CN86105386A - Curable compositions and manufacture method thereof and application - Google Patents

Abstract

A kind of curable compositions comprises (A) and contains the mixture formed with the aromatic ethenyl compound of aliphatics polyfunctional group (methyl) acrylate of 20 to 80% weight and 80 to the 20% weight a kind of monomer mixture as its main component, (B) a kind of average particulate diameter is no more than 5 microns the mineral filler and (C) initiators for polymerization of catalytic amount, and the amount of dispersive mineral filler (B) in the monomer mixture (A) of per 100 parts of weights is 250 to 800 parts of weights.

Description

Curable compositions and manufacture method thereof and application

The invention relates to the curable compositions of the good cured article of production thermostability, particularly hydrothermal stability, the production method of said composition and application thereof.Particularly, the invention relates to the mineral filler of specific particle diameter is dispersed in the curable compositions that makes in the specific liquid monomer mixture, the production method of said composition and said composition can be made the purposes of artificial marble products.

Various mineral fillers are dispersed in the thermosetting resin slurries prepare curable resin composition, such thermosetting resin has unsaturated polyester resin that the methacrylic acid epoxy is set, ester is dissolved in the vinyl ester resin that obtains in the vinylbenzene, and this Resins, epoxy is that prior art is known.They have been used to the casting artificial marble products, and are used for combining with glass fibre mold glass steel (FRP).People have known the resin combination that fillers dispersed is made in the thermoplastic resin slurries, for example make solidifying agent, the mixture of aluminium hydroxide and methyl methacrylate (U.S.P.3,847 with organo-peroxide, 865), can be used to the molding artificial marble products.Usually these thermosetting resins or thermoplastic resin slurries are injected the mould of different shape, or inject the space between the moving belt, heating then, temperature range from normal room temperature to nearly 60 ℃.In metal pattern, under heating and pressurized conditions, the curable resin composition of the type of pressing mold or extrusion molding also is that prior art is known.Resin slurries or give mix moulding compound with as if unsaturated polyester resin and the such class thermosetting resin of vinyl ester resin and various filler and aggregate are mixed must, in order to increase viscosity, in resulting mixture, can arbitrarily add glass fibre and thickening material.

Because require composition to keep enough low viscosity to process to be suitable for casting, so use curable resin composition slurries and that can be used for casting, wherein the amount of filler that effectively can use and globule size have the restriction of itself.In order to obtain the cured article of the good high filler content of thermostability and flame retardant resistance, when amount of filler was big, because in the process of preparation composition, filler is difficult for diffusion in slurries, the cured article outward appearance that makes was bad.For example,, can use a kind of like this method, promptly select the big as far as possible filler of non-setting particle diameter for use for preventing the high viscosity that can increase the curable compositions that makes of filler content.Because fillers dispersed is insufficient, or because the filler particles diameter is big, the solidifying product that is made by the polymerization of foregoing curable resin combination has the shortcoming that the surface produces flaw, when the result is immersed in the boiling water, can have water, reddens very soon and loses its good surface appearance.

Use the resin slurries or give under the situation of mixing aforementioned curable resin combination moulding compound and that be used for molding at the same time under the heating and pressurizing, in the pressing mold process, during the well behaved dough shape of process for processing block, the amount of filler that permission adds has the restriction of itself.In general, be benchmark with the resin of 100 parts of weights, be limited to 200 parts of weights on the amount of filler.In the cured article that is made by such curable resin composition polymerization, resin is poor to the clinging power of filler or aggregate, the poor water resistance of resin.When being immersed in the boiling water, the cured article surface is damaged rapidly, reddens and tarnishes.And these cured article poor heat stability at high temperature can be faded.In the burning smoke test, contaminated significantly.In using as bathtub, dressing table, button, electronic original part, kitchen sales counter etc., general curable resin composition can not satisfy these performances.

Be coated with this solidifying product of stain with unsaturated polyester resin or vinyl ester resin gel, improve the method for the hydrothermal stability of the solidifying product that such curable resin composition makes, obtained confirming.But this solidifying product of handling through gel coat has the defective of poor heat stability, when consequently being exposed in burning smoke or the hot water, can stay irremediable sand holes and other similar defectives.

Therefore, the purpose of this invention is to provide a kind of new curable compositions, the production method of this curable compositions and application thereof.

Another object of the present invention provides a kind of curable compositions, and this curable compositions can be produced without any need for the good solidifying product of gel coat processing, thermostability and flame retardant resistance, the production method of this curable resin composition and application thereof.

An available curable compositions achieves the above object, this curable compositions contains (A) and contains monomer mixture as main component, this monomer mixture is made up of 20-80% heavy aliphatics polyfunctional group (methyl) acrylate and the heavy aromatic ethenyl compound of 80-20%, (B) average particulate diameter is not more than 5 microns mineral filler, disperse the mineral filler (B) of 250 to 800 parts of weights in (C) initiators for polymerization of catalytic amount, the monomer mixture of 100 parts of weights (A).

The method of available production curable compositions further achieves the above object, this method comprises makes (A), (B) and (C) mix (A) and comprise monomer mixture as main component, this monomer mixture is made up of 20-80% heavy aliphatics polyfunctional group (methyl) acrylate and the heavy aromatic ethenyl compound of 80-20%, (B) average particulate diameter is not more than 5 microns mineral filler, (C) initiators for polymerization of catalytic amount, monomer mixture (A) with 100 parts of weights is a benchmark, the consumption of mineral filler (B) is 250 to 500 parts of weights, in homogenizer, mix, until forming the liquid form mixt that viscosity is 2 to 100 pools.

The method of also available production curable compositions achieves the above object, this method comprises makes (A), (B) and (C) mix, (A) contain monomer mixture as main component, this monomer mixture is made up of aliphatics polyfunctional group (methyl) acrylate of 20 to 80% weight and the aromatic ethenyl compound of 80-20% weight, (B) average particulate diameter is not more than 5 microns mineral filler, (C) initiators for polymerization of catalytic amount, aforementioned monomer mixture with 100 parts of weights is a benchmark, the consumption of mineral filler (B) is 250 to 800 parts of weights, in the low speed kneader, mix, until the block that forms the dough shape.

Can use separately or inject mould with foregoing curable composition that fortifying fibre combines use, heating then can be pressurizeed arbitrarily simultaneously, obtains various solidifying products, for example artificial marble products and glass reinforced plastic (FRP) goods.This curable compositions can be used for flooding fortifying fibre or strengthens staple fibre, or combines with these fibers and to obtain fibre-reinforced thermoplastic molding material or to give mixed moulding compound.In the widespread use of various uses, this curable compositions shows outstanding performance like this.

Can be used for aliphatics polyfunctional group of the present invention (methyl) acrylate and comprise ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, glycerol trimethacrylate, trimethylolpropane trimethacrylate and Dipentaerythritol six (methyl) acrylate.

The example of aromatic ethenyl compound comprises vinylbenzene, alpha-methyl styrene, P-vinyl toluene and Vinylstyrene.

The ratio of aliphatics polyfunctional group (methyl) acrylate and aromatic ethenyl compound, the former is a 20-80% weight, and the latter is a 80-20% weight, and ratio is that the former is that the 30-70% weight and the latter are 70-30% weight preferably.For the monomer mixture that uses in the curable compositions of the present invention (A), above-mentioned two kinds of monomers are its main components.Yet, can be various methacrylate monomer, for example methacrylic acid or its ester, methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester or trifluoroethyl (methyl) acrylate use as the part of monomer mixture (A), various big monomers, or other monomers or oligopolymer, as unsaturated polyester ester oligomer, fumarate or maleimide, also can be used as the part of monomer mixture (A).The use of these other monomers or oligopolymer can make the solidifying product of high filler content make difficulty, or the solidifying product that causes making lacks thermostability or hydrothermal stability.

