KR910008607B1 - Curing composition - Google Patents

Abstract

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Description

Curable composition

The present invention relates to a curable composition capable of producing a cured article excellent in thermal stability, in particular hydrotheraml stability, a method for producing the composition and the use thereof. More specifically, the present invention relates to a curable composition obtained by dispersing an inorganic filler of defined particle diameter in a defined liquid monomer mixture, a process for preparing the composition and the use of the composition in artificial marble products.

Unsaturated polyester resins, vinyl ester resins obtained by dissolving epoxy (meth) acrylates in styrene, and curable resin compositions prepared by dispersing various fillers in syrups of thermosetting resins such as epoxy resins are well known in the art. have. It has been used for injection molding artificial marble products and for FRP molding in combination with glass fibers. It is known to mold artificial marble products by curing them with organic peroxides as curing agents in resin compositions obtained by dispersing fillers in thermoplastic resin syrups, for example in combinations of methyl methacrylate syrups and aluminum hydroxide (US Pat. No. 3,847,865). . These thermosetting resins or thermoplastic resin syrups are conventionally molded by injecting into various spaces between molds or flow belts of various types and heating them to temperatures around normal room temperature to about 60 ° C. Curable resin compositions in the form of compression molding or extrusion molding in a metal mold by applying heat and pressure are also known in the art. Resin mortars or premixes prepared by, for example, mixing thermoset resins such as unsaturated polyester resins and vinyl ester resins with various fillers and aggregates and optionally mixing glass fibers and viscosity enhancing thickeners in the resulting mixture. ) Molding material.

Curable resin composition for injection molding using a syrup has a limitation in the amount and size of fillers that can be used because the viscosity must maintain a low viscosity to a suitable degree for injection molding. When a large amount of filler is used for the purpose of obtaining a cured article having a high filler content excellent in thermal stability and flame retardancy, the cured article produced has a poor appearance because the filler does not readily diffuse in the syrup during composition preparation. In order to prevent the viscosity of the produced resin composition from increasing due to the high filler content, a method of selecting a filler of the largest particle size possible, for example without sedimentation, is used. Therefore, the cured product obtained by polymerizing the above-mentioned curable resin composition has a disadvantage in that the surface is cracked due to insufficient dispersion of the filler or large particle size of the filler. As a result, water penetrates and bleaches rapidly when immersed in boiling water. Good appearance is lost.

In the case of the above-mentioned curable resin composition which uses a resin mortar or a premix molding material and is used for molding under simultaneous application of heat and pressure, there is a limit to the amount of fillers that can be mixed to prepare a dough-like lump having excellent workability during compression molding. There is. Generally, the upper limit is 200 weight part based on 100 weight part of resin. In the cured product obtained by polymerizing such a curable resin composition, the resin has a weak adhesive force to a filler or an aggregate, and the resin has a weak water resistance. This hardened product has the drawback that the surface is quickly damaged, whitened and loses luster when immersed in boiling water. These cured articles also lack thermal stability and are liable to discolor at high temperatures. This is a marked blot of tar in the burning cigarette test. Inadequate performance of conventional curable resin compositions is evident in applications such as bathtubs, dressing tables, button materials, electrical components, and kitchen countertops that require flame resistance, heat resistance, and hot water resistance.

It has been recognized that a gel coating of a cured product with an unsaturated polyester resin or a vinyl ester resin improves the hydrothermal stability of the cured product of such a curable resin composition. However, gel-coated cured products suffer from thermal stability and suffer from bubbles or similar defects that cannot be recovered when exposed to combustion tobacco or hot water.

It is therefore an object of the present invention to provide novel curable compositions, methods for preparing such curable compositions and uses thereof.

It is still another object of the present invention to provide a curable composition capable of providing a cured product having excellent thermal stability and flame retardancy without performing a gel coating treatment, a method for producing such a curable composition, and its use.

The above object is (A) a monomer mixture containing, as an essential component, 20-80% by weight of an aliphatic polyvalent (meth) acrylate and 80-20% by weight of an aromatic vinyl compound, (B) an inorganic having an average particle diameter of 5 microns or less. It is achieved by the curable composition which consists of a filler and (C) catalytic amount of a polymerization initiator, and an inorganic filler (B) is disperse | distributed by 250-800 weight part in 100 weight part of monomer mixtures (A).

In addition, the above object is (A) a monomer mixture containing a mixture of 20-80% by weight of an aliphatic polyvalent (meth) acrylate and 80-20% by weight of an aromatic vinyl compound as an essential component, (B) an average particle diameter of 5 microns or less With respect to the inorganic filler and (C) the catalytic amount of the polymerization initiator, by using a 250-500 parts by weight of the inorganic filler (B) per 100 parts by weight of the monomer mixture (A), mixed with a high speed stirrer to have a viscosity of 2-100 poise It is achieved by a method of preparing a curable composition that is configured to form a liquid mixture.

In addition, the above object is (A) a monomer mixture containing a mixture of 20-80% by weight of an aliphatic polyvalent (meth) acrylate and 80-20% by weight of an aromatic vinyl compound as an essential component, (B) an average particle diameter of 5 microns or less With respect to the inorganic filler and (C) the catalytic amount of the polymerization initiator, by using a 250-800 parts by weight of the inorganic filler (B) per 100 parts by weight of the monomer mixture (A), mixed with a low speed kneader to kneaded mass It is achieved in a method for producing a curable composition composed to form a.

The above-mentioned curable compositions are used alone or in combination with reinforcing fibers, which are filled in a mold and optionally heated under pressure to produce various cured products such as artificial marble products and FRP products. This curable composition is used to impregnate reinforcing fibers or shortening fibers for reinforcement or in combination with these fibers to make a fiber reinforced thermosetting molding material or premix molding material. This curable composition thus exhibits excellent performance for a wide range of applications.

Examples of aliphatic polyvalent (meth) acrylates usable in the present invention include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipanthaerythritol hexa (meth) acrylate.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, P-methylstyrene and divinylbenzene.

The ratio of aliphatic polyvalent (meth) acrylate and aromatic vinyl compound is 20-80 wt% in the former and 80-20 wt% in the latter. This ratio is preferably 30-70% by weight of the former and 70-30% by weight of the latter. Two monomers are an essential component in the monomer mixture (A) used in the curable composition of the present invention. However, as part of the monomer mixture (A), various (meth) acrylates such as (meth) acrylic acid or salts thereof, methyl (meth) acrylate, isobutyl (meth) acrylate, or trifluoroethyl (meth) acrylate Various macro monomers such as monomers, unsaturated polyester oligomers, fumaric acid esters, or maleimides, or other monomers or oligomers can be used. However, it should be noted that the use of such other monomers or oligomers results in difficulty in producing high filler content cured articles or in the lack of thermal stability or hydrothermal stability in the cured articles made.

The monomer mixture (A) used in the present invention can be used in a form in which a thermoplastic polymer is dissolved or dispersed for the purpose of suppressing shrinkage of the cured product. Thermoplastic polymers used for suppressing shrinkage and preventing cracking of cured products and improving surface smoothness are polymers generally used for suppressing shrinkage, and may be either soluble or dispersible in the monomer mixture (A). Examples of polymers meeting these conditions include (meth) acrylic polymers such as polymethyl methacrylate, (meth) acryl-styrene copolymers, polystyrene, polyvinyl acetate, styrene-vinyl acetate copolymers, polyvinyl chloride, polybutadiene , Polyethylene, polycaprolactam and saturated polyesters. These conventional low-shrinkage polymers are used alone or in the form of mixtures of two or more elements. When the low-shrinkage thermoplastic polymer is used in large quantities, the viscosity of the monomer mixture (A) is increased, making it difficult to prepare a high filler content curable composition suitable for injection molding, and the cured product exhibits satisfactory transparency and thermal stability. Can interfere with things. Therefore, low-shrinkage thermoplastic polymers are preferably used in as small amounts as possible. The polymer may be used in an amount of 40 parts by weight or less, preferably 5-30 parts by weight, based on 100 parts by weight of the monomer mixture (A).

Thickening thermoplastic polymers can be used in this curable composition to control the viscosity of the composition and to improve the workability of the composition during compression molding operations. The thickener thermoplastic polymer should be one capable of increasing the viscosity using various thickeners. For metal oxide-based thickeners such as magnesium oxide or calcium oxide or metal hydroxide-based thickeners such as magnesium hydroxide or calcium hydroxide, polymers containing carboxyl groups of two or more molecular units can be used. Examples of thermoplastic polymers that meet these conditions include terpolymers copolymerized with methyl methacrylate, methyl methacrylate and tertiary polymers with minor amounts of (meth) acrylic acid copolymerized with styrene, butadiene or a combination of isoprene and maleic acid Maleic rubber polymers, and terminal carboxyl saturated polyesters.

