JP3538982B2 - Resin particles for FRP and FRP composition - Google Patents

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 a resin particle for P and an FRP composition containing the resin particle. More specifically, the present invention relates to a resin particle blended with a resin when producing FRP, especially FRP called SMC and BMC, especially FR called artificial marble.
The present invention relates to resin particles suitably used for forming P and a resin composition capable of producing a molded article having a marble-like appearance containing the particles. Further, the present invention relates to a resin particle capable of forming a molded article having a low shrinkage property with little reduction in boiling resistance, transparency, coloring property, mechanical strength and the like, and a resin composition containing the resin particle. .

[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 their mechanical strength, chemical resistance, productivity, etc. Many studies have been made to improve the performance required for each application. Has been done.

[0003] For example, a method of molding at a high temperature is employed in order to shorten the curing time and improve the productivity when producing an FRP molded body. By raising the molding temperature to a high temperature, the curing time can be shortened, but on the other hand, cracks occur in the molded body due to internal stress caused by volume shrinkage of the composition accompanying curing, or the dimensional accuracy of the molded body due to volume shrinkage Decreases. Further, since the surface smoothness of the molded body is easily deteriorated, there is a problem that the surface gloss of the molded body is reduced.

As a method of solving such a problem, F
The RP composition employs a method of adding an additive called a low-shrinkage agent or a non-shrinkage agent. However, the addition of this additive causes a new problem such as a decrease in the colorability and transparency of the FRP molded article. Further, when a molded article containing such an additive is observed over time, performances called water resistance, boiling resistance, hot water resistance and the like are also reduced.

[0005] Artificial marble is one of the fields of FRP molded articles. Among them, BMC artificial marble is excellent in productivity. This artificial marble is an FRP molded product which is obtained by mixing a resin with an inorganic powder or the like and is colored like marble, and is used as a countertop or a bathtub in a kitchen or a washbasin. From the use of such artificial marble, this FRP has transparency, uniform coloring,
The characteristics that make up the aesthetics of the molded product, such as surface gloss, are emphasized,
It is necessary to select an additive so that the coloring property and the transparency of the molded article are not reduced by the addition of the additive.

[0006] Further, since the bathtub, which is a molded product of this FRP, is exposed to warm water at about 40 ° C, deterioration of the molded product due to the addition of additives (usually such characteristics are referred to as “boiling resistance”). It is a big problem. Particularly recently, a 24-hour bath system, which is always available for bathing, has become widespread. In such a system, an artificial marble bathtub is always in contact with warm water at about 40 ° C. More than a bathtub,
The above-mentioned boiling resistance has become an important property. In other words, when a conventional BMC artificial marble bathtub is used, the bathtub is significantly deteriorated under the conditions of use, and the appearance of the bathtub becomes less aesthetic in a short time.

[0007] Various improvements have been proposed for the problem of boiling resistance of a bathtub formed from artificial marble. For example, as a filler used in FRP compositions,
A method using an inorganic substance treated with a coupling agent such as an alkylsilane compound or a silane coupling agent, or when preparing an FRP composition, a coupling agent such as a silane coupling agent may be used in combination with another FRP composition. Methods such as adding and kneading the constituent materials are known (for example, Japanese Patent Application Laid-Open No. 58-173114,
JP-A-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).

[0008] Although the boiling resistance of the bathtub as an FRP molded article is improved to some extent by such an improvement, it is still not possible to withstand use under severe conditions such as a bath for 24 hours. This is because these improvements generally improve the state of the interface between the resin for FRP and the inorganic filler to improve the boiling resistance of the molded article. Alternatively, the problem that the boiling resistance of the molded article is reduced by the crack preventing agent cannot be solved.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide novel resin particles to be added to an FRP molded article.

Further, the present invention provides a resin particle for FRP which can form a resin molded article having excellent transparency, coloring property, mechanical properties, surface gloss, boiling resistance and low shrinkage when added to a resin. It is intended to provide.

[0011] Further, the present invention, by adding to the resin, the appearance of the molded article such as coloring, transparency, surface gloss, etc.
In addition, the resin particles and the resin particles capable of reducing the shrinkage during molding of the molded article, as well as the mechanical strength of the molded article, as well as the boiling resistance of the molded article, are blended. Accordingly, an object of the present invention is to provide an FRP composition capable of producing a molded article having the above-described properties.