For suppressing the contraction of solidifying product, the monomer mixture (A) that the present invention uses can be to dissolve or to be dispersed in the form use of thermoplastic polymer wherein.Be used to suppress to shrink, prevent that solidifying product from flaw occurring and increasing the thermosetting polymer of surface smoothness, can be to be generally used for any polymkeric substance of suppressing to shrink, and only require that it can be dispersed or dissolved in the monomer mixture (A).The example that satisfies the polymkeric substance of this requirement has methacrylic acid type polymkeric substance, as polymethylmethacrylate, methacrylic acid-styrol copolymer, polystyrene, polyvinyl acetate (PVA), vinylbenzene-vinyl acetate copolymer, polyvinyl chloride, polyhutadiene, polycaprolactam and saturated polyester.These common low-shrinkage polymkeric substance can use separately, perhaps use with the form of binary or multicomponent mixture.When the thermoplastic polymer of a large amount of these low-shrinkages of use, may increase the viscosity of monomer mixture (A), the curing composition that is used in the high filler content of casting is made difficulty, and hinders this solidifying product to demonstrate satisfied transparency and thermostability.Therefore, require the consumption of the thermoplastic polymer of this low-shrinkage should be the least possible.Being 100 parts with the weight of monomer mixture (A) is benchmark, requires the consumption of this polymkeric substance to be not more than 40 parts of weights, and amount ranges is 5 to 30 parts of weights preferably.

For regulating the viscosity of said composition, further strengthen the processing characteristics of said composition in the pressing mold process, this curing composition can use the thermoplastic polymer of thickening.By using various thickening materials, requiring the type of this thickening thermoplastic compounds is prerequisite can increase viscosity.This thickening material is the basis with metal oxide as magnesium oxide or calcium oxide, perhaps based on metal hydroxides such as magnesium hydroxide or calcium hydroxide, can use the polymkeric substance that two or more carboxyls are arranged in the molecular structure unit.The example that satisfies the thermoplastic polymer of this requirement comprises the binary polymethylmethacrylate base polymer of the methacrylic acid that contains a small amount of and methyl methacrylate copolymer, contain a small amount of and methyl methacrylate and styrene copolymerized acrylic acid terpolymer, because diene or isoprene combine Malaysia rubber polymer and the end carboxyl saturated polyester that forms with toxilic acid.

As the thermoplastic polymer of other thickenings, can enumerate the polymkeric substance that two or more hydroxyls are arranged in the molecular structure unit.These polymkeric substance increase viscosity by forming urethanum with polyfunctional isocyanate's compound bonding.The example that satisfies the thickening thermoplastic polymer of this requirement comprises polyol, for example polyoxyethylene glycol, terminal hydroxy group saturated polyester and by the polymkeric substance of a small amount of (methyl) Hydroxyethyl acrylate with the methyl methacrylate copolymer generation.

Foregoing thickening thermoplastic polymer is dissolved in the monomer mixture (A) and uses.Weight with monomer mixture (A) is benchmark for 100 parts, and the consumption of this polymkeric substance is not more than 100 parts of weights, and scope is 5 to 40 parts of weights preferably.But the amount of this thickening thermoplastic polymer of appropriate change in this scope makes it be suitable for the increase of required viscosity.The final curable compositions that generates in heating and pressure moulding process, has outstanding processing characteristics and flowing property.

The mineral filler of using among the present invention (B) is no more than 5 microns except requiring average particulate diameter, does not have other special qualifications.Any common mineral filler, as lime carbonate, mica, clay, silicon-dioxide, aluminum oxide, quartz and Calucium Silicate powder, and hydrated metal oxide, all can use as aluminium hydroxide, magnesium hydroxide and calcium hydroxide.In these average particulate diameters were no more than 5 microns mineral filler, hydrated metal oxide was desirable especially, because their consumptions are big, can stably be distributed in the solidifying product, makes solidifying product have extra high thermostability and flame retardant resistance.In the above-mentioned hydrated metal oxide of enumerating, aluminium hydroxide is desirable especially, because the cured article of producing with its has the good appearance resemble the marble, promptly is the very high artificial marble of a kind of commercial value.

Use average particulate diameter to be no more than 5 microns, the mineral filler (B) that is preferably in 0.5 to 4 micrometer range is comparatively favourable.If use average particulate diameter to surpass 5 microns mineral filler, be difficult to stably be dispersed in the monomer mixture, the cured article that the curable compositions that curing obtains makes when being immersed in the boiling water, reddens rapidly, and thermostability reduces.If the use average particulate diameter less than 5 microns mineral filler, owing to the secondary clinging power of filler, has fillers dispersed required power in monomer mixture the trend of increase.

Obtain curable compositions of the present invention, mineral filler (B) must be dispersed in the monomer mixture (A).According to dispersing method of the present invention, curable compositions can use high filler content and be suitable for the low-viscosity (mobile) liquid of casting, or at the block of the good dough shape of pressure current downflow.

When mineral filler (B) and monomer mixture (A) are used high speed agitator, during as decollator or similar mixing tank mixing, even when the consumption of mineral filler is 250 to about 500 parts heavy (being 100 parts with the weight of monomer mixture (A) is benchmark), in mixing process, temporary transient thixotropy appears in mixture, basically lose flowability fully, but finally obtain being suitable for low-viscosity (mobile) liquid mold, that be equivalent to 2 to 100 pools.

When using slow-speed mixer, when mixing as double arm kneading mixer, increase along with mineral filler (B) addition, mixture presents the viscosity block of dough shape gradually, being 100 parts with the weight of monomer mixture (A) is benchmark, even when the add-on of mineral filler (B) is increased to about 8.00 parts heavy, still continue to keep this state, under pressure, finally generate the block of the good dough shape of flowing property.

Available various method is dispersed in mineral filler (B) in the monomer mixture (A), a kind of method is to be to use slow-speed mixer by means of various super mixer another kind methods, also has a kind of method to be to use the colo(u)rant dispersion device or is suitable for preparing the kneading cylinder of coating usually.When particularly producing the aqueous curable compositions of the low viscosity be suitable for casting, use high speed agitator for example rotating speed surpass 1000 rev/mins, be preferably 1100 to 1500 rev/mins decollator or similarly mixing tank is comparatively favourable.Produce curable compositions with the dough shape block that is suitable for pressing mold, the low speed kneader that can use paddle wheel, screw rod, cylinder or paddle to mediate is better, and rotating speed is no more than 100 rev/mins.The example that satisfies the low speed kneader of this requirement comprises double arm kneading mixer, grinds kneader, interior kneader, paddle mixer, (kneader altogether), stirring rake blade profile mixing tank, piece feed mixer, short groove mixing tank, tumbling mill and screwe-type xtruder.

The block of above-mentioned low-viscosity (mobile) liquid that obtains or dough shape heats at the same time and adds and depresses, and is easy to solidify by casting or molding.Particularly the weight when monomer mixture (A) is benchmark with 100 parts, when curable compositions uses the aluminium hydroxide of 250 to 400 parts of weights, makes the good artificial marble of a kind of translucent milky outward appearance.When curable compositions uses the aluminium hydroxide of 400 to 800 parts of weights, make a kind of artificial marble of milky high flame retardant.

Monomer mixture (A) with 100 parts of weights is a benchmark, and the consumption of mineral filler (B) is in the scope of 250 to 800 parts of weights.The curable compositions that particularly production low viscosity is aqueous, the amount that requires mineral filler (B) is in 250 to 500 parts heavy scopes, and 300 to 400 parts of weights are better.For producing the curable compositions of dough shape block form, the amount that requires mineral filler (B) is in the scope of 250 to 800 parts of weights, and 300 to 600 parts of weights are better.If the consumption of mineral filler is lower than 250 parts of weights, this curable compositions just can not production thermostability and hydrothermal stability and the good solidifying product of flame retardant resistance.If the consumption of mineral filler surpasses 800 parts of weights, the dispersion of mineral filler (B) in monomer mixture (A) be difficulty so, so that the preparation of the curable compositions of the good solidifying product of hydrothermal stability can not be implemented.The amount of the mineral filler of using in curable compositions (B) surpasses 500 parts of weights, this curable compositions is used to flood fortifying fibre or strengthens staple fibre, or when combining with these fibers, can not obtain satisfied dipping or combination, the curing mold goods that the result obtains can not obtain higher hydrothermal stability and high physical strength.

In monomer mixture (A) and mineral filler (B) mixing process, use silane coupling agent, obtained the water-repellancy effect of the solidifying product that gratifying enhancing obtains.The exemplary of silane coupling agent has r-methyl allyl acyloxypropyl trimethoxysilane, r-Racemic glycidol oxygen propyl trimethoxy silicane, vinyltriethoxysilane and vinyltriacetoxy silane.Weight with mineral filler (B) is benchmark, the ideal dosage of silane coupling agent is 0.1 to 2.0%, be preferably 0.2 to 1.0%, this mineral filler (B) is dissolved or is dispersed in the foregoing monomer mixture (A), or is added in and gives in the used reagent of treatment inorganic filling material (B).