As another thickening thermoplastic polymer, a polymer containing two or more hydroxyl groups in a molecular unit can be exemplified. These compounds can form urethane bonds with polyhydric isocyanate compounds to enhance viscosity. Examples of thickening thermoplastic polymers that meet these conditions include polyols such as polyethylene glycol, terminal hydroxyl group saturated polyesters, and polymers resulting from copolymerization of methyl methacrylate with a small amount of hydroxyethyl (meth) acrylate. .

The above-mentioned thickening thermoplastic polymer is used after being dissolved in the monomer mixture (A). The amount of such polymer used is 100 parts by weight or less, preferably 5-40 parts by weight, based on 100 parts by weight of the monomer mixture (A). The final resulting curable composition by varying the amount of thickening thermoplastic polymer within the above-mentioned ranges and increasing the viscosity as necessary has excellent workability and flowability during molding under heat and pressure applications.

The inorganic filler (B) used in the present invention is not particularly limited as long as it has an average particle diameter of 5 microns or less. Any conventional inorganic filler may be used, such as calcium carbonate, talc, clay, silica, alumina, quartz and calcium silicate, and hydrated metal oxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide. Of these inorganic fillers (B) having an average particle diameter of 5 microns or less, hydrated metal oxides are particularly preferred because they can be dispersed in large quantities stably and can impart particularly high thermal stability and flame retardancy to the resulting cured product. Among the above-mentioned hydrated metal oxides, aluminum hydroxide is found to be particularly preferred because it allows the production of cured articles having a good appearance resembling marble, ie, artificial marble of high commercial value.

The inorganic filler (B) preferably has an average particle diameter of 5 microns or less, preferably 0.5-4 microns. If the average particle diameter of the inorganic filler is more than 5 microns, it is difficult to stably disperse in the monomer mixture and the cured product obtained by curing the resulting curable composition rapidly whitens when subjected to boiling water and undergoes degradation of hydrothermal stability. If an inorganic filler having an average particle diameter of less than 0.5 micron is used, the labor required to disperse the filler in the monomer mixture is likely to increase due to the secondary cohesion of the filler.

In order to obtain the curable composition of the present invention, the inorganic filler (B) must be dispersed in the monomer mixture (A). According to the dispersion method of the present invention, the curable composition may take the form of a liquid having a high filler content and a low viscosity to be suitable for injection molding or in the form of a dough mass having excellent flowability under pressure application.

When mixing the inorganic filler (B) and the monomer mixture (A) using a high speed stirrer such as a disperser or a homo-mixer, the inorganic filler (B) 250 per 100 parts by weight of the monomer mixture (A) 250 Although using about 500 parts by weight, the resulting mixture temporarily shows thixotropy during the mixing process and substantially loses fluidity, but results in a low viscosity liquid on the order of 2-100 poise suitable for injection molding.

When mixing using a low speed mixer such as a two-arm kneader, even if the addition amount of the inorganic filler (B) increases to a level of about 800 parts by weight relative to 100 parts by weight of the monomer mixture (A), the mixture is As the addition amount of the inorganic filler (B) increases, it takes the form of a kneaded viscous mass, and maintains this form, thereby forming a kneaded mass having excellent fluidity under pressure.

There are several methods for dispersing the inorganic filler (B) in the monomer mixture (A), including the use of various high speed stirrers, the use of low speed kneaders, and pigment dispersers or kneading rates generally employed in the manufacture of coating materials. How to use, etc. It is particularly preferred to use a disperser or homo mixer rotating at a speed of at least 1000 rpm, preferably at a speed of 1,100-1,500 rpm, for the preparation of curable compositions in low viscosity liquid form suitable for injection molding. It is preferable to use a low speed kneader kneading using a stirring blade, a screw, a roll or a plate having a speed of 100 rpm or less for preparing a curable composition in the form of a dough-like mass suitable for compression molding. Examples of low-speed kneaders that meet these conditions include double kneaders, muller kneaders, internal mixers, paddle mixers, cokneaders, stirring blade mixers, cake mixers, pony mixers, roll mills and screws. There is a mold extruder.

The curable compositions in the form of low viscosity liquids or pasty lumps described above can be readily cured by injection molding or molding under simultaneous application of heat and pressure. In particular, when this curable composition uses 250-400 parts by weight of aluminum hydroxide with respect to 100 parts by weight of the monomer mixture (A), this produces a translucent milky white artificial marble having a good appearance. When this curable composition uses 400-800 parts by weight of aluminum hydroxide, this produces a high flame retardant milky white artificial marble.

The usage-amount of an inorganic filler (B) is 250-800 weight part with respect to 100 weight part of monomer mixtures (A). In particular for the production of curable compositions in the form of low viscosity liquids, the amount of inorganic filler (B) is 250-500 parts by weight, preferably 300-400 parts by weight. In order to prepare the curable composition in the form of dough type, the amount of the inorganic filler (B) should be within the range of 250-800 parts by weight, preferably 300-600 parts by weight. If the amount of the inorganic filler is less than 250 parts by weight, such a composition cannot produce a cured product having excellent thermal stability and hydrothermal stability and exhibiting flame retardancy. If the amount of the inorganic filler used exceeds 800 parts by weight, it is difficult to disperse the inorganic filler (B) in the monomer mixture (A), thereby making it impossible to prepare a curable composition capable of producing a cured product having excellent hydrothermal stability. In addition, when the curable composition using the inorganic filler in excess of 500 parts by weight is used to impregnate the reinforcing fibers or the reinforcing short fibers, or when combined with such fibers, such impregnation or combination cannot be sufficiently obtained. High hydrothermal stability and high mechanical strength can be obtained.

The use of a silane coupling agent when mixing the monomer mixture (A) and the inorganic filler (B) yields desirable results of improving the water resistance of the resulting cured product. Typical examples of silane coupling agents include r-methacryloxy propyltrimethoxysilane, r-glycidoxy propyl trimethoxy silane, vinyltriethoxysilane and vinyltriacetoxy silane. The amount of the silane coupling agent used is 0.1-2.0%, preferably 0.2-to the weight of the inorganic filler (B), dissolved or dispersed in the monomer mixture (A) described above, or mixed with the pretreatment agent of the inorganic filler (B). 1.0% is good.

Examples of the polymerization initiator used in the present invention include benzoyl peroxide, cyclohexanone peroxide, methylethylketone peroxide, bis (4-t-butyl cyclohexyl) peroxy dicarbonate, t-butyl peroxy benzoate, and t Organic peroxides and azo compounds such as -butyl peroxy octoate. Among the above-mentioned polymerization initiators, t-butyl peroxy octoate and benzoyl peroxide, which are mediums to the high temperature polymerization initiator, are particularly preferable because they impart high transparency without causing cracks in the resulting cured product. When the curable composition is molded to a low temperature used for normal temperature compression or resin injection, low temperature polymerization such as methyl ether ketone peroxide, cyclohexanone peroxide and bis (4-t-butyl cyclohexyl) peroxy dicarbonate The medium for the initiator is used independently or in combination with an organic amine or polyvalent metal salt as accelerator. For injection molding, it is particularly preferable to use bis (4-t-butyl cyclohexyl) peroxy dicarbonate (Nippon Kayaku Co., Ltd., brand name: Parcadox PX-16 "). The weight of the silver monomer mixture (A) is generally 0.2-3.0%, preferably 0.5-2.0%.

In preparing the curable composition of the present invention, in addition to the monomer mixture (A), the inorganic filler (B) having an average particle diameter of 5 microns or less, and the polymerization initiator (C), various fillers, release agents such as zinc stearate, thixotropic agents, and plasticizers Additives such as flame retardants, flame retardants, and colorants can be used in amounts that do not impair the effects of the present invention.

The curable composition of the present invention obtained as described above is cured into various products when heated. For example, when the curable composition in the form of a low viscosity liquid is injected into a desired mold and cured by heating, it is converted into injection molded articles of various forms. In the case of injection molding, for example, it is pre-cured at a temperature of about 60 ° C., and after heating, it is continuously heated to a high temperature of 80 ° C. to 120 ° C. to obtain a desired product. When the curable composition in the form of a kneaded lump is cured by various extrusion methods such as press, injection, extrusion and transfer molding under heat and pressure, it is converted into various types of compression molded articles. In the case of compression molding under the simultaneous application of heat and pressure, a mold temperature of 80 to 180 ° C., preferably 100 to 150 ° C., is cured at a pressure of 5 to 200 kg / cm 2 and preferably 10 to 150 kg / cm 2. Get the product.