[0012]

SUMMARY OF THE INVENTION The resin particles for FRP of the present invention have an average particle size of
It is characterized by comprising a polymer particle core material having a diameter in the range of 10 to 100 μm , and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material.

Further, the FRP composition of the present invention has an average particle diameter in a range of 10 to 100 μm in a resin matrix .
Wherein 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.

The FRP resin particles of the present invention are particles in which one or both of an alkylsilane compound and a coupling agent are bonded to the surface of polymer particles serving as a core material (namely, a nucleus). By adding the resin particles for molding, it is possible to produce a molded article having excellent properties such as colorability, transparency, and surface glossiness of the FRP molded article. In addition, by using such resin particles, not only the strength and the like of the molded body but also the shrinkage rate during molding of the molded body is reduced without lowering the boiling resistance of the molded body, and cracks are formed. And a molded article having excellent dimensional accuracy can be manufactured.

[0015]

Next, the FRP resin particles of the present invention and the FRP composition containing the resin particles will be described in detail.

The resin particles of the present invention comprise polymer particles forming a core, and an alkylsilane compound and / or a coupling agent bonded to the surface of the core. 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 the resin used for forming the FRP molded product are used. It is preferably formed of a resin that is not dissolved in the polymerizable monomer used as a solvent of the FRP composition contained therein and has a swelling property with respect to any of the components constituting the FRP composition.

Here, "the polymer particles swell in the polymerizable monomer" refers to a property determined by measuring the degree of swelling of a polymer according to the measuring method described below.

The method for measuring the degree of swelling of the polymer particles in the present invention is as follows. Inside diameter 14mm, height 135mm,
A 0.5 g sample is accurately weighed and placed in a 0.2 ml graduated scale, 20 ml colorless glass graduated cylinder, and tapped several times. Thereafter, 20 g of the styrene monomer was gently transmitted through the wall surface and poured, and the height of the swollen polymer particle phase when left at room temperature for 24 hours was read in ml, and the value calculated from the measured value by the following equation was used. Defined as swelling degree. Degree of swelling = (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, 2-hydroxy (meth) acrylate (Meth) acrylate monomers such as ethyl, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate; vinyl 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 monomer is (co)
It is preferable that a crosslinked structure is formed in the polymer particles produced by the polymerization. That is, the degree of swelling of the above-mentioned polymer particles can be adjusted by forming a bridge structure in the polymer particles, and the cross-linking structure is controlled by the amount of the difunctional monomer or 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 monomers constituting the FRP composition. Examples of bifunctional or polyfunctional monomers used to form a 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 bifunctional reactive monomer or the polyfunctional reactive monomer as described above varies depending on the type thereof, but the monofunctional monomer 1 used for forming the polymer particles may be used.
It is used in an amount of usually 0.005 to 2.0 parts by weight, preferably 0.1 to 1.0 part by weight, based on 00 parts by weight.

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

The polymer particles are usually from 10 to 100
μm, preferably having an average particle size of 30 to 70 μm, especially when the resin particles of the present invention are used as particles for producing artificial marble, having an average particle size of 40 to 60 μm. Is preferred. Further, the polymer particles preferably have a uniform particle size, and are preferably spherical monodisperse particles having a relative standard deviation of 30% or less.

The FRP resin particles of the present invention are particles in which an alkylsilane compound and / or a coupling agent are bonded to the surface of 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, more preferably 3 to 10 carbon atoms, and preferably has a linear structure. . That is, when an FRP composition is produced by blending an alkylsilane compound having an alkyl group as described above with a resin, for example, the alkyl groups resulting from the alkylsilane compound are physically entangled with the FRP resin at the molecular level. Thus, the FRP resin particles of the present invention can be stabilized in the resin (resin composition) forming the FRP. When the number of carbon atoms of the alkyl group is less than 3, the lipophilicity of the alkyl group portion is not so high, and 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, when the alkyl group has 1 carbon atom
If it exceeds 0, the lipophilicity of the alkylsilane becomes excessively high, so that the treatment efficiency when treating the resin particles with the alkylsilane may be reduced. Further, those having a straight-chain alkyl group have a longer molecular chain length than the alkyl group having a branched structure, and more effectively penetrate into the FRP resin in the FRP molded article to improve the dispersion stability of the particles. 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 polymer particle surface. Examples of the hydrolyzable group include an alkoxy group and an acetoxy group. Among them, an alkoxy group having good reactivity with the surface of the 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 n, the stronger the bond of the alkylsilane compound to the layer due to the surface of the polymer particles, and at the same time, the number of the alkyl groups in the alkylsilane molecule. By reducing the number, it is possible to prevent adverse effects due to steric hindrance between the alkyl groups.