Be used for initiators for polymerization of the present invention and comprise organo-peroxide, as benzoyl peroxide, cyclohexanone peroxide, methyl-ethyl-ketone peroxide, two (4-tert-butylcyclohexyl) peroxodicarbonate, t-butyl peroxy benzoic ether and t-butyl peroxy octanoate and azo-compound.In the above-mentioned polymerization starter of enumerating, prove that t-butyl peroxy octanoate and benzoyl peroxide are satisfactory especially, they can be used as the medium of high temperature polymerization initiator, high-temperature initiator can production transparency high and do not have a solidifying product of flaw.This curable resin composition is molding at low temperatures, comprise cold press process or resin injection method, thereby can use the medium that resembles methyl-ethyl-ketone peroxide, pimelinketone superoxide and the such class low temperature polymerization initiator of two (4-tert-butylcyclohexyl) peroxodicarbonate, can use separately, perhaps combine use with organic amine or polyvalent metal salt as promotor.In casting, use two (4-tert-butylcyclohexyl) peroxodicarbonate (Japanese Kayaku company limited product, trade(brand)name be the commercially available prod of " Parcadox PX-16 ") ideal especially.In general, be benchmark with the weight of monomer mixture (A), the consumption of polymerization starter is 0.2 to 3.0%, is preferably 0.5 to 2.0%.

When the preparation curable compositions, except using monomer mixture (A), average particulate diameter is not more than 5 microns mineral filler (B) and initiators for polymerization (C) in addition, also can use the such additive of various fillers, releasing agent such as Zinic stearas, thixotropic compound, softening agent, fire retardant or flame-proofing agent and tinting material, their consumption can not influence effect of the present invention.

The above-mentioned curable compositions heating curable of the present invention that obtains becomes various products.For example, the curable compositions that low viscosity is aqueous is pressed the desired shape casting, when being heating and curing then, becomes the casting article of different shape.During casting, in the time of about 60 ℃, carry out primary solidification, subsequently, as required, can under 80 ℃ to 120 ℃ high temperature, continue to solidify, so just obtain required solidifying product.The curable compositions of dough shape block shape, when it with various compression moulding methods as suppressing, inject, extrude and transfer moudling, when heating and pressurizing is solidified, become the moulded product of different shape.Heating and pressurizing is carried out under the situation of pressing mold at the same time, is cured and obtains desired product, and pressure range is 5 to 200 kilograms per centimeter ², be preferably 10 to 150 kilograms per centimeter ², temperature range is 80 ℃ to 180 ℃, is preferably 100 to 150 ℃.

Curable compositions of the present invention can combine with fortifying fibre with various glass reinforced plastic (FRP) moulding method, as hand be coated with, spray, cold pressing, resin injection, supporting metal pattern, stretching and the coil of wire around.In this case, curable compositions is poured on the fortifying fibre, until soaking into, solidify the fortifying fibre that soaks into then, or fortifying fibre is immersed in the curable compositions, until soaking into, with the fortifying fibre that after fixing soaks into, obtain required glass reinforced plastic (FRP) goods.Solidification value changes with the kind of molding methods or used polymerization starter, generally from normal room temperature to nearly 150 ℃.

Usually use glass fibre to make fortifying fibre.Also can use carbon fiber and tynex.They use with the form of supatex fabric, braided fiber, debris fabric or integral body (band shape) fabric, can use separately or use with mixed state.

The amount of fortifying fibre has no particular limits, but can rationally determine consumption according to the characteristic of glass reinforced plastic (FRP) layered product or required physical strength.Generally the weight with curable compositions is benchmark for 100 parts, and the amount ranges of fortifying fibre is 5 to 70 parts of weights, and 10 to 50 parts of weights are better.

When curable compositions of the present invention directly mixes with the enhancing staple fibre, when soaking into, just become and give mixed moulding compound.In addition the enhancing staple fibre is added in the mixed system of monomer mixture (A) and mineral filler (B) and initiators for polymerization (C), disperses, soak into and blended effect fully, obtain giving mixed moulding compound so that produce simultaneously.Facts have proved that the method that the enhancing staple fibre is added in the curable compositions is even more ideal, because it mixes fully mineral filler and prevents to strengthen the undesirable damage of staple fibre.

The example that strengthens staple fibre has glass fibre, carbon fiber, tynex and length to be no more than 12 millimeters the quite whisker of short various grades.

Do not have special restriction although strengthen the amount of staple fibre, can rationally determine consumption according to the character or the desired physical strength of the solidifying product that makes by pre-mixing molding compound.Generally, be benchmark with the curable compositions of 100 parts of weights, the amount ranges of fortifying fibre is 5 to 50 parts of weights, 10 to 25 parts of weights are better.

The pre-mixing molding compound that exists with the block form has appropriate toughness, required viscosity, and processing easily.It can be by the whole bag of tricks that heats simultaneously and pressurize; carry out molding and curing as methods such as extrusion molding, pressing mold, injection-molded and transfer moulds; particularly when it with supporting metal pattern or when being heated to 100 to 160 ℃ forcing machine molding, become the good glass reinforced plastic of surface luster (FRP) layered product.

In curable compositions of the present invention, add foregoing thickening thermoplastic polymer, when this curable compositions combines and makes its dipping fortifying fibre with thickening material, just become fibre-reinforced duroplastic moulding materials, as sheet molding compound (SMC) and block molding compounds (BMC).

For the thickening thermoplastic polymer that two or more carboxyls are arranged in molecular structure unit, can use to resemble magnesium oxide or the such quasi-metal oxides of magnesium hydroxide or metal hydroxides and make thickening material.For the thickening thermoplastic polymer that two or more hydroxyls are arranged in molecular structure unit, can use the two isocyanic ester of your ketone of two isocyanic ester of tolylene or inferior fluorine to make thickening material as polyfunctional isocyanate's compound of representative.

In the steeping process neutralization weathering process subsequently of fortifying fibre, thickening material acts on the thermoplastic polymer of thickening, increases the viscosity of curable compositions, is enough to make composition to obtain satisfied processing characteristics.

According to the range of viscosities of required increase, rationally determine the consumption of thickening material.In general, be benchmark with the monomer mixture (A) of 100 parts of weights, the consumption of thickening material is 0.1 to 10 part of weight, is preferably 0.5 to 5 part of weight.About adding the time of thickening material, thickening material and mineral filler (B) can join in the monomer mixture (A) simultaneously.Yet, obtain the ability of satisfied dipping fortifying fibre for the curable compositions that makes high filler content, it is desirable to after making curable compositions, before with curable compositions dipping fortifying fibre, at once thickening material is joined in the curable compositions, this curable compositions joins mineral filler (B) and polymerization starter in the monomer mixture (A) and makes, and disperses to stir the mixture of gained fully for making mineral filler.

Fibre-reinforced thermoset molding material is to flood fortifying fibre simply with the curable compositions that contains thickening material to make.Particularly, flood fortifying fibre with curable compositions, the tight contact by each other can make SMC, can make the aging and increase viscosity of fortifying fibre of dipping in case of necessity.On the contrary, add fortifying fibre simultaneously,, can make BMC so that make mixing and flood generation effect simultaneously at monomer mixture (A) and mineral filler (B) blended.When producing BMC, requirement mineral filler (B) with add fortifying fibre again after monomer mixture (A) mixes, monomer mixture (A) is through fully handling, guaranteeing that like this mineral filler (B) disperses fully, and can prevent the undesirable damage of fortifying fibre.

The example of the fortifying fibre that uses in preparation SMC and BMC comprises various organic and inorganic materials, as glass fibre, carbon fiber, tynex and all kinds of whisker.

The consumption of these fortifying fibres has no particular limits, but reasonably determines consumption, with casting characteristic and the desired physical strength of solidifying product that is suitable for moulding material.In general, be benchmark with the curable compositions of 100 parts of weights, the amount ranges of fortifying fibre is 5 to 70 parts of weights, is 10 to 50 parts of weights preferably.

Flood fortifying fibre with curable compositions, and make the aging and increase viscosity of fortifying fibre, make these moulding materials, SMC and BMC.They do not have viscosity, and satisfied processing characteristics can be provided.

Obtain the goods of definite shape, can pass through cured fiber enhanced Themoplastic molding materials, adopt the various molding methods heat simultaneously and pressurize, for example extrusion molding, pressing mold, injection-molded and process common SMC and the used transfer moudling of SMC.