The curable compositions of the present invention may be combined with reinforcing fibers to hand lay up, spray up, cold press, resin injection, matched metal die, drawing and filament winding. It is applied to various FRP molding methods such as (winding). In this case, the curable composition is poured until it is impregnated onto the reinforcing fibers, and the impregnated reinforcing fibers are cured or immersed in the curable composition from the time of impregnation of the reinforcing fibers, followed by curing the impregnated reinforcing fibers to obtain the desired FRP product. The curing temperature varies depending on the molding method or the type of polymerization initiator, but is generally in the range from normal room temperature to around 150 ° C.

Glass fibers are generally used as reinforcing fibers. Carbon fibers and polyamide fibers can also be used. They are used alone or in combination as nonwoven, woven, chopped mat, or continuous fiber mat form.

The amount of reinforcing fibers is not particularly limited but is appropriately determined depending on the use of the FRP molded article or the required mechanical strength. It is generally 5 to 70 parts by weight, preferably 10 to 50 parts by weight with respect to 100 parts by weight of the curable composition.

The curable composition of the present invention can be converted to a premix molding material when mixed well until it is impregnated with the reinforcing short fibers. As another method, a premix molding material can be obtained by dispersing, impregnating and mixing the monomer short (A) with the inorganic filler (B) and the polymerization initiator (C) by adding reinforcing short fibers. The method of adding the reinforcing short fibers to the curable composition is more preferable because it enables complete mixing of the inorganic filler and prevents the breaking short fibers from breaking.

Examples of reinforcing short fibers include relatively small glass fibers, carbon fibers, polyamide fibers and various grades of whiskers up to 12 mm in length.

The amount of the reinforcing short fibers is not particularly limited but is appropriately determined according to the use of the cured product obtained from the premix molding material or the required mechanical strength, which is generally 5 to 50 parts by weight, preferably 10 to 100 parts by weight of the curable composition. It is-25 weight part.

This premix molding material is in the form of agglomerates with adequate toughness, lack of tackiness and ease of handling. It can be molded and cured by various methods that simultaneously apply heat and pressure, such as extrusion, press molding, injection molding and transfer molding. In particular, it can be converted to FRP moldings with good surface gloss when molded in matched metal dies or extruders heated to 100 ° to 160 ° C.

When the curable composition of the present invention blended with the above-mentioned thickening thermoplastic polymer is combined with a thickener and impregnated the reinforcing fibers, it can be converted into a fiber reinforced thermosetting molding material such as sheet molding compound (SMC) and bulk molding compound (BMC). have.

In the thickener thermoplastic polymer containing two or more carboxyl groups in the molecular unit, a metal oxide or metal hydroxide such as magnesium oxide or magnesium hydroxide is used as the thickener. The polyvalent isocyanate compound represented by tolylene diisocyanate or isopolone diisocyanate is used for the thickening thermoplastic polymer containing 2 or more hydroxyl groups in a molecular unit.

The thickener acts on the thickening thermoplastic polymer to increase the viscosity of the curable composition so that the composition has satisfactory workability in the step of incorporation of the reinforcing fibers and in the subsequent aging step.

The amount of thickener used is appropriately determined depending on the degree of viscosity increase required. It is generally 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight based on 100 parts by weight of the monomer composition (A). Regarding the addition time of the thickener, the thickener can be added to the monomer mixture (A) simultaneously with the inorganic filler (B). However, in order for the high filler content of the curable composition to have a satisfactory ability to impregnate the reinforcing fibers, the inorganic filler (B) and the polymerization initiator are added to the monomer mixture (A) and the mixture is stirred to sufficiently disperse the inorganic filler to form a curable composition. After preparation, it is preferred to add a thickener to the curable composition just before the reinforcing fibers are impregnated with the curable composition.

Fiber-reinforced thermosetting molding materials are made by simply impregnating the reinforcing fibers with a curable composition that already contains a thickener. More specifically, SMC can be prepared by impregnating the reinforcing fibers with the curable composition under intimate contact with each other, and aging the impregnated reinforcing fibers and obtaining a viscosity if necessary. On the other hand, BMC can be prepared by adding reinforcing fibers when mixing the monomer mixture (A) with the inorganic filler (B) and simultaneously performing mixing and impregnation. In the case of BMC, it is advisable to add the reinforcing fibers after sufficient mixing of the monomer mixture (A) and the inorganic filler (B) in order to sufficiently disperse the inorganic filler (B) and to completely prevent unwanted destruction of the reinforcing fibers.

Examples of reinforcing fibers usable in the production of SMC and BMC are various organic and inorganic materials such as glass fibers, carbon fibers, polyamide fibers and whiskers of various grades.

The amount of such reinforcing fibers is not particularly limited, but is appropriately determined depending on the use of the molding material or the mechanical strength required for the cured product. It is generally 5-70 parts by weight, preferably 10-50 parts by weight, based on 100 parts by weight of the curable composition.

These molding materials SMC and BMC are prepared by impregnating the reinforcing fibers with the curable composition and aging the impregnated reinforcing fibers to obtain a viscosity. Therefore it is not sticky and shows satisfactory workability.

In order to obtain a molded article by curing the fiber-reinforced thermosetting molding material, various molding methods adopted for conventional SMC and BMC, such as extrusion, press molding, injection molding, and transfer molding, may be used by applying heat and pressure simultaneously.

When selecting aluminum hydroxide as the inorganic filler (B), the curable composition of the present invention is very useful for the production of translucent to milky white artificial marble of good appearance from which a bathtub, a kitchen countertop or the like can be manufactured. Artificial marble obtained by injection molding or simultaneous application of heat and pressure to the curable composition contains an inorganic filler (B) in a high-charge state, and thus is flame retardant and maintains its original appearance even after being left in boiling water for more than 500 hours. The results also show good results in tests with high thermal strain points and resistance to the adhesion of contaminants such as tobacco tar. In particular, the artificial marble molded article obtained by thermoforming the curable composition in the form of a kneaded agglomerate under pressure has a high size precision, few deformations, an excellent surface free from cracking, and excellent productivity.

In addition, the cured product obtained by curing the curable composition of the present invention exhibits excellent performance in flame retardancy, heat resistance and hydrothermal resistance, which is why a conventional thermosetting composition lacks flame retardancy, thermal stability and hydrothermal stability, and thus cannot be satisfied with a bathtub, waterproofing pot, and kitchen countertop. It can be safely used in applications such as, conduits, electrical components, automotive parts, and tableware.

The present invention will now be described in more detail with reference to the following examples. However, these examples do not represent the full scope of the invention. In these examples all parts are by weight.

Example 1

"로 시판됨]를 사용하여 1,000rpm의 회전속도로 20분간 상기 액체 단량체 혼합물에 평균입경이 3.5미크론인 수산화알루미늄[Showa Light Metal Ind.,Ltd 제조, 상표"HIGILITE H-320"으로 시판됨]300부를 분산시켰다. 계속해서 결과의 혼합물에 중합개시제 비스(4-t-부틸시클로헥실)퍼옥시 디카르보네이트[Nippon Kayaku Co., Ltd 제조; 상표 "Parkadocks PX-16"으로 시판됨]0.8부를 혼합하여 본발명의 경화성 조성물(I)을 수득하였다. 이 경화성 조성물(I)은 30℃에서 점도 19poise를 보였다.Trimethyl was added to 50 parts of propane trimethacrylate, 50 parts of styrene and a silane coupling agent [Shin-etsu Chemical Ind. Co., Ltd., sold under the product number "KBM-503"] 0.5 parts were mixed to prepare a liquid monomer mixture. And high speed stirrer [Manufactured by Asada Iron Works, Trademark "DESPA

Aluminum hydroxide having an average particle diameter of 3.5 microns in the liquid monomer mixture for 20 minutes at a rotational speed of 1,000 rpm using "Available as", sold under the trademark "HIGILITE H-320". 300 parts were dispersed in the resulting mixture. 0.8 parts of the polymerization initiator bis (4-t-butylcyclohexyl) peroxy dicarbonate (manufactured by Nippon Kayaku Co., Ltd; sold under the trademark "Parkadocks PX-16") Mixing yielded the curable composition (I) of the present invention, which exhibited a viscosity of 19 poise at 30 ° C.