Among such alkylsilane compounds,
Preferred examples include normal propyl trimethoxy silane, normal hexyl trimethoxy silane, normal decyl trimethoxy silane, normal propyl triethoxy silane, normal hexyl triethoxy silane, normal decyl triethoxy silane, and the like.

Two or more alkylsilane compounds can be used in combination as long as their performance is not affected. In the present invention, the coupling agent used separately from or together with the alkylsilane compound is a compound that causes a coupling reaction between an inorganic substance and an organic substance, or a polymer particle surface and an FRP composition. And a compound that causes a coupling reaction between the silane coupling agent, 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 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 resin constituting the resin for FRP, or a functional group having reactivity with a polymerizable monomer compounded as a solvent of the resin, R is an organic group, and Y is a hydrolyzable group. Means
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. Particularly, in the present invention, a methacryloxy group is 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 this hydrocarbon group. This organic group may be linear or branched. In the FRP molded body, a functional group having reactivity with the FRP resin and the polymerizable monomer added as a solvent of the resin in the silane coupling agent molecule is added as the FRP resin or the solvent of the resin. It is considered that the polymer has reacted with the polymerizable monomer.

The hydrolyzable group in the above formula representing the silane coupling agent is a group which is hydrolyzed to become a silanol group and to be dehydrated and condensed with the polymer particle surface. Examples of the hydrolyzable group include a general alkoxy group and an acetoxy group, and 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 preferred.

Further, in the above formula, n is usually 1
And n is preferably 1. This is because, in the resin particles of the present invention, the smaller the number n, the stronger the bond of the silane coupling agent to the surface of the polymer particles. By reducing the number of organic groups, the adverse effects due to steric hindrance between the organic groups can be prevented.

Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, β- (3,4-
(Epoxycyclohexyl) ethyltrimethoxysilane,
γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like can be mentioned.

Examples of the organic titanium-based coupling agent include tripropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphite) titanate, tetraoctylbis (dioctylphosphite) 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 isostearyl titanate, isopropyl tri (dioctylphosphonate) 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 coupling agent,
Chromium methacrylate complex and parchrome 5015
(Trade name: Vakcarome5015, manufactured by Valchem).

Further, examples of the silyl peroxide include pentyltrimethylsilyl peroxide, butyltrimethylsilyl peroxide, tert-butyldimethylsilyl peroxide, tert-butyldimethylphenoxysilyl peroxide, bis (tert-butyldimethylsilyl) peroxide and dimethylphenylsilyl peroxide. Can be mentioned.

Further, examples of the organic phosphoric acid-based coupling agent include the following formula: RO-PO (OH) ₂ (where R represents an ethyl group, a butyl group, and an isoamyl group); -PO (OR) ₂
(Wherein, R is each independently a methyl group, an ethyl group,
Butyl group, 2-ethylhexyl group, phenyl group),
The following formula: HO-PO (OR) ₂ (wherein, R independently represents a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group, a phenyl group). .

Further, examples of the aluminum-based coupling agent include acetoalkoxyaluminum diisopropionate. In the present invention, any of the above coupling agents can be used as the coupling agent, but a silane coupling agent is preferably used in view of coupling performance, ease 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 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 parts by weight, based on 100 parts by weight of the polymer particles.
It is used in an amount ranging from 5 to 2.0 parts by weight.

By using the alkylsilane compound and / or the coupling agent in the above amounts, the boiling resistance of the FRP molded article containing the additive particles becomes very good. Even if a large amount is used outside the above range, it is difficult for the properties of the obtained molded article to show the improvement of the properties corresponding to the compounding amount, but the properties do not decrease and the cost is disadvantageous. It just becomes.

The amount of the alkylsilane compound and / or the coupling agent described above indicates a standard amount. In the present invention, the average particle size, particle size distribution, state, the minimum to be due to the type of alkyl silane compound or coupling agent to be used
The amount of use can be appropriately set in accordance with the area covered or the like.