When selecting aluminium hydroxide as mineral filler (B), curable compositions of the present invention is used for making the translucent artificial marble of the good oyster white of outward appearance more, is used to make bathtub, kitchen sales counter and similar products like.By casting or heat simultaneously and pressurize, the artificial marble that cure curable compositions obtains, because it contains high-load mineral filler (B), so be the good goods of incombustible outward appearance, even after in boiling water, soaking more than 500 hours, still keep its original good appearance, have high heat distortion point, and in the adhiesion test of anti-pollution thing such as cigarette stain, demonstrate outstanding effect.Particularly under pressure, the artificial marble products of those definite shapes that the curable compositions of hot-moulded dough shape block form obtains has the dimensional precision height, and adhesion amount is few, keep producing the excellent surface of flaw, and throughput is big.

And, have outstanding flame retardant resistance, thermotolerance and humidity resistance by solidifying the solidifying product that curable compositions of the present invention makes, therefore can be used for bathtub, fluid-tight container, kitchen sales counter, conduit, electronic component, auto parts and platform safely, common curable compositions can not satisfy these requirements, because they lack flame retardant resistance, thermally-stabilised and hydrothermal stability.

Now, describe the present invention in more detail, but be noted that these embodiment do not represent four corner of the present invention with the following example.

Embodiment 1

The trimethylolpropane trimethacrylate of 50 parts of weights, the silane coupling agent of 50 parts of heavy vinylbenzene and 0.5 part of weight (produced by Shin-etsu chemical industry company limited, product is marked with " KBM-503 " mark) mixes, preparation liquid monomer mixture.Then, is 300 parts of heavy average particulate diameters that 3.5 microns aluminium hydroxide (is produced by Showa light metals industry company limited, trade(brand)name is the commercially available prod of " HIGILITE H-320 ") be dispersed in the liquid monomer mixture, (produced by Asada ironworks, trade(brand)name is " DESPA with homogenizer

") with 1,100 rev/min rotating speed, stirred 20 minutes.(Japanese Kayaku company limited produces with two (4-tert-butylcyclohexyl) peroxide two carbonic ethers of the initiators for polymerization of the mixture that obtains and 0.8 part of weight subsequently, trade(brand)name is " Parkadocks PX-16 ") mix, obtain curable compositions of the present invention (1).The viscosity of this curable compositions in the time of 30 ℃ is 19 pools.

Then, this curable compositions (1) is injected 200 * 150 * 6 millimeters mold, and solidified 55 minutes at 45 ℃.120 ℃ of regelates 2 hours.Cured plate has the translucent texture resemble the marble, sends beautiful oyster white gloss and has flame retardant resistance.The performance of this plate is listed in the table 1, has the performance that high heat distortion point and good resistant thing adhere to by visible this plate in the table.

Embodiment 2

The trimethylolpropane trimethacrylate of 70 parts of weights, the silane coupling agent of 30 parts of heavy vinylbenzene and 0.5 part of weight (is produced by the limited worker of Shin-etsu chemical industry company, product is marked with the mark of " KBM-503 ") mix preparation liquid monomer mixture.Then, is 300 parts of heavy average particulate diameters that 2.5 microns aluminium hydroxide (is produced by Sumitomo chemical industry company limited, product is marked with the mark of " CE-30E ") be dispersed in the liquid monomer mixture, (Asada ironworks produces, and trade(brand)name is " DESPA with homogenizer

"), stirred 20 minutes with 1100 rev/mins rotating speeds.

Subsequently, (Japanese Kayaku company limited produces with two (4-tert-butylcyclohexyl) peroxide two carbonic ethers of the initiators for polymerization of the mixture that makes and 0.8 part of weight, trade(brand)name is " Parkadocks PX-16 ") mix, obtain curable compositions of the present invention (2).The viscosity of this curable compositions (2) in the time of 30 ℃ is 56 pools.

Then, curable compositions (2) is injected 200 * 150 * 6 millimeters mold, solidified 50 minutes at 45 ℃.120 ℃ of regelates 2 hours.This cured plate has the translucent texture resemble the marble, sends beautiful oyster white gloss and has flame retardant resistance.This plate has the performance that high heat distortion point and good resistant thing adhere to.

Embodiment 3

The vinylbenzene of 50 parts of heavy trimethylolpropane trimethacrylates and 50 parts of weights is mixed preparation liquid monomer mixture.Be 400 parts of heavy average particulate diameters 3 microns aluminium hydroxide (Showa light metals industry company limited production then, trade(brand)name is " HIGILITE H-320ST ") be dispersed in this liquid monomer mixture, (Asada ironworks produces, and trade(brand)name is " DESPA with homogenizer

") stirred 30 minutes with 1300 rev/mins rotating speeds.

Subsequently, (Japanese Kayaku company limited produces with two (6-tert-butylcyclohexyl) peroxide two carbonic ethers of the initiators for polymerization of the mixture that makes and 0.8 part of weight, trade(brand)name is " Parkadocks PX-16 ") mix, obtain curable compositions of the present invention (3).The viscosity of this curable compositions in the time of 30 ℃ is 37 pools.

Then, this curable compositions (3) is injected 200 * 150 * 6 millimeters mold, solidified 50 minutes, further 120 ℃ of regelates 2 hours at 45 ℃.This cured plate has the translucent texture resemble the marble, sends beautiful oyster white gloss and has flame retardant resistance.The performance of this plate is listed in the table 1, and visible this plate has the performance that high thermal deformation point and good resistant thing adhere in the table.

Embodiment 4

The trimethylolpropane trimethacrylate of 40 parts of weights, the isobutyl-methacrylic ester of 40 parts of heavy vinylbenzene and 20 parts of weights mixes, preparation liquid monomer mixture.Be 400 parts of heavy average particulate diameters that 3 microns aluminium hydroxide (is produced by Showa light metals industry company limited then, trade(brand)name is " HIGILITE-320ST ") be dispersed in this liquid monomer mixture, (produced by Asada ironworks, trade(brand)name is " DESPA with homogenizer "), with 1300 rev/mins rotating speed, stirred 30 minutes.

Subsequently, (Japanese Kayaku company limited produces with two (4-tert-butylcyclohexyl) peroxide two carbonic ethers of the initiators for polymerization of the mixture that makes and 0.8 part of weight, trade(brand)name is " Parkadocks PX-16 ") mix, obtain curable compositions of the present invention (4).The viscosity of this curable compositions in the time of 30 ℃ is 33 pools.

This curable compositions (4) is injected 200 * 150 * 6 millimeters mold, solidified 45 minutes, further 120 ℃ of following regelates 2 hours at 45 ℃.Cured plate has the translucent texture resemble the marble, sends beautiful oyster white gloss and has flame retardant resistance.The performance of this plate is listed in the table 1, and by this table as seen, this plate has the performance that high heat distortion point and good resistant thing adhere to.

Embodiment 5

The Dipentaerythritol hexamethyl acrylate of 40 parts of weights, the silane coupling agent of 60 parts of heavy vinylbenzene and 0.5 part of weight (produced by Shin-etsu chemical industry company limited, product is marked with the mark of " KBM-503 ") mixes, preparation liquid monomer mixture.Then, is 300 parts of heavy average particulate diameters that (Showa light metals industry company limited produces for 3.5 microns aluminium hydroxide, trade(brand)name is " HIGILITEHH-320 ") be dispersed in the liquid monomer mixture, (Asada ironworks produces, and trade(brand)name is " DESPA with homogenizer

"), with 1100 rev/mins rotating speed, stirred 20 minutes.

Subsequently, (Japanese Kayaku company limited produces with two (4-tert-butylcyclohexyl) peroxide two carbonic ethers of the initiators for polymerization of the mixture that makes and 0.8 part of weight, trade(brand)name is " Parkadocks PX-16 ") mix, obtain curable compositions of the present invention (5).The viscosity of this curable compositions (5) in the time of 30 ℃ is 67 pools.

Then, this curable compositions is injected 200 * 150 * 6 millimeters mold, solidified 40 minutes, further 120 ℃ of following regelates 2 hours at 45 ℃.Cured plate has the translucent texture resemble the marble, sends beautiful oyster white gloss, and has flame retardant resistance.The performance of this plate is listed in the table 1, and by this table as seen, this plate has the performance that high heat distortion point and good resistant thing adhere to.