This curable composition (I) was poured into a casting mold of 200 × 150 × 6 mm and cured at 45 ° C. for 55 minutes. And it hardened | cured after 2 hours at 120 degreeC. The cured plate had a marbled translucent texture that emitted beautiful milky light and was flame retardant. The properties of this plate are shown in Table 1. It can be seen from this table that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants.

Example 2

"로 시판됨]를 사용하여 1100rpm의 속도로 20분간 상기한 액체 단량체 혼합물에 평균입경이 2.5미크론인 수산화알루미늄[Sumitomo Chemical Co.,Ltd 제조; 제품번호 "CE-30E"로 시판됨]300부를 분산시켰다.Trimethyl was added to 70 parts of propane trimethacrylate, 30 parts of styrene and a silane coupling agent [Shin-etsu Chemical Ind. Co., Ltd manufacture; Commercially available as product number "KBM-503"] 0.5 parts were mixed to prepare a liquid monomer mixture. And high speed stirrer [Manufactured by Asada Iron Works, Trademark "DESPA

300 parts of aluminum hydroxide having an average particle diameter of 2.5 microns [manufactured by Sumitomo Chemical Co., Ltd; sold under the product number "CE-30E"] for 20 minutes at the speed of 1100 rpm using "Available as" Dispersed.

Subsequently, in the resulting mixture, the polymerization initiator bis [4-t-butylcyclohexyl) peroxy dicarbonate [manufactured by Nippon Kayyaku Co., Ltd; Sold under the trademark "Parkadocks PX-16"] 0.8 parts were mixed to obtain a curable composition (2) of the present invention. This curable composition (2) showed a viscosity of 56 poise at 30 ° C.

The curable composition (2) was poured into an injection mold of 200 × 150 × 6 mm, cured at 45 ° C. for 50 minutes, and cured at 120 ° C. for 2 hours. The cured plate had a marble-like translucent structure that emits beautiful milky white light and is flame retardant. The properties of this plate are shown in Table 1. It can be seen from this table that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants.

Example 3

"로 시판됨]를 사용하여 1300rpm의 회전속도로 30분간 상기 액체 단량체 혼합물에 평균 입경이 3.0미크론인 수산화 알루미늄[Showa Light Metal Ind.,Ltd 제조, 상표"HIGILITE H-320ST"으로 시판됨]400부를 분산시켰다.Trimethyl was mixed with 50 parts of propane trimethacrylate and 50 parts of styrene to prepare a liquid monomer mixture. And high speed stirrer [manufactured by Asada Iron Works, brand "DESPA

Aluminum hydroxide having an average particle diameter of 3.0 microns in the liquid monomer mixture for 30 minutes at a rotational speed of 1300 rpm using "Available as"; manufactured by Showa Light Metal Ind., Ltd, sold under the trademark "HIGILITE H-320ST". Wealth was dispersed.

Subsequently, the polymerization mixture bis (4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Nippon Kayaku Co., Ltd.) was added to the resulting mixture. Sold under the trademark "Parkadocks PX-16"] 0.8 parts were mixed to obtain the curable composition (3) of the present invention. This curable composition (3) showed a viscosity of 37 poise at 30 ° C.

This curable composition (3) was poured into a 200 x 150 x 6 mm injection mold and cured at 45 占 폚 for 50 minutes. And cured after 2 hours at 120 ℃. The cured plate had a marbled translucent texture that emitted beautiful milky light and was flame retardant. The properties of this plate are shown in Table 1. It can be seen from this table that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants.

Example 4

"로 시판됨]를 사용하여 1300rpm의 회전속도로 30분간 상기 액체 단량체 혼합물에 평균직경이 3.0미크론인 수산화알루미늄[Showa Light Metal Ind.,Ltd 제조; 상표"HIGILITE H-320ST"으로 시판됨] 400부를 분산시켰다.Trimethyl was mixed with 40 parts of propane trimethacrylate, 40 parts of styrene and 20 parts of isobutyl methacrylate to prepare a liquid monomer mixture. And high speed stirrer [manufactured by Asada Iron Works, brand "DESPA

Aluminum hydroxide having an average diameter of 3.0 microns in the liquid monomer mixture for 30 minutes at a rotational speed of 1300 rpm using "traded by"; manufactured by Showa Light Metal Ind., Ltd; sold under the trademark "HIGILITE H-320ST" 400 Wealth was dispersed.

Subsequently, the polymerization mixture bis (4-t-butylcyclohexane) peroxydicarbonate [manufactured by Nippon Kayaku Co., Ltd.] was added to the resulting mixture. Commercially available under the trademark " Parkadocks PX-16 "] to yield a curable composition 4 of the present invention. This curable composition (4) showed the viscosity 33 poise at 30 degreeC.

And this curable composition (4) was poured into the injection mold of 200x150x6mm, and it hardened at 45 degreeC for 45 minutes. And it hardened | cured after 2 hours at 120 degreeC. The cured plate had a marbled translucent texture that emitted beautiful milky light and was flame retardant. The properties of this plate are shown in Table 1. It can be seen from this table that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants.

Example 5

"로 시판됨]를 사용하여 1100rpm의 회전속도로 20분간 상기 액체 단량체 혼합물에 평균 입경이 3.5미크론인 수산화알루미늄[Showa Light Metal Ind.,Ltd 제조; 상표"HIGILITE H-320"으로 시판됨]300부를 분산시켰다.40 parts of dipentaerythritol hexamethacrylate, 60 parts of styrene and a silane coupling agent [Shin-etsu Chemical Ind. Co., Ltd manufacture; Commercially available as product number "KBM-503"] 0.5 parts were mixed to prepare a liquid monomer mixture. And high speed stirrer [manufactured by Asada Iron Works, brand "DESPA

Aluminum hydroxide having an average particle diameter of 3.5 microns in the liquid monomer mixture for 20 minutes at a rotational speed of 1100 rpm using "available as" [manufactured by Showa Light Metal Ind., Ltd; sold under the trademark "HIGILITE H-320"] 300 Wealth was dispersed.

Subsequently, the polymerization mixture bis (4-t-butylcyclohexyl) peroxy dicarbonate [manufactured by Nippon Kayaku Co., Ltd.] was added to the resulting mixture. Commercially available under the trademark " Parkadocks PX-16 "] to obtain a curable composition 5 of the present invention. This curable composition (5) showed the viscosity 67 poise at 30 degreeC.

This curable composition (5) was poured into a 200 x 150 x 6 mm injection mold and cured at 45 占 폚 for 40 minutes. And it hardened | cured after 2 hours at 120 degreeC. The cured plate had a surrogate translucent structure that emitted beautiful milky light and was flame retardant. The properties of this plate are shown in Table 1. It can be seen from this table that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants.

Example 6

30 parts of propane trimethacrylate, 70 parts of styrene, a silane coupling agent (manufactured by Shin-etsu Chemical Ind. Co., Ltd; sold under the product symbol "KBM-503"), and 0.5 parts; 0.5 parts of t-butyl-peroxyoctoate (manufactured by Nippon Oil & Fats Co., Ltd .; sold under the trademark: Perbutyl 0 ") was mixed to prepare a liquid monomer mixture. Manufactured by Moriyama MFG Works Ltd; sold under the symbol "MS Open Type"; the liquid monomer mixture described above for 5 minutes, rotating the front blade at 68 rpm and the rear blade at 38 rpm, with an average particle diameter of 3.5 microns. The curable composition of the present invention was kneaded by kneading 300 parts of aluminum hydroxide [manufactured by Showa Light Metal Ind., Ltd. (commercially available under the trademark "HIGILITE H-320") to form a dough mass. 6), this curable composition was type B helipad When measured by a rotary viscometer, it was found that the viscosity was 42,000 poise at 30 ° C. The molding material was introduced into a 200 × 150 × 6 mm compression molding die and cured at 130 kg / cm 2 at 100 ° C. for 8 minutes. The plate has a marbled translucent structure that emits beautiful milky white light and is flame retardant.The properties of this plate are shown in Table 1. From the table, it can be seen that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants. have.