As a method for reacting such an alkylsilane compound and / or a coupling agent with the surface of the polymer particles, the alkylsilane compound and / or the coupling agent is added to the polymer particles as they are or under an appropriate condition. Examples thereof include a method of dissolving with a solvent and spraying, and a method of mixing an alkylsilane compound and / or a coupling agent dissolved in an appropriate solvent with polymer particles to form a slurry, followed by dehydration and drying. In the case of producing resin particles by this method, it is necessary to treat the polymer particles at a suitable temperature for a sufficient time after drying so that the alkylsilane compound and / or the coupling agent sufficiently react with the surface of the polymer particles. 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 adjust the pH value of the solvent to about 3 to 4 by adding an acidic compound such as acetic acid to the solvent. By adding the acidic compound in this manner, the solubility of the alkylsilane compound or the coupling agent in the solvent is improved, and the hydrolysis of the alkoxy group is promoted by the presence of the acidic compound. Stabilization also improves.

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

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

The FRP composition of the present invention comprises the above-mentioned FRP composition.
RP resin particles are dispersed in the resin forming the 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, and a thermosetting acrylic resin is preferably used. You can do it. Among these, it is particularly preferable to use unsaturated polyester and vinyl ester (epoxy acrylate) resins.

As these resins, generally 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 where the unsaturated polyester resin is dissolved in a vinyl monomer. A small amount of a polymerization inhibitor is contained in the vinyl monomer serving as the solvent. Accordingly, commercially available unsaturated polyester resin compositions are often vinyl monomer solutions of unsaturated polyester resins.

Examples of unsaturated dibasic acids used as raw materials for such unsaturated polyester resins include maleic anhydride and fumaric acid. Examples of the saturated dibasic acid include phthalic acid, isophthalic acid, terephthalic acid, adipic acid, tetrabromophthalic anhydride,
Hymic acid and the like can be mentioned.

Examples of the glycol used as a raw material for the unsaturated polyester resin include polypropylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, propylene oxide-added bisphenol A, and the like. Can be.

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

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

Examples of the epoxy resin used as a raw material of the vinyl ester resin composition include bisphenol A, novolak phenol and bisphenol F.
Resins, brominated epoxy resins, cyclic aliphatic resins, glycidyl ester resins, glycidylamine heterocyclic epoxy resins, and the like.

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

In the FRP composition of the present invention, the above-mentioned FRP resin particles are usually used in an amount of 0.1 to 10 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the FRP resin composition forming a molded article. It is blended in an amount of 5 parts by weight. By blending the FRP resin particles in the amount described above, F
Without reducing the aesthetic appearance and boiling resistance of the RP resin composition, volume shrinkage during molding using the FRP composition can be sufficiently reduced, and cracks due to volume shrinkage in the molded article can be reduced. It is possible to prevent the occurrence of a molded article and to obtain a molded article having a desired size.

The FRP composition of the present invention can further contain a curing agent, a filler, a fibrous filler, a heat stabilizer, a weather stabilizer, a release agent, a colorant, a pressure-sensitive adhesive, and the like. . For example, examples of the curing agent include methyl ethyl ketone peroxide, tert-butyl (2-ethylhexanoate), 1,1-bis-tert-butylperoxy- (3,3,5-trimethylcyclohexane), cumylperoxy. Neodecanoate can be mentioned. 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, and powders obtained by subjecting the surface of these powders to a functional treatment. Of these, glass and aluminum hydroxide powder 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 based on 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 can be used alone or in combination. This amount is usually 1 to 50 parts by weight based on 100 parts by weight of the FRP composition.

Further, examples of the release agent include metal salts of phosphoric acid esters and stearic acid.
Particularly, zinc stearate is preferable. The release agent as described above is used by being compounded in the FRP composition. In addition to the release agent (internal release agent) to be compounded in such an FRP composition,
There is a release agent (external release agent) applied to a mold at the time of molding the FRP composition, and in the present invention, as such an external release agent, for example, wax, polyvinyl alcohol, or the like is used. 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 preferred.

Using the FRP composition as described above, FRP molding methods generally performed, for example, hand lay-up molding method, spray-up molding method, resin injection molding method, injection molding method, filament winding molding method, pull-out molding method By using the breath molding method, an FRP molded body having a desired shape can be manufactured with desired dimensions.

Using the FRP composition of the present invention, the ordinary FR
Although a P compact can be produced, it is particularly suitable for producing a compact called artificial marble. Since artificial marble is excellent in transparency and coloring property, it is used for counter tops and bathtubs of kitchens, wash basins and the like, and is required to have boiling resistance. The resin particles contained in the FRP composition of the present invention, while imparting sufficient low shrinkage to the FRP molded article, do not impair the appearance of the molded article and further do not lower the boiling resistance, so that an artificial marble is produced. Suitable for In particular, it is suitable for producing a molded body that comes into contact with warm water for a long time, such as a BMC artificial marble bathtub.