Embodiment 6

The trimethylolpropane trimethacrylate of 30 parts of weights, the vinylbenzene of 70 parts of weights, 0.5 a part heavy silane coupling agent (is produced by Shin-etsu chemical industry company limited, product is marked with the mark of " KBM-503 ") and the tert-butyl peroctoate of 0.5 part of weight (produce by Japanese grease company limited, trade(brand)name is " Perbutyl 0 ") mix preparation liquid monomer mixture.Then, (produce at double arm kneading mixer by Moriyama MFG equipment company limited, product is marked with " Ms Open Type " mark) in, with 300 parts of heavy average particulate diameters is that (Showa light metals industry company limited produces for 3.5 microns aluminium hydroxide, trade(brand)name is " HIGILITE H-320 ") and the Zinic stearas of 3 parts of weights, mediate with the liquid monomer mixture, preceding paddle rotating speed is 68 rev/mins, back paddle rotating speed is 38 rev/mins, mediated about 5 minutes, block until the mixture formation dough shape that obtains makes curable compositions of the present invention (6).Measure with Type B helipass rotor viscometer, the viscosity of this curable compositions in the time of 30 ℃ is 42,000 pools.Then, this moulding compound is injected 200 * 200 * 6 millimeters mold, 100 ℃ and 330 kilograms per centimeter ²Pressure solidified 8 minutes down.Pressuring template has the translucent texture resemble the marble, sends beautiful oyster white gloss, and has flame retardant resistance.The performance of this plate is listed in the table 1, and by this table as seen, this plate has the performance that high heat distortion point and good resistant thing adhere to.

Embodiment 7

The trimethylolpropane trimethacrylate of 30 parts of weights, the vinylbenzene of 70 parts of weights, 0.5 a part heavy silane coupling agent (is produced by Shin-etsu chemical industry company limited, product is marked with the mark of " KBM-503 ") and the t-butyl peroxy octanoate of 0.5 part of weight (Japanese grease company limited produces, trade(brand)name is " Perbutyl 0 ") mix preparation liquid monomer mixture.Then, (produce at double arm kneading mixer by Moriyama MFG equipment company limited, product is marked with " Ms Open Type " mark) in, be 300 parts of heavy average particulate diameters that (produced by Kyowa chemical industry company limited, trade(brand)name is " Kisuma for 0.8 micron magnesium hydroxide

5E ") and the Zinic stearas of 3 parts of weights and liquid monomer mixture mediate; preceding blade rotating speed is 68 rev/mins; back blade rotating speed is 38 rev/mins; mediated about 5 minutes; form the block of dough shape until the mixture that obtains, make curable compositions of the present invention (7), measure with Type B helipass rotor viscometer; the viscosity of this curable compositions in the time of 30 ℃ is 60,000 pools.

Then, moulding compound is injected 200 * 200 * 6 millimeters pressing mold, 100 ℃ and 130 kilograms per centimeter ²Pressure solidified 8 minutes down.Pressuring template has the translucent texture resemble the marble, sends beautiful oyster white gloss, and has flame retardant resistance.The performance of this plate is listed in the table 1, and by table 1 as seen, this plate has the performance that high heat distortion point and good resistant thing adhere to.

Embodiment 8

The trimethylolpropane trimethacrylate of 30 parts of weights, the vinylbenzene of 70 parts of weights, 0.5 a part heavy silane coupling agent (is produced by Shinetsu chemical industry company limited, product is marked with " KBM-503 " mark) and the t-butyl peroxy octanoate of 0.5 part of weight (Japanese grease company limited produces, trade(brand)name is " Perbutyl 0 ") mix preparation liquid monomer mixture.Then, (produce at double arm kneading mixer by Moriyama MFG equipment company limited, product is marked with " Ms Open Type " mark) in, with 260 parts of heavy average particulate diameters is that 2.1 microns lime carbonate (is produced by Nitto efflorescence Industrial Co., Ltd, product is marked with the mark of " NS-100 ") and the Zinic stearas of 3 parts of weights and liquid monomer mixture mediate, preceding blade rotating speed is 68 rev/mins, back blade rotating speed is 38 rev/mins, mediated about 5 minutes, block until the mixture formation dough shape that obtains makes curable compositions of the present invention (8).Measure with Type B helipass viscometer, the viscosity of this curable compositions in the time of 30 ℃ is 65,000 pools.Then, moulding compound is injected 200 * 200 * 6 millimeters pressing mold, 100 ℃ and 130 kilograms per centimeter ²Pressure solidified 8 minutes down.Pressuring template has the translucent texture resemble the marble, sends beautiful faint yellow gloss.The performance of this plate is listed in the table 1.By table 1 as seen, this plate has the performance that high heat distortion point and good resistant thing adhere to.

Comparative Examples 1

The polymethylmethacrylate of 27 parts of weights (produced by Mitsubishi Rayon, trade(brand)name is " Acrypet MD001 ") is dissolved in the methyl methacrylate of 73 parts of weights, and obtaining viscosity is the methyl methacrylate slurries of 5 pools.Then, is 200 parts of heavy average particulate diameters that 17 microns aluminium hydroxide (is produced by Showa light metals industry company limited, trade(brand)name is " HIGILITE H-310 ") be dispersed in these slurries, (produced by Asada ironworks, trade(brand)name is " DESPA to use homogenizer

"), stirred 20 minutes with 1100 rev/mins rotating speeds.The initiators for polymerization of the dispersion liquid that obtains and 0.8 part of weight (is produced by Japanese Kayaku company limited, trade(brand)name is " Parkadocks PX-16 ") mix, obtain being used for correlated curable resin composition, the viscosity of this curable resin composition in the time of 30 ℃ is 230 pools.Even when it removes air under vacuum, still have bubble.Because mobile poor, this resin combination is difficult in casting in the mould.This resin combination is injected in 200 * 150 * 6 millimeters the mold, solidified 50 minutes down, further 110 ℃ of following regelates 2 hours at 45 ℃.The performance of cured plate is listed in the table 1, shows as seen thus, and this plate lacks thermostability and hydrothermal stability.

Comparative Examples 2

The vinyl ester resin of 100 parts of weights (55 parts heavy bisphenol-A type Epocryls are dissolved in obtain in the vinylbenzene of 45 parts of weights) and the silane coupling agent of 0.5 part of weight (are produced by Shin-etsu chemical industry company limited, product is marked with the mark of " KBM-503 ") mix, make and be used for correlated resin combination, be 200 parts of heavy average particulate diameters that 17 microns aluminium hydroxide (is produced by Showa light metals industry company limited again, trade(brand)name is " HIGILITE H-310 ") be dispersed in the resin combination that obtains, (produced by Asada ironworks, trade(brand)name is " DESPA with homogenizer

"), stirred 20 minutes with 1100 rev/mins rotating speeds,, then, the initiators for polymerization of the dispersion liquid of gained and 0.8 part of weight (produced by Japanese Kayaku company limited, trade(brand)name is " Parkadocks PX-16 ") mixing.The viscosity of this resin combination in the time of 30 ℃ is 180 pools, even behind the excluding air, still have numerous air-bubble under vacuum, because mobile poor, this resin combination is difficult to inject mold.This resin combination is injected 200 * 150 * 6 millimeters mold, solidified 60 minutes down, further 110 ℃ of following regelates 2 hours at 45 ℃.The performance of cured plate is listed in the table 1, and by table 1 as seen, this resin combination lacks thermostability and hydrothermal stability.

Embodiment 9

The polymethylmethacrylate of 18 parts of weights (is produced by Mitsubishi Rayon company limited, trade(brand)name is " Acrypet MD001 ") be dissolved in the vinylbenzene of 18 parts of heavy trimethylolpropane trimethacrylates and 64 parts of weights, preparation liquid monomer mixture, the Zinic stearas as interior remover of 3 parts of weights, 0.8 part heavy mixing with gained solution as the t-butyl peroxy octanoate of initiators for polymerization and the silane coupling agent of 0.5 part of weight (produced by Shin-etsu chemical industry company limited, product is marked with the mark of " KBM-503 ").Then, in the liquid monomer mixture, the aluminium hydroxide that adds 300 parts of heavy average particulate diameters and be 3.5 microns (is produced by Showa light metals industry company limited, trade(brand)name is " HIGILITE H-320 "), (produce with double arm kneading mixer by Moriyama MFG equipment company limited, product is marked with the mark of " MS Open Type ") mediate, the rotating speed of preceding blade is 68 rev/mins, the rotating speed of back blade is 38 rev/mins, mediated about 5 minutes, block until forming the dough shape makes curable compositions of the present invention (9).