Example 7

5E"으로 시판됨] 300부 및 아연스테아레이트 3부를 혼련시켜서 결과의 혼합물이 반죽형 덩어리를 형성하도록 하여 본 발명의 경화성 조성물(7)을 수득하였다. 이 경화성 조성물은 B형 헬리패스 로타리 점도계로 측정할 때 30℃점도가 60,000poise임이 밝혀졌다. 그리고 이 성형 재료를 200×150×6mm인 압축 성형 다이에 도입시키고 130kg/㎠, 100℃에서 8분간 경화시켰다. 이렇게 압축성형된 판은 아름다운 유백색광을 발하고 난연성을 갖는 대리석형 반투명조직을 가졌다. 이 판의 성질을 표 1에 보였다. 표로부터 상기한 판은 열변형점이 높고 오염물질의 부착에 대한 저항성이 우수함을 알 수 있다.Trimethyl, propane trimethacrylate 30 parts, styrene 70 parts, silane coupling agent [Shin-Etsu Chemical Co .; Sold under the product symbol "KBM-503"] 0.5 parts and t-butyl-peroxy octoate [manufactured by Nippon Oil &Fat; Commercially available under the trademark “Perbutyl 0”] to prepare a liquid monomer mixture. And two kneaders [Moriyama MFG Works; Product symbol "commercially available as" MS Open Type "] The liquid monomer mixture described above for 5 minutes while rotating the front blade at 68 rpm and the rear blade at 38 rpm, with magnesium hydroxide having an average particle diameter of 0.8 micron [Kyowa Chem. Ind. Co., Ldt) manufacture; Brand "Kisuma

Commercially available at 5E "] and 300 parts of zinc stearate were kneaded to obtain a curable composition 7 of the present invention by forming a kneaded mass. The curable composition was obtained by a type B helipath rotary viscometer. When measured, it was found that the viscosity of 30 ° C. was 60,000 poise, and the molding material was introduced into a compression molding die of 200 × 150 × 6 mm and cured at 130 kg / cm 2 at 100 ° C. for 8 minutes. It has a marble-like translucent structure that emits white light and is flame retardant.The properties of this plate are shown in Table 1. From the table, it can be seen that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants.

Example 8

30 parts of trimethylol propane trimethacrylate, 70 parts of styrene, a silane coupling agent [Shin-Etsu Chemical Co., Ltd. make; Sold under the product symbol “KBM-503”] 0.5 parts and t-butyl-peroxyoctoate [manufactured by Nippon Oil &Fat; Commercially available as "Perbutyl 0"] 0.5 parts were mixed to prepare a liquid monomer mixture. And two kneaders [Moriyama MFG Works Ltd. manufacture; Product symbol "commercially available as" MS Open Type "] The liquid monomer mixture described above for 5 minutes while rotating the front blade at 68 rpm and the rear blade at 38 rpm [Nitto Pulverizing lnd. Co. ., Ltd) Manufacture; Sold under the product symbol “NS-100”] 260 parts and 3 parts of zinc stearate were kneaded to obtain a curable composition 8 of the present invention by causing the resulting mixture to form a kneaded mass.

This curable composition was found to have a viscosity of 65,000 poise at 30 ° C. as measured by a Type B helipath rotary viscometer. The molding material was then introduced into a 200 x 150 x 6 mm compression molding die and cured at 130 kg / cm 2 and 100 DEG C for 8 minutes. This compacted plate had a marble-like translucent structure that emitted beautiful yellow light. The properties of this plate are shown in Table 1. It can be seen from the table that the plate has a high thermal strain point and excellent resistance to adhesion of contaminants.

[Control Example 1]

"로 시판됨]를 사용하여 회전속도 1,000rpm으로 20분간, 평균입경이 17미크론인 수산화알루미늄[쇼와경금속산업제조; 상표"HIGILITE H-320"으로 시판됨] 200부를 상기한 시럽에 분산시켰다. 결과의 분산에 중합개시제 [닛뽕 가야꾸사제조 ;상표"Parkadocks PX-16"으로 시판됨]0.8부를 혼합하여 비교용 경화성 수지 조성물을 수득하였다. 이 수지 조성물은 30℃에서 점도가 230poise이었다.Polymethyl methacrylate [Mitsubishi Rayon manufactured by 73 parts of methyl methacrylate; Sold under the trademark “Acrypet MD001”] Methyl methacrylate syrup having a viscosity of 5 poise was prepared by dissolving 27 parts. And high speed stirrers [manufactured by Asada Iron Works; Trademark "DESPA

200 parts of aluminum hydroxide [Showa Light Metal Industry Co., Ltd .; sold under the trademark "HIGILITE H-320") having an average particle diameter of 17 microns for 20 minutes at "rotational speed" was dispersed in the above syrup. 0.8 parts of a polymerization initiator (manufactured by Nippon Kayaku Co., Ltd .; sold under the trademark "Parkadocks PX-16") were mixed with the resulting dispersion to obtain a curable resin composition for comparison, which had a viscosity of 230 poise at 30 ° C.

It still contained bubbles even when degassed under reduced pressure. This resin composition was difficult to be injected into a mold because of poor fluidity. The resin composition was poured into a 200 × 150 × 6 mm injection mold, cured at 45 ° C. for 50 minutes, and then cured at 110 ° C. for 2 hours. Table 1 shows the properties of the cured plate. It can be seen from the table that the plates lack thermal stability and hydrothermal stability.

[Control Example 2]

100 parts of vinyl ester resins [obtained by dissolving 55 parts of phenolic-A type epoxy acrylate resins in 45 parts of styrene], and a silane coupling agent [Shin-Etsu Chemical Co., Ltd. make; Commercially available under the product symbol "KBM-503"] After mixing 0.5 parts of a high speed stirrer [Asada Ai Works manufacture; Commercially available under the trademark "DESPA"; aluminum hydroxide having a mean particle diameter of 17 microns in the obtained resin solution for 20 minutes at a rotational speed of 1,100 rpm; 200 parts of the trademark "HIGILITE H-320ST" were dispersed, and 0.8 parts of a polymerization initiator (manufactured by Nippon Kayaku Co .; trademark "Parkadocks PX-16") was mixed with the resulting dispersion to obtain a comparative resin composition. This resin composition had a 180poise viscosity at 30 degreeC. It still contained many bubbles even if degassed under reduced pressure. Since this resin composition had poor fluidity, it was difficult to swell the injection mold. The resin composition was poured into an injection mold of 200 × 150 × 6 mm, cured at 45 ° C. for 60 minutes, and cured after 2 hours at 110 ° C. Table 1 shows the properties of the cured plate. It can be seen from the table that the plates lack thermal stability and hydrothermal stability.

TABLE 1

(*) Dishwashing detergent prepared by detergent (Lion Fat & Oil Co., Ltd.) after 24 hours of staining adhered on a sample at 20 ° C; Sold under the trademark "Mamma Royal". The degree of blemish was evaluated by three grades of ○, △, and ×.

Example 9

Polymethylmethacrylate (produced by Mitsubishi Rayon and sold under the trademark "Acrypet MD001") 18 parts of trimethylolpropanetrimethacrylate and 64 parts of styrene were dissolved in a monomer solution mixture. In addition, 0.8 parts of t-butylperoxy octoate as the polymerization initiator and 0.5 parts of the silane coupling agent (produced by Shin-Etsu Chemical Co., Ltd. and sold under the product symbol "KBM-503") were mixed. And 300 parts of aluminum hydroxide having an average particle diameter of 3.5 microns [produced by the Showa Light Metal Industry and sold under the trademark "HIGILITE H-320"), 2 parts kneader [Moriyama MFG Works Ltd. ; Sold under the product symbol "MS Open Type". The front blade is rotated at 68 rpm and the rear blade at 38 rpm for 5 minutes to form the resulting mixture in a kneaded mass to obtain the curable composition 9 of the present invention.

The curable composition 9 obtained in the form of a lump was not sticky enough to stick to the hand. The mass was cut with a knife and separated into 2 kg pieces. The pieces were placed in a box metal die having a base area of 270 × 380 mm and a height of 80 mm and press-molded at 120 ° C. under a pressure of 60 tons for 5 minutes. The resulting beautiful box-shaped cured product has excellent surface gloss, deep milky translucent, and does not crack or deform. The properties of this molded article are shown in Table 2. It should be noted in the table that the product has a high thermal strain point and excellent resistance to the attachment of contaminants.

Example 10

40 parts of trimethylol propane trimatacrylate and 60 parts of styrene were used as internal mold release agents, 3 parts of zinc stearate, 0.8 parts of t-butylperoxyoctoate as polymerization initiator, and a silane coupling agent produced by Shin-Etsu Chemical Co., Ltd. Sold as a commercially available symbol “503” to obtain a monomer solution mixture. In this monomer solution mixture, 600 parts of aluminum hydroxide having an average particle diameter of 3.5 microns [produced by the Showa Light Metal Industry and sold under the trade name "HIGILITE H-320"), 2 parts kneader [produced by Moriyama MFG Works, Inc.] Sold under the trade name HIGILITE H-320 ". 600 parts were kneaded with a two kneader (manufactured by Moriyaz MFG, Inc., sold under the symbol" MS Open Type "). The front blade is rotated at 68 rpm and the rear blade at 38 rpm for about 10 minutes to form a dough mass to obtain the curable composition 10 of the present invention.

