle core material and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material are dispersed in a resin matrix. FRP composition.