The curable compositions (9) that exists with the block form that obtains not is sticking sticking hand.Cut with this block of hilt, be divided into the piece of 2 kilogram weights, put into floorage and be 270 * 380 millimeters, high 80 millimeters box metal pattern, then, 120 ℃ and 60 tons of pressure dip molds 5 minutes.Thereby obtain beautiful box-shaped solidifying product, this product has fabulous surface luster, the dark oyster white that is translucent, and do not have flaw or distortion.The performance of this layered product is listed in the table 2, and by table 2 as seen, this product has the performance that high heat distortion point and good resistant thing adhere to.

Embodiment 10

The stearic acid zinc salt as inner pattern releasing agent applicable of 40 parts of heavy trimethylolpropane trimethacrylates and 60 parts of heavy vinylbenzene and 3 parts heavy, 0.8 part heavy (Shin-etsu chemical industry company limited produces as the t-butyl peroxy octanoate of initiators for polymerization and the silane coupling agent of 0.5 part of weight, product is marked with " KBM-503 " mark) mix, obtain the liquid monomer mixture.In this liquid monomer mixture, (Showa light metals industry company limited produces to add 600 parts of heavy average particulate diameters and be 3.5 microns aluminium hydroxide, trade(brand)name is " HIGILITE H-320 "), (produce with double arm kneading mixer by Moriyama MFG equipment company limited, product is marked with " MS Open Type " mark) mediate, 68 rev/mins of preceding blade rotating speeds, 38 rev/mins of back blade rotating speeds, mediated about 10 minutes, form the block of dough shape up to the mixture of gained, obtain curable compositions of the present invention (10).

The resulting blocky curable compositions (10) that is not is sticking sticking hand.With cutter it is cut into the piece of 2 kilogram weights, this piece is put into 270 * 380 millimeters of floorages, in the high 80 millimeters box metal die, 110 ℃ of temperature, 60 tons of pressure dip molds 5 minutes, thus beautiful box-shaped solidifying product obtained, and this product has fabulous surface luster, the dark oyster white that is translucent, and do not have flaw or distortion.The performance of this layered product is listed in the table 2, has write down the performance that product has high heat distortion point and good resistant thing to adhere in the table.

Embodiment 11

In the vinylbenzene of 25 parts of heavy trimethylolpropane trimethacrylates and 55 parts of weights, (Kuraray produces the liquid Malaysia polyisoprene of 20 parts of weights of dissolving, trade(brand)name is " Kuraprene ") as thickening polymer, its molecular-weight average is 25000, and per 100 isoprene repeating units contain 3.5 carboxyls, then the stearic acid zinc salt as inner pattern releasing agent applicable of the solution that obtains and 3 parts of weights, 0.8 part heavy (Shin-etsu chemical industry company limited produces as the t-butyl peroxy octanoate of initiators for polymerization and the silane coupling agent of 0.5 part of weight, product is marked with " KBM-503 " mark) mix, obtain the liquid monomer mixture.Use double arm kneading mixer (to produce then by Moriyama MFG equipment company limited, product is marked with " MS Open Type " mark) mediate this liquid monomer mixture, 68 rev/mins of preceding blade rotating speeds, 38 rev/mins of back blade rotating speeds, again the aluminium hydroxide of 3.5 microns of 300 parts of heavy average particulate diameters (is produced by Showa light metals industry company limited, trade(brand)name is " HIGILITE H-320 ") be added in the monomer mixture of mediating, continue to mediate about 5 minutes, form the block of dough shape until the mixture of gained.Then, the mixture that obtains mixes with the magnesium oxide that is added to 1 part of weight wherein (produced by Kyowa chemical industry company limited, trade(brand)name is " Kyowamag #20 "), makes curable compositions of the present invention (11).

The blocky curable compositions (11) that is that obtains not is sticking sticking hand.With cutter it is cut into the piece of 2 kilogram weights, this piece is put into 270 * 280 millimeters of floorages, high 80 millimeters box metal die, at 120 ℃, 60 tons of pressure dip molds 5 minutes.Thereby obtain beautiful box-shaped solidifying product, this product has fabulous surface luster, and translucent dark oyster white does not have flaw or distortion.The performance of this layered product is listed in the table 2, has write down the performance that product has high heat distortion point and good resistant thing to adhere in the table.

Embodiment 12

In the vinylbenzene of 30 parts of heavy trimethylolpropane trimethacrylates and 60 parts of weights, (company limited produces the polystyrene of the low shrinkable polymer of conduct of 10 parts of weights of dissolving by the Sumitomo chemistry, trade(brand)name is " S-bright T-2 Beads "), then the stearic acid zinc salt as inner pattern releasing agent applicable of the solution that obtains and 3 parts of weights, 0.8 part heavy (producing by Shin-etsu chemical industry company limited as the t-butyl peroxy octanoate of initiators for polymerization and the silane coupling agent of 0.5 part of weight, product be marked with " the KBM-503 mark) mix preparation liquid monomer mixture.Then, (produce with double arm kneading mixer by Moriyama MFG equipment company limited, product is marked with " MSOpen Type " mark) before 68 rev/mins of blade rotating speeds, 38 rev/mins of back blade rotating speeds, mediate this liquid monomer mixture, again the aluminium hydroxide of 3.5 microns of 300 parts of heavy average particulate diameters (is produced by Showa light metals industry company limited, trade(brand)name is " HIGILITE H-320 ") join in the liquid monomer mixture of mediating, continue to mediate about 5 minutes, form the block of dough shape until the mixture of gained, make curable compositions of the present invention (12).

The blocky curable compositions (12) that is that obtains not is sticking sticking hand.Be cut into the piece of 2 kilogram weights by knife, and piece put into 270 * 380 millimeters of floorages, in the high 80 millimeters box metal die, 120 ℃, 60 tons pressure dip molds 5 minutes, thereby obtain beautiful box-shaped solidifying product, this product has fabulous surface luster, translucent dark oyster white, not flaw or distortion.The performance that this layered product has high heat distortion point and good resistant thing to adhere to.

Comparative Examples 3

0.7 mole maleic anhydride, 0.3 mole of m-phthalic acid, 0.3 mole of neopentyl glycol, 0.6 mole of propylene glycol and 0.15 mole of Hydrogenated Bisphenol A condensation, obtain a kind of unsaturated polyester, these unsaturated polyesters of 45 parts heavy are dissolved in the vinylbenzene of 45 parts of weights, and in resulting solution, add the Resorcinol used as stabilizers of 0.005 part of weight, make a kind of resin solution of unsaturated polyester thus.In this resin solution, (company limited produces the polystyrene of 10 parts of weights of dissolving by the Sumitomo chemistry, trade(brand)name is " S-bright T-2 Beads ") as low shrinkable polymer, with the double arm kneading mixer similar to embodiment 9, stearic acid zinc salt with resulting solution and 3 parts of weights as inner pattern releasing agent applicable, 0.8 part heavy t-butyl peroxy octanoate as initiators for polymerization, 0.5 a part heavy silane coupling agent (is produced by Shin-etsu chemical industry company limited, product is marked with " KBM-503 " mark) and 210 parts of heavy average particulate diameters be that 17 microns aluminium hydroxide (is produced by Showa light metals industry company limited, trade(brand)name is " HIGILITE H-310 ") mix, obtain to be used for correlated curable resin composition.Obtain like this be used for correlated curable compositions sticking sticking hand, therefore lack workability.

When the amount of the aluminium hydroxide that is added surpasses 210 parts heavy, discovery can make the mixture of making form a monoblock on be limited to 250 parts of weights.When the aluminium hydroxide that adds surpassed arbitrary quantity of 250 parts of weights, prepared mixture separation became not have some groups, the piece of viscosity.

Method pressing mold by embodiment 9 is used for correlated resin combination, obtains a kind of layered product.The performance of this product is listed in the table 2, has write down this layered product in the table and has lacked thermostability and hydrothermal stability.