The curable composition 10 obtained in the form of agglomerates was not sticky enough to stick to the hand. The mass was cut with a knife and separated into 2 kg pieces. The pieces were placed in a box metal die having a base area of 270 × 380 mm and a height of 80 mm and press-molded at 110 ° C. at a pressure of 60 tons for 5 minutes.

The resulting beautiful box-shaped cured product is excellent in surface gloss, deep in milky white translucency, and does not crack or deform. The properties of this molded article are shown in Table 2. It should be noted in the table that the product has a high thermal strain point and excellent resistance to the attachment of contaminants.

Example 11

20 parts of liquid methyl polyisoprene (produced by Kuraray, sold under the trade name "Kuraprene") having an average molecular weight of 25,000 and having 3.5 carboxyl groups per 100 units of isoprene as a polymer for thickening 25 parts of trimethyl propane trimethacrylate and styrene 55 It is dissolved in parts and contained 3 parts of zinc stearate as an internal mold release agent, 0.8 parts of t-butylperoxy octoate as a polymerization initiator, and a silane coupling agent produced by Shin-Etsu Chemical Co., Ltd. and sold under the product symbol "KBM-503". ] 0.5 parts is mixed to obtain a monomer liquid mixture. Then, the monomer liquid mixture was kneaded with a two kneader (manufactured by Moriyama MFG Works, sold under the symbol "MS Open Type"). The front blade was rotated at 68 rpm and the rear blade was rotated at 38 rpm with an average particle diameter. 300 parts of this 3.5 micron aluminum hydroxide (produced by Showa Light Metal Industries, Inc., sold under the trade name "HIGLITE H-320") is added and kneading is continued for about 5 minutes to form a dough mass. 1.0 parts of magnesium (produced by Kyowa Chemical Co., Ltd. and sold under the trade name "Kyowamang # 20") are added and mixed to obtain a curable composition (11) of the present invention.

The curable composition 11 obtained in the form of agglomerate was not sticky enough to stick to a hand. Cut it with a knife and cut it into 2kg pieces. The pieces are placed in a box metal die with a base area of 270 × 380 mm and a height of 80 mm. The resulting beautiful box-shaped cured product has excellent surface gloss, deep milky translucent, and does not crack or deform. The properties of this molded article are shown in Table 2. It should be noted in the table that the product has a high thermal strain point and is highly resistant to contaminant adhesion.

Example 12

10 parts of polystyrene (produced by Sumitomo Chemical Co., Ltd. and sold under the trade name "S-bright T-2 Beads") as a low hydrophobic polymer, are dissolved in 30 parts of trimethylol propane trimethacrylate and 60 parts of styrene and used as an internal release agent in the solution. 3 parts of zinc stearate, 0.8 parts of t-butylperoxy octoate as polymerization initiator, and 0.5 parts of silane coupling agent (produced by Shin-Etsu Chemical Co., Ltd. and sold under the product symbol "KBM-530"). Get This was kneaded with a double kneader (sold under the trade name "MS Open Type" manufactured by Moriyama MFG Works, Inc.). The front blade is rotated at 68 rpm and the rear blade at 38 rpm with an average particle diameter of 3.5 microns of aluminum hydroxide (produced by the Showa Light Metal Industry, sold under the trade name HIGLITE H-320 "). Subsequently, a dough mass is formed, and the curable composition 12 of this invention is obtained.

The curable composition 12 obtained in the form of a lump was not sticky enough to stick to the hand. Cut it with a knife and separate it into 2kg pieces. The pieces are placed in a box metal die having a base area of 270 × 380 mm and a height of 80 mm.

The resulting beautiful box-shaped cured product is excellent in surface gloss, deep milky and translucent, and does not crack or deform. This molded part has a high heat deflection point and excellent resistance to adhesion of contaminants.

[Control Example 3]

45 parts of unsaturated polyester obtained by condensation of 0.7 moles of maleic anhydride, 0.3 moles of isophthalic acid, 0.3 moles of neopentyl glycol, 0.6 moles of propylene glycol, and 0.15 moles of bisphenol A were dissolved in 45 parts of styrene, and 0.005 parts of hydroquinone was added to the solution as a stabilizer. A polyester resin solution is prepared. For comparison, 10 parts of polystyrene (commercially available from Sumitomo Chemical, sold under the trade name "S-bright T-2 Beads") as an exponential polymer are dissolved in a resin solution, 3 parts of zinc stearate as an internal release agent, 0.8 parts of t-butylperoxy octoate as polymerization initiator, 0.5 parts of silane coupling agent (produced by Shin-Etsu Chemical Co., Ltd. and sold under the product symbol "KBM-503") and aluminum hydroxide having an average particle diameter of 17 microns [ Produced by Showa Light Metal Industries, Inc. and sold under the trade name " HIGILITE H-310 "] 210 parts were mixed using a two kneader as in Example 9.

The curable composition thus obtained was poor in workability because it was sticky and stuck to the hand.

When the amount of aluminum hydroxide added exceeded 210 parts, it was found that the upper limit of the amount above which the resulting mixture could become a whole mass was 250 parts. When the amount of aluminum hydroxide added exceeded 250 parts, the resulting mixture was separated into non-sticky masses.

In order to compare, the resin composition was compression-molded in accordance with the process of Example 9, and the molded article was obtained. The properties of this molded article are shown in Table 2. It should be noted in the table that the moldings lack thermal and hydrothermal stability.

TABLE 2

Example 13

"로 시판)를 이용하여, 3.5미크론의 평균 입자직경을 갖는 수산화알루미늄(쇼와 경금속산업제품, 등록상표 "HIGILITE H-320"로 시판) 300부 및 내부 이형제인 아연 스테아레이트 3부를 1,100r.p.m의 회전속도로 20분 동안 액체 단량체 혼합물에 분산시키고, 생성된 분산액을 중합 개시제인 0.8부의 t-부틸 퍼옥시옥토에이트(닛뽕유지제품, 등록상표 "퍼부틸 0"로 시판)와 혼합함으로써 본 발명의 경화성 조성물(13)을 수득한다. 이 경화성 조성물(13)은 30℃에서 19포와즈의 점도를 갖는다. 프레스 주형기내에 미리 장치한 금속다이(직경 200㎜ 및 깊이 10㎜인 판의 생산을 위한것)을 120℃로 가열하고, 금속 다이안에 세단한(Chopped) 세개의 유리매트, #450(450g/㎡)을 놓는다. 유리매트와 150g의 경화성 조성물(13)을 가하고 생성물 표면적 ㎠ 당 30㎏의 압력으로 3분가 압축시킴으로써 두께가 3㎜인 FRP 성형품을 수득한다.A liquid monomer mixture is prepared by mixing 50 parts trimethylol propane trimethacrylate, 50 parts styrene and 0.5 parts silane coupling agent (available from Shin-Etsu Chemical Co., registered under the trademark "KBM-503"). High speed agitator (product of Asada Iron Works, registered trademark "DESPA

300 parts of aluminum hydroxide (showa light metal industry product, sold under the trademark "HIGILITE H-320") having an average particle diameter of 3.5 microns and 3 parts of zinc stearate as an internal release agent Dispersion was carried out in a liquid monomer mixture for 20 minutes at rotational speed, and the resulting dispersion was mixed with 0.8 parts of t-butyl peroxyoctoate (Nippon Oil, sold under the trademark "Perbutyl 0") as a polymerization initiator. A curable composition 13 is obtained, which has a viscosity of 19 poise at 30 ° C. For the production of a metal die (200 mm in diameter and 10 mm in depth) pre-installed in a press molding machine. Heat to 120 ° C. and place three chopped glass mats, # 450 (450 g / m 2), into a metal die, adding a glass mat and 150 g of the curable composition 13 and 30 kg per cm 2 of product surface area. 3 minutes compression at a pressure of An FRP molded article having a thickness of 3 mm is obtained.

FRP moldings have a beautiful milky white texture, although the glass matrix is visible. The characteristics of the FRP molded article are shown in Table 3. It can be seen from the table that the molded article is excellent in flame retardancy, thermal stability and hydrothermal stability.