[0063]

The FRP resin particles of the present invention are composed of an alkylsilane compound and / or a coupling agent bonded to the surface of polymer particles as a core material. Therefore, an FRP composition containing such resin particles. The molded article formed from has good low shrinkage and crack resistance without deteriorating boiling resistance, transparency, coloring property, mechanical strength and the like.

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

[0065]

Next, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

[0066]

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

Separately, a solution was prepared by adding and dissolving 2 parts by weight of polyvinyl alcohol to 300 parts by weight of ion-exchanged water, and this solution was added to the above-mentioned glass reaction vessel and dispersed by vigorous stirring with a homomixer. The reaction vessel was equipped with a nitrogen gas inlet tube, a thermometer, and a condenser. After nitrogen gas was introduced and purged, the dispersion was heated to 80 ° C. while stirring.

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

The obtained polymer particles were redispersed in 100 parts by weight of methyl alcohol, stirred for 1 hour, and then separated by filtration. The obtained polymer particles were
After drying for 8 hours using a drier kept at 0 ° C., it was crushed. 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 normal hexyltrimethoxysilane (HTS-M, manufactured by Chisso Corporation) in 60 parts by weight of a 50% by weight aqueous solution of methyl alcohol was used.
100 parts by weight of the polymer particles obtained above were added and stirred to form a slurry.

The obtained slurry was sufficiently dried while being stirred by a vacuum drier, and then normal hexyltrimethoxysilane was bonded to the surface of the polymer particles in a drier 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 with a laser diffraction type particle size distribution analyzer, the average particle size was 45.8 μm.

[0073]

Example 2 To 100 parts by weight of the polymer particles prepared in Example 1 was added 0.2 parts by weight of a commercially available γ-glycoxypropyltrimethoxysilane (A-187, manufactured by Nippon Yunika Co., Ltd.) to 5 parts by weight.
A FRP resin-added particle was prepared in the same manner as above except that the slurry was added to a solution of 60% by weight of a 0% by weight aqueous methyl alcohol 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 (AZ-6167, manufactured by Nippon Unicar Co., Ltd.).
3 parts by weight were added to a solution in which 60 parts by weight of a 50% by weight aqueous methyl alcohol solution was added, and the mixture was stirred to form a slurry. FRP resin-added particles were prepared in the same manner except that this slurry was used.

[0075]

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

Separately, after adding 0.4 parts by weight of sodium dodecylbenzenesulfonate to 190 parts by weight of ion-exchanged water, 10 parts by weight of hydroxyapatite (Super Tight 10 manufactured by Nippon Chemical Industry Co., Ltd.) (solid content: 10 parts by weight) Parts, 90 parts by weight of water) were dispersed vigorously with a homomixer. This hydroxyapatite dispersion was added to a glass reaction vessel, and further dispersed vigorously with a homomixer. The glass reaction vessel was equipped with a nitrogen inlet tube, a thermometer, and a condenser. After the glass reaction vessel was purged with nitrogen gas, the dispersion was heated to 85 ° 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 aqueous sodium dodecylbenzenesulfonate solution as a dispersion medium.

100 parts by weight of the obtained polymer was 5% by weight.
Re-dispersed in 200 parts by weight of hydrochloric acid aqueous solution, stirred for 8 hours,
After dissolving the hydroxyapatite, polymer particles were separated by filtration.

The polymer particles from which hydroxyapatite had been removed were mixed with 0.2 parts by weight of commercially available normal hexyltrimethoxysilane (HTS-M, manufactured by Chisso Corporation) in an amount of 5 parts by weight.
It was added to a solution dissolved in 65 parts by weight of an aqueous isopropyl alcohol solution by weight and stirred to form a slurry.

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

[0081]

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

Separately, 2.5 parts by weight of polyacrylic acid sodium salt and 6 parts by weight of sodium sulfate were added to 290 parts by weight of ion-exchanged water and dissolved, and then added to the above-mentioned glass reaction vessel, and further homogenized with a homomixer. Disperse with vigorous stirring. Nitrogen gas inlet tube into the reaction container, by mounting a thermometer and a condenser, was purged by introducing nitrogen gas, was heated with stirring to 75 ° C. The dispersion.