Embodiment 13

With the trimethylolpropane trimethacrylate of 50 parts of weights, the silane coupling agent of 50 parts of heavy vinylbenzene and 0.5 part of weight (being marked with " KBM-503 " mark by the production of Shin-etsu chemical industry company limited and at product) is mixed and made into the liquid monomer mixture.With homogenizer (Asada ironworks produce and be marked with " DESPA at trade mark

") with 1100 rev/mins of rotating speeds; stirred 20 minutes; with 300 parts of heavy average particulate diameters is that 3.5 microns the aluminium hydroxide (Showa light metals industry company limited produces; trade(brand)name be " HIGILITE H-320 ") and the Zinic stearas salt as inner pattern releasing agent applicable of 3 parts of weights is dispersed in this liquid monomer mixture; the t-butyl peroxy octanoate as initiators for polymerization of resulting dispersion liquid and 0.8 part of weight (Japanese grease company limited production; trade(brand)name is " Perbutylo ") mixing, just obtained curable compositions of the present invention (13) again.This curable compositions (13), viscosity is 19 pools in the time of 30 ℃.Then; the metal die (confession production usefulness, diameter 200mm, the dish of dark 10mm) that is positioned in advance on the press molding machine is heated to 120 ℃; three broken glass fiber fabrics are placed in this metal die, the glasscloth specification be #450(450 gram/square metre).150 gram curable compositions (13) of these glasscloths and adding are used 30Kg/cm ²Pressure on product surface, be extruded 3 minutes, just make the thick FRP layered product of 3mm.

The FRP layered product has beautiful oyster white texture, although glasscloth wherein is visible.The performance of this FRP layered product is listed in the table 3.Outstanding flame retardant resistance and the thermostability and the hydrothermal stability of this product have been write down in the table.

Embodiment 14

(Mitsubish Rayon company limited produces the polymethylmethacrylate of 18 parts of weights of dissolving in 30 parts of heavy trimethylolpropane trimethacrylates and 52 parts of heavy vinylbenzene, trade(brand)name is " Acrypet MDOC01 ") silane coupling agent of resulting solution and 0.5 part of weight (is produced with Shin-etsu chemical industry company limited, product be marked with " KBM-503 " and mark) coagulation closes, and makes the liquid monomer mixture.Then, (Asada ironworks produces, and trade(brand)name is DESSPA with high-speed stirring ") stirred 20 minutes with 1100 rev/mins rotating speeds; with 300 parts of heavy average particulate diameters is that 3.5 microns the aluminium hydroxide (Showa light metals industry company limited produces, and trade(brand)name is " HIGILITE H-320 ") and the Zinic stearas salt that adds as inner pattern releasing agent applicable of 3 parts of weights is dispersed in this liquid monomer mixture.The t-butyl peroxy octanoate as initiators for polymerization of resulting dispersion liquid and 0.8 part of weight (Japanese grease company limited produce name call " PerbutylO ") is mixed, produce curable compositions of the present invention (14).This curable compositions (14) viscosity in the time of 30 ℃ is 86 pools.Press the method for embodiment 13, obtain the FRP layered product with curable compositions (14).

This layered product has very slick and has hidden the beautiful oyster white texture of fiber reinforced glass matrix wherein fully.The performance of this product is listed in the table 3, has write down outstanding flame retardant resistance and thermostability and the hydrothermal stability of this product in the table.

Comparative Examples 4

0.3 the m-phthalic acid of mole, 0.7 the maleic anhydride of mole, 0.3 the neopentyl glycol of mole, 0.6 the propylene glycol of mole and 0.15 mole Hydrogenated Bisphenol A condensation obtain a kind of unsaturated polyester, these unsaturated polyesters of 47.5 parts heavy are dissolved in the vinylbenzene of 47.5 parts of weights, in the solution of gained, add Resorcinol, make a kind of resin solution of unsaturated polyester thus as 0.005 part of weight of stablizer.In this resin solution, and the polymethylmethacrylate of 5 parts of weights of dissolving (Mits-ubishi Rayon company limited produces, and trade(brand)name is Acrypet MD001 ") (Asada ironworks produces, and trade(brand)name is " DESPA with homogenizer

") stirred 20 minutes with 1100 rev/mins rotating speeds; thus with the silane coupling agent (producing by Shin-etsu chemical industry company limited; product is marked with " KBM-503 " mark) of 0.5 part of weight of aforementioned resin solution that is dissolved with polymethylmethacrylate and adding; the stearic acid zinc salt as inner pattern releasing agent applicable of 3 parts of weights; 0.8 part heavy be that 3.5 microns aluminium hydroxide (being produced by Showa light metals industry company limited; trade(brand)name is " HIGILITE H-320 ") mixes as the t-butyl peroxy octylate of initiators for polymerization and 130 parts of heavy average particulate diameters, just produced a kind of curable resin combination, in the time of 30 ℃, its viscosity is 110 pools.Then, press the method for embodiment 13, produce the FRP layered product with this resin combination.

The FRP layered product of Sheng Chaning has beautiful oyster white texture like this, little fiber reinforced glass matrix that exposes wherein.The performance of this product is listed in the table 3, has write down the thermostability of this product in the table, the deficiency of hydrothermal stability and flame retardant resistance aspect.

Embodiment 15

The liquid monomer mixture that to form by 25 parts of heavy trimethylolpropane trimethacrylates and 75 parts of heavy vinylbenzene and the stearic acid zinc salt of 3 parts of weights, 0.8 (Japanese grease company limited produces part heavy t-butyl peroxy octanoate as initiators for polymerization, trade(brand)name is " PerbutylO ") and the silane coupling agent of 0.5 part of weight (Shin-etsu chemical industry company limited produces, and product is marked with " KBM-503 " mark) mix.Resulting liquid mixture is placed in the double arm kneading mixer.Then, (Showa light metals industry company limited produces to add 300 parts of heavy average particulate diameters again and be 3.5 microns aluminium hydroxide in kneader, trade(brand)name is " HIGILITE H-320 "), mediated about 5 minutes, form the block of dough shape until the mixture of gained, produce curable composition of the present invention (15), the broken glass fiber that is cut into long 6mm of this curable composition (15) and 45 parts heavy was mediated 5 minutes together, make pre-mixing molding compound.This pre-mixing molding compound is not have viscosity and the agglomerate of the workability that meets the requirements.With cutter pre-mixing molding compound is cut into the piece of 2 kilogram weights, is placed in the box-shaped metal die (temperature remains on 120 ℃ for its floorage 270 * 380mm, dark 80mm) that is positioned on the press molding machine, extruding is 5 minutes under 60 tons of pressure.Thereby obtain the translucent product of beautiful oyster white, this product has fabulous surface luster, does not have flaw or distortion.The performance of this product is listed in the table 4, has write down this product outstanding thermostability, hydrothermal stability and flame retardant resistance in the table.

Embodiment 16

In the liquid monomer mixture of forming by the vinylbenzene of 30 parts of heavy trimethylolpropane trimethacrylates and 50 parts of weights, dissolving 20 parts of heavy molecular-weight average is 25,000, and per 100 isoprene repeating units contain liquid Malaysia polyisoprene (the Kuraray company limited production of 3.5 hydroxyls, trade(brand)name is " Kuraprene "), thus the polymer slurries of 100 parts of weights obtained.(Asada ironworks produces, and trade(brand)name is " DESPA with homogenizer

") stirred 20 minutes with 1100 rev/mins; with the silane coupling agent (Shin-etsu chemical industry company limited produces; product is marked with " KBM-503 " mark) of this polymer slurries and 0.5 part of weight; the t-butyl peroxy benzoic ether as initiators for polymerization of 1.0 parts of weights (Japanese grease company limited produces; trade(brand)name is " Perbutyl Z "); 1 part heavy be 3.5 microns aluminium hydroxide (Showa light metals industry company limited production as the stearic acid zinc salt of inner pattern releasing agent applicable and 300 parts of heavy average particulate diameters, trade(brand)name is " HIGILITE H-320 ") mix, produce curable compositions of the present invention (16).In the time of 30 ℃, this curable compositions (16) viscosity is 80 pools.The composition that this is curable (16) obtains a kind of soaker that is used to prepare sheet molding compound (SMC) with the magnesium oxide as thickening material (Kyowa chemical industry company limited produces, and trade(brand)name is " the Kyowamag#20 ") mixing of 1 part of weight.In the device of producing SMC, with this soaker impregnated glass fiber fragment, produce a kind of impregnated sheet, its every weight per square meter 4kg, and contain 25% heavy glass fibre fragment, these glass fibre fragments are that fibre glass roving (Nitto Bosehi company limited produces, and product is marked with " RS-240F-546 " mark) is cut into 1 inch long obtaining.Impregnated sheet material is placed in the curing chamber, and slaking is 20 hours under 40 ℃ of temperature, obtains the SMC product, and it lacks tackiness, glass fibre is fully flooded and is imbued with workability.Pressing mold (135 ℃, 100kg/cm ²Condition dip mold 3 minutes) SMC obtains being of a size of the plate-like product of 200 * 200 * 3mm, and its performance is listed in the table 4, has write down this product outstanding thermostability, hydrothermal stability and flame retardant resistance in the table.