Example 14

"로 시판)를 이용하여, 3.5미크론의 평균 입자직경을 갖는 수산화알루미늄(쇼와경금속 산업제품, 등록상표 "HIGILITE H-320"로 시판) 300중량부 및 내부 이형제인 아연 스테아레이트 3부를 1,100r.p.m의 회전속도로 20분 동안 액체 단량체 혼합물에 분산시키고, 생성된 분산액을 중합 개시제인 0.8부의 t-부틸 퍼옥시옥토에이트(닛뽕유지제품, 등록상표 "퍼부틸 0"로 시판)와 혼합함으로써 본 발명의 경화성 조성물(14)을 수득한다. 이 경화성 조성물(14)은 30℃에서 86포와즈의 점도를 갖는다. 실시예 13과 동일하게 처리함으로써 이 경화성 조성물(14)로부터 FRP 성형품을 수득한다.A liquid monomer mixture is prepared by combining 30 parts trimethylol propane trimethacrylate, 52 parts styrene with 18 parts polymethyl methacrylate (available from Mitsubishi Rayon, trade name "Acrypet MD001"). High Speed Agitator (Asada Iron Works, registered trademark "DESPA

300 parts by weight of aluminum hydroxide having a mean particle size of 3.5 microns (available under the trade name "HIGILITE H-320") and 3 parts of zinc stearate as an internal mold release agent using 1,100 rpm, The present invention was dispersed in a liquid monomer mixture at a rotational speed of 20 minutes, and the resulting dispersion was mixed with 0.8 parts of t-butyl peroxyoctoate (Nippon Oil, sold under the trademark "perbutyl 0") as a polymerization initiator. The curable composition 14 is obtained.The curable composition 14 has a viscosity of 86 poise at 30 ° C. The FRP molded article is obtained from this curable composition 14 by treating in the same manner as in Example 13.

FRP moldings are very smooth and have a beautiful milky texture with the underlying glass matrix completely hidden. The characteristics of the FRP molded article are shown in Table 3. It can be seen from the table that the molded article is excellent in flame retardancy, thermal stability and hydrothermal stability.

[Control Example 4]

"로 시판)를 이용하여, 1,100r.p.m의 회전속도로 20분 동안 혼합함으로써 경화성 수지 조성물을 수득한다.47.5 parts of unsaturated polyester obtained by condensation of 0.3 moles of isophthalic acid, 0.7 moles of maleic anhydride, 0.3 moles of neopentyl glycol, 0.6 moles of propylene glycol, and 0.15 moles of hydrogenated bisphenol A were dissolved in 47.5 parts of styrene and formed. An unsaturated polyester resin solution is obtained by adding 0.005 parts of hydroquinone as a stabilizer to the prepared solution. 5 parts of polymethyl methacrylate (manufactured by Mitsubishi Rayon, registered under the trademark "Acrypet MD001") is dissolved in this resin solution. In the resulting solution, 0.5 part of a silane coupling agent (from Shin-Etsu Chemical Co., Ltd., sold under the trademark "KBM-503"), 3 parts of zinc stearate as an internal release agent, 0.8 parts of t-butyl pioxyoctoate as a polymerization initiator, and 130 parts of aluminum hydroxide (showa light metal industry product, sold under the trademark "HIGILITE H-320") having an average particle diameter of 3.5 microns was added, and a high-speed stirrer (manufactured by Asada Theory Works, registered trademark "DESPA"

Commercially available) to obtain a curable resin composition by mixing at a rotational speed of 1,100 rpm for 20 minutes.

This curable resin composition has the viscosity of 100 poise at 30 degreeC. Thereafter, an FRP molded article is obtained from the resin composition by carrying out the same method as in Example 13.

The comparative FRP molded article thus obtained had almost no visible glass matrix and had a beautiful white texture. The characteristics of this X-shaped article are shown in Table 3. It can be seen from the table that the molded article is of poor quality in thermal stability, hydrothermal stability and flame retardancy.

TABLE 3

Example 15

A liquid monomer mixture containing 25 parts of trimethylol propane trimethacrylate and 75 parts of styrene was mixed with 3 parts of zinc stearate and 0.8 parts of t-butyl peroxyoctoate as a polymerization initiator. Commercially available) and 0.5 part of silane coupling agent (Shin-Etsu Chemical Co., Ltd., commercially available under the product number "KBM-503"). The resulting liquid mixture is placed in a two kneader. 300 parts of aluminum hydroxide having an average particle diameter of 3.5 microns was kneaded for about 5 minutes until the mixture produced in the kneader became a kneaded mass to produce the curable composition 15 of the present invention. 45 parts of fine glass fibers, which have a length of 6 mm and the curable composition 15, are kneaded similarly for 5 minutes to produce a premix molding material. This premix molding material is agglomerates that have no tack and provide desirable processability. A 2 kg piece cut by a knife from the premix molding material is placed in a box metal die equipped with a press molding machine (stored at 120 ° C with a bottom surface area of 270 x 380 mm and a depth of 80 mm) at a pressure of 60 tons. Compress for 5 minutes. The result is a beautiful milky, translucent molded article with excellent surface gloss and no cracks or deformations. The properties of this molded article are shown in Table 4.

It can be seen from the table that the molded article is excellent in thermal stability, hydrothermal stability and flame retardancy.

Example 16

"로 시판)를 이용하여 회전속도 1,100r.p.m.에서 20분간 혼합함으로써 본발명의 경화성 조성물(16)을 수득한다. 이 경화성 조성물은 30℃에서 80포와즈의 점도를 나타낸다. 이 경화성 조성물(16)을 증점제인 산화마그네슘(교와 화학공업제품, 등록상표 "Kyowamag #20"으로 시판) 1부와 혼합함으로써 시이트 성형 컴파운드(SMC) 제조용 합침제를 수득한다. SMC 생산기내에서, 유리로우빙[닛또 보세끼사(Nitto Boseki Co., Ltd.)제품, 제품번호 "RS-240F-546"으로 시판)을 1인치의 길이로 절단하여 수득한 유리촙(glass chop)에 상기한 합침제를 합침시킴으로써 4kg/㎡의 무게를 가지며 상기 유리촙 25중량%를 함유하는 합침된 시이트를 제조한다. 숙성실에서 40℃에서 20시간 동안 상기 합침 시이트를 숙성시킴으로써 SMC를 수득한다. SMC는 점착성을 갖지 않으며 유리 섬유를 완전히 합침된 상태로 보관할 수 있으며 가공성이 풍부하다. SMC를 압축성형함으로써(135℃, 100kg/㎠, 3분의 조건)200×200×3mm의 판형제품을 수득하고 특성을 표 4에 나타낸다. 표로부터 본 생성물이 열 안정성 및 열수 안정성 및 난연성에 뛰어남을 알 수 있다.20 parts of liquid maleic polyisoprene (from Kuraray Co., Ltd., trade name "Kuraprene") having an average molecular weight of 25,000 and 3.5 carboxyl groups per 100 isoprene units, 30 parts of trimethylol propane trimethacryl 100 parts of polymeric syrup are obtained by dissolving in a liquid monomer mixture consisting of late and 50 parts of styrene. Polymeric syrup and 0.5 part of a silane coupling agent (Shin-Etsu Chemical Co., Ltd., commercially available under the product number "KBM-503") t-butylperoxybenzoate (Nippon Holdings, registered trademark "Perbutyl Z") as a polymerization initiator. 300 parts of aluminum hydroxide (showa light metal industry product, registered under the trademark "HIGILITE H-320") having 1.0 part, internal release agent zinc stearate and 3.5 micron average particle diameter was added, and a high speed stirrer was used. Iron Works product, trademark "DESPA

By mixing for 20 minutes at a rotational speed of 1,100 rpm to obtain a curable composition 16 of the present invention. The curable composition exhibits a viscosity of 80 poise at 30 ° C. The curable composition 16 Mixing with one part of the thickening agent magnesium oxide (Kyowa Chemical Co., Ltd., sold under the trademark "Kyowamag # 20") yields a coagulant for the manufacture of sheet forming compounds (SMC). 4 kg / by incorporating the above-mentioned binder into a glass chop obtained by cutting a Chisa (Nitto Boseki Co., Ltd. product, commercially available as "RS-240F-546") length of 1 inch. An impregnated sheet having a weight of 2 m 2 and containing 25 wt% of the glass 촙 is prepared, SMC is obtained by aging the impregnated sheet for 20 hours at 40 ° C. The SMC is not tacky and the glass fiber is completely Merged phase The SMC is compression molded (135 ° C., 100 kg / cm 2, 3 min conditions) to give a plate product of 200 × 200 × 3 mm and the properties are shown in Table 4. It can be seen that it is excellent in thermal stability, hydrothermal stability and flame retardancy.