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, 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 aqueous isopropyl alcohol solution.
After stirring for an hour, the polymer particles were separated by filtration.
While drying the obtained polymer particles (wet body) in a fluidized-bed dryer at 80 ° C., 100 parts by weight of the polymer particles were added to 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) in 99 parts by weight of water was sprayed.

Then, the titanium-based coupling agent was allowed to react with the surface of the polymer particles for 5 hours using a dryer heated to 105 ° C. to prepare resin particles for FRP.
When the average particle diameter of the FRP resin particles was measured by a laser diffraction particle size distribution analyzer, 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 using a drier kept at 80 ° C., and then crushed.

100 parts by weight of the obtained particles were mixed with a commercially available γ-
Methacryloxypropylmethoxysilane (Nihon Unicar
AZ-6167 (manufactured by K.K.) in a solution prepared by dissolving 0.2 part by weight of a 50% by weight aqueous solution of methyl alcohol in 60 parts by weight,
Add and stir to a slurry.

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

[0089]

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

[0090]

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

[0092]

Example 7 and Comparative Example 4 F obtained as described above
5 parts by weight of the resin particles for RP were individually added to 100 parts by weight of an unsaturated polyester resin composition for BMC (Yupika 7885X-1, a styrene solution of an unsaturated polyether resin, manufactured by Nippon Yupica Co., Ltd.), and an inorganic filler (Japan). 300 parts by weight of Frit Co., Ltd., GF-2-10A), 1 part by weight of polymerization initiator (Nippon Oil & Fats Co., Ltd., Perbutyl I), silane coupling agent (Nippon Unicar Co., Ltd.
A-174) 3 parts by weight, 3 parts by weight of an internal mold release agent (Zinc stearate, manufactured by NOF CORPORATION), and 4.5 parts by weight of a thickener (Kyowa Mag # 150, manufactured by Kyowa Chemical Industry Co., Ltd.) Twin-screw kneader (PNV-1 manufactured by Irie Shokai Co., Ltd.)
) And aged at 40 ° C for 2 to 4 days.

The ripened BMC composition was heated to a thickness of 8 m by pressing and heating the FRP composition thus obtained using a reciprocating hydraulic molding machine in which a mold having a built-in heating device was set.
m flat plate.

The moldability and the molded body were evaluated using the obtained flat plate.

[0095]

[Method for Evaluating Resin Particles] (1) Evaluation and Transparency of Molded Article The obtained BMC molded article was visually judged. When the molded product was significantly clouded and the transparency was significantly reduced as compared with the molded product (hereinafter referred to as a blank) to which the resin particles of Examples and Comparative Examples of the present invention were not added, x: slightly decreased Was given when the test was performed, and when no difference from the blank was observed, the test was performed as ○.

Colorability The obtained BMC molded product was visually judged. When the shading of the molded article was more intense than that of the blank, the evaluation was x; when a slight unevenness was observed, the evaluation was Δ; when the difference from the blank was not observed, the evaluation was O.

Mechanical strength The surface hardness of the obtained BMC molded body was measured by a Barcol hardness tester and evaluated. When the Barcol hardness decreased by 10% or more as compared with the blank, X was given when a decrease of 5% to less than 10% was seen, and ○ was given when there was no difference from the blank.

Boil resistance The obtained BMC compact was continuously boiled in hot water at 90 ° C. for 500 hours, and the color change (whitening and yellowing) of the compact was measured using a color difference meter. When the change in color was remarkably intense compared to the blank, the evaluation was x, when the change in color was slightly observed, and when the difference from the blank was not observed.

Low Shrinkage and Crack Prevention The dimensions of the obtained BMC molded body and the dimensions of the mold were measured using calipers, and the shrinkage was calculated. Here, the shrinkage ratio is (dimension of mold-dimension of molded body) / (dimension of mold). ○, 0.011 when the shrinkage is 0 to 0.01%
△ 0.02% and ２１0.021% or more.

The following Table. 1 shows the evaluation results of the examples of the FRP additive of the present invention and the evaluation results of the comparative examples.

[0101]

[Table 1]

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J 3/12-3/16 C08J 5/04-5/10 C08L 61/00-101/16

Claims (2)

(57) [Claims] (1) The average particle diameter is in the range of 10 to 100 μm.
Resin particles for FRP, 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 resin matrix having an average particle size of 10
An FRP composition characterized in that resin particles comprising a polymer particle core material having a size within a range of from 100 to 100 μm and an alkylsilane compound and / or a coupling agent bonded to the surface of the polymer particle core material are dispersed. .