Embodiment 17:

Method by embodiment 16 prepares curable compositions (16), continues to mediate in double arm kneading mixer then, (Showa light metals industry company limited produces to add 100 parts of heavy average particulate diameters again and be 3.5 microns aluminium hydroxide, trade(brand)name is " HIGILITE H-320 "), and mix with the curable compositions of mediating (16), produce curable compositions of the present invention (17).In the time of 30 ℃, the viscosity of curable compositions (17) is 960 pools, (Kyowa chemical industry company limited produces the magnesium oxide of the composition that this is curable (17) and 1 part of weight, trade(brand)name is " Kyowamag#20 "), the glass fibre fragment of 90 parts of weights mixes, and obtains a block, and this glass fibre fragment is by (Nitto Bosehi company limited produces fibre glass roving, product is marked with " RS-240F-546 " mark), be cut into 1/4 inch long obtaining.40 ℃ this block slaking 20 hours, just produce a kind of Unitarily molded compound (BMC).It lacks tackiness, can make glass fibre fully flood highly processable.The performance of the layered product that obtains by the method pressing mold BMC of embodiment 16 is listed in the table 4, has write down the outstanding thermostability of this product in the table, hydrothermal stability and flame retardant resistance.

Comparative Examples 5

0.3 mole m-phthalic acid, 0.7 mole of maleic anhydride, 0.3 mole of neopentyl glycol, 0.6 mole of propylene glycol and 0.15 mole of Hydrogenated Bisphenol A condensation obtain unsaturated polyester, 40 parts heavy this unsaturated polyesters are dissolved in the vinylbenzene of 40 parts of weights, the two dihydroxy-benzenes that add 0.005 part of weight in the solution of gained are made a kind of resin solution of unsaturated polyester thus as stablizer.In this resin solution, dissolve 20 parts of heavy molecular-weight average and be 25000 Malaysia polyisoprene (Kuraray company limited produces, and trade(brand)name is " Kuraprene ").Then, (Asada ironworks produces, and trade(brand)name is " DESPA with homogenizer

") stirred 20 minutes with 1100 rev/mins rotating speeds; the t-butyl peroxy benzoic ether as initiators for polymerization of the resin solution that obtains and 1.0 parts of weights; the stearic acid zinc salt as inner pattern releasing agent applicable of 1.0 parts of weights; the silane coupling agent of 0.5 part of weight (Shin-etsu chemical industry company limited production; product is marked with " KBM-503 " mark) and 150 parts of heavy average particulate diameters are that 17 microns aluminium hydroxide (being produced by Showa light metals industry company limited; trade(brand)name is " HIGILITE H-310 ") mixes, and produce a kind of correlated resin combination that is used for.The viscosity of this resin combination in the time of 30 ℃ is 150 pools.The magnesium oxide as thickening material (produced by Kyowa chemical industry company limited, trade(brand)name is " Kyowamag #20 ") of this resin combination and 1 part of weight is mixed, obtain being used to produce the soaker (Comparative Examples) of SMC.Press the method for embodiment 16, be used for correlated SMC with this soaker production.When pressing the method pressing mold SMC of embodiment 16, the performance that compression-moulded product presented is listed in the table 4.

Claims (30)

1, a kind of curable composition comprises (A) and contains the mixture formed with the aromatic ethenyl compound of aliphatics polyfunctional group (methyl) acrylate of 20 to 80% weight and 80 to the 20% weight a kind of monomer mixture as its main component, (B) a kind of average particulate diameter is no more than 5 microns the mineral filler and (C) initiators for polymerization of catalytic amount, and disperses the above-mentioned mineral filler (B) of 250-800 part weight in the above-mentioned monomer mixture (A) of per 100 parts of weights.

2, according to the composition of claim 1, wherein the consumption of initiators for polymerization is in 0.2 to 0.3% scope of the weight of above-mentioned monomer mixture (A).

3, according to the composition of claim 1, wherein said mineral filler (B) is a kind of hydrated metal oxide.

4, according to the composition of claim 1, wherein said mineral filler (B) is an aluminium hydroxide.

5, according to the composition of claim 1, the dispersion of wherein said mineral filler (B) in described monomer mixture (A) realizes by using homogenizer.

6, according to the composition of claim 5, wherein said homogenizer rotates with the speed that is not less than 1000 rev/mins.

7, according to the composition of claim 1, the dispersion of wherein said mineral filler (B) in described monomer mixture (A) realizes by using the low speed kneader.

8, according to the composition of claim 7, wherein said low speed kneader is a double arm kneading mixer.

9, according to the composition of claim 1, wherein said monomer mixture (A) comprises the thickening material of 5 to 40 parts of heavy thickening thermoplastic polymers and 0.5 to 5 part of weight, is benchmark with the monomer mixture (A) of 100 parts of weights.

10, according to the composition of claim 9, wherein said thickening thermoplastic polymer has two carboxyls at least in its molecular cell, and described thickening material is metal oxide or metal hydroxides.

11, according to the composition of claim 9, wherein said thickening thermoplastic polymer has two hydroxyls at least in its molecular cell, and described thickening material is multi-functional isocyanate compound.

12, a kind of method of producing curable compositions, this method comprises with homogenizer mixes (A) a kind of monomer mixture that contains the mixture formed with the aromatic ethenyl compound of aliphatics polyfunctional group (methyl) acrylate of 20 to 80% weight and 80 to 20% weight as its main component, (B) a kind of average particulate diameter is no more than 5 microns the mineral filler and (C) initiators for polymerization of catalytic amount, described monomer mixture (A) with 100 parts of weights is a benchmark, the total amount of described mineral filler (B) forms the liquid that viscosity is 2 to 100 pools up to the gained mixture in 250 to 500 parts heavy scopes.

13, according to the method for claim 12, wherein said homogenizer rotates with the speed that is not less than 1000 rev/mins.

14, according to the method for claim 12, wherein said homogenizer is a dispersion mixer.

15, according to the method for claim 12, wherein said mineral filler (B) is a hydrated metal oxide.

16, according to the method for claim 12, wherein said mineral filler (B) is an aluminium hydroxide.

17, according to the method for claim 12, wherein said monomer mixture (A) comprises the thickening material of 5 to 40 parts of heavy thickening thermoplastic polymers and 0.5 to 5 part of weight, is benchmark with the monomer mixture (A) of 100 parts of weights.

18, a kind of method of producing curable compositions, this method comprises with the low speed kneader mixes (A) a kind of monomer mixture that contains the mixture formed with the aromatic ethenyl compound of aliphatics polyfunctional group (methyl) acrylate of 20 to 80% weight and 80 to 20% weight as its main component, (B) a kind of average particulate diameter is no more than 5 microns the mineral filler and (C) initiators for polymerization of catalytic amount, monomer mixture (A) with 100 parts of weights is a benchmark, the total amount of described mineral filler (B) forms the block of dough shape up to the mixture of gained in the scope of 250 to 800 parts of weights.

19, according to the method for claim 18, wherein said low speed kneader rotates with the speed that is no more than 100 rev/mins.

20, according to the method for claim 18, wherein said low speed kneader is a double arm kneading mixer.

21, according to the method for claim 18, wherein said mineral filler (B) is a hydrated metal oxide.

22, according to the method for claim 18, wherein said mineral filler (B) is an aluminium hydroxide.

23, according to the method for claim 18, wherein said monomer mixture (A) comprises the thickening material of 5 to 40 parts of heavy thickening thermoplastic polymers and 0.5 to 5 part of weight, is benchmark with the described monomer mixture (A) of 100 parts of weights.

24, a kind of goods that obtain by the curable compositions described in the claim 1 that is heating and curing.

25, according to the goods of claim 24, wherein said goods are artificial marbles.

26, a kind of by the curable compositions described in the casting claim 5, and under heating, solidify the casting article that above-mentioned composition obtains.

27, a kind ofly depress the moulded product that the curable compositions described in the claim 7 that is heating and curing obtains adding.

28, a kind ofly strengthen the mixed moulding compound that gives that staple fibre obtains with the curable compositions described in the claim 1 dipping.

29, a kind of fibre-reinforced plastics that obtain by following method, curable compositions described in the claim 1 is added to the fortifying fibre that is placed on the metal die that is used for flooding fortifying fibre in advance, and depresses the impregnated fortifying fibre that is heating and curing adding.

30, a kind of fibre-reinforced duroplastic moulding materials that obtains with the dipping of the curable compositions described in the claim 9 fortifying fibre.