Example 17

By performing the same method as in Example 16, the curable composition 16 is produced.

In a double kneader, the curable composition 16 was continuously kneaded and 100 parts of aluminum hydroxide (available from Showa Light Metal Industries, registered under the trademark "HIGLITE H-320") having an average particle diameter of 3.5 microns was added and kneaded. The curable composition 17 of the present invention is obtained by mixing with the composition 16. The curable composition 17 has a viscosity of 960 poise at 30 ° C.

1/4 part of magnesium oxide (Kyowa Chemical Co., Ltd., sold under the trademark "Kyowamag # 20") and Glass Roving (available under Nitto Bonded Co., Ltd., "RS-240F-546") A lump is obtained by mixing the curable composition 17 together with 90 parts of glass chopped to length, which is aged for 20 hours at 40 ° C. to produce a bulk molding compound (BMC). It can be completely impregnated with glass fibers and has excellent processability, and the molded article obtained by compression molding this BMC in the same manner as in Example 16 has the properties shown in Table 4. From the table, the product shows thermal stability and hydrothermal stability and egg temperature. We can see that we are excellent in spirituality.

[Control Example 5]

"로 시판)를 이용하여 회전속도 1.100r.p.m에서 20분간 혼합함으로써 비교용 수지 조성물을 수득한다. 이 수지 조성물은 30℃에서 150포화즈의 점도를 갖는다. 이 수지 조성물과 증점제인 산화마그네슘(고와 화학공업제품 등록상표 ""Kyowamag #20"으로 시판) 1부를 혼합함으로써 SMC생산용 함침제(대조)를 생산한다. 실시예 16의 방법을 실시함으로써 이 함침제로부터 비교옹 SMC를 생산한다. 실시예 16의 방법에 따라 상기 SMC를 압축 성형시킴으로써 표 4에 나타낸 특성을 갖는 압축 성형품을 수득한다.40 parts of unsaturated polyester obtained by condensation of 0.3 moles of isophthalic acid, 0.7 moles of maleic anhydride, 0.3 moles of neopentyl glycol, 0.6 moles of propylene glycol, and 0.15 moles of addressed bisphenol-A are dissolved in 40 parts of styrene. And unsaturated polyester resin solution is prepared by adding 0.005 parts of hydroquinone as a stabilizer to the resulting solution. 20 parts of liquid maleic acid polyisoprene (manufactured by Kuraray Co., registered under the trademark "Kureprene") having an average molecular weight of 25,000 are dissolved in this resin solution. 1.0 part of the resulting solution and a polymerization initiator of t-butyl peroxybenzoate 1.0 part of zinc stearate as an internal release agent, 0.5 part of a silane coupling agent (commercially available from Shin-Etsu Chemical Co., product number "KBM-503"), and Add 150 parts of pure aluminum oxide with average particle diameter of 17 micron (Showa Light Metal Industry Co., Ltd., commercially available under the product name "HIGILITE H-310") and add a high speed stirrer (product of Asada Iron Works, registered trademark) DESPA

A commercially available resin composition was obtained by mixing at a rotational speed of 1.100 rpm for 20 minutes using ", commercially available. &Quot; This resin composition had a viscosity of 150 saturations at 30 DEG C. This resin composition and a thickener of magnesium oxide (Kowa) 1) Impregnating agent (control) for SMC production is produced by mixing 1 part of the commercially available chemical trademark "Kyowamag # 20". Non-conductive SMC is produced from this impregnating agent by carrying out the method of Example 16. Compression molding the SMC according to the method of Example 16 yields a compression molded article having the properties shown in Table 4.

TABLE 4

Claims (29)

Monomer mixture (A) containing a mixture of 20 to 80% by weight of aliphatic polyvalent (meth) acrylate and 80 to 20% by weight of an aromatic vinyl compound, inorganic filler (B) having an average particle diameter of 5 microns or less, and polymerization of a catalytic amount Curable composition comprising an initiator (C), wherein the inorganic filler (B) is dispersed by 250 to 800 parts by weight per 100 parts by weight of the monomer mixture (A). The curable composition according to claim 1, wherein the amount of the polymerization initiator is 0.2 to 3.0% by weight based on the weight of the monomer mixture (a). The composition according to claim 1, wherein the inorganic filler (B) is a hydrated metal oxide. The composition according to claim 1, wherein the inorganic filler (B) is aluminum hydroxide. The composition as claimed in claim 1, wherein said monomer mixture (A) is carried out using a high speed stirrer for dispersing said inorganic filler (B). The method of claim 5, wherein the high speed stirrer is 1.000r.p.m. The composition characterized by rotating at the above speed. The composition according to claim 1, wherein the dispersion of the inorganic filler (B) in the monomer mixture (A) is performed using a low speed kneader. 8. The composition of claim 7, wherein the low speed kneader is a double kneader. The composition according to claim 1, wherein the monomer mixture (A) contains 5 to 40 parts by weight of a thickening thermoplastic polymer and 0.5 to 5 parts by weight of a thickener based on 100 parts by weight of the monomer mixture (A). The composition according to claim 9, wherein said thickening thermoplastic polymer contains at least two carboxyl groups in its molecular unit and said thickening agent is a metal oxide or a metal hydroxide. The composition according to claim 9, wherein the thickener thermoplastic polymer contains at least two hydroxyl groups in its molecular unit is a polyvalent isocyanate compound. Monomer mixture (A) containing a mixture of 20 to 80% by weight of aliphatic polyvalent (meth) acrylate and 80 to 20% by weight of aromatic vinyl compound, inorganic filler (B) having an average particle diameter of 5 microns or less, and polymerization of catalytic amount The initiator (C) was mixed with a high speed stirrer so that the total amount of the inorganic filler (B) was in the range of 250 to 500 parts by weight based on 100 parts by weight of the monomer mixture (A), and the resulting mixture had a viscosity of 2 to 100 poise. Method for producing a curable composition consisting of mixing until forming a liquid having a. The method of claim 12, wherein the high speed stirrer is 1,000r.p.m. Method for rotating the above speed. 13. The method according to claim 12, wherein the inorganic filler (B) is a hydrated metal oxide. 13. The method according to claim 12, wherein the inorganic filler (B) is aluminum hydroxide. The process according to claim 12, wherein the monomer mixture (A) contains 5 to 40 parts by weight of a thickening thermoplastic polymer and 0.5 to 5 parts by weight of a thickener based on 100 parts by weight of the monomer mixture (A). Monomer mixture (A) containing a mixture of 20 to 80% by weight of aliphatic polyvalent (meth) acrylate and 80 to 20% by weight of an aromatic vinyl compound as an essential component, an inorganic filler (B) having an average particle diameter of 5 microns or less, and a polymerization of a catalytic amount The initiator (C) was mixed with a low-speed kneader so that the total amount of the above-mentioned inorganic filler (B) was in the range of 250 to 800 parts by weight based on 100 parts by weight of the monomer mixture (A), and the resulting mixture was kneaded into a dough mass. A method of making a curable composition consisting of mixing until forming. 18. The method of claim 17, wherein the low speed kneader is 100r.p.m. Rotating at the following speeds. 18. The method of claim 17, wherein the low speed kneader is a double kneader. 18. The method of claim 17, wherein the inorganic filler (B) is a hydrated metal oxide. 18. The method of claim 17, wherein the inorganic filler (B) is aluminum hydroxide. 18. The method according to claim 17, wherein the monomer mixture (A) contains 5 to 40 parts by weight of a thickening thermoplastic polymer and 0.5 to 5 parts by weight of a thickener based on 100 parts by weight of the monomer mixture (A). A product obtained by thermally curing the curable composition of claim 1. The product of claim 23, wherein said product is artificial marble. An injection molded article obtained by injecting the curable composition according to claim 5 and curing under thermal application. The compression molded article obtained by heat-hardening the curable composition of Claim 7 under pressure application. A premix molding material obtained by impregnating reinforcing short fibers with the curable composition according to claim 1. A fiber-reinforced plastic product obtained by adding the curable composition according to claim 1 to a reinforcing fiber previously put in a metal die to impregnate the reinforcing fiber and thermosetting the impregnated reinforcing fiber under pressure application. A fiber-reinforced thermosetting molding material obtained by impregnating a reinforcing fiber with the curable composition according to claim 9.