JP2860113B2 - Composition for artificial marble - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composition for artificial marble having a deep appearance unique to marble, and having high strength and abrasion resistance.

[Conventional technology and its problems] Conventionally, artificial marble has been widely used for sanitary wear such as vanities, bathtubs, kitchen counters, etc., or interior and exterior materials for buildings.

When artificial marble is obtained as a resin molded product, a composition obtained by blending and kneading, for example, an inorganic filler or a fibrous reinforcing material with a resin as a matrix constituting the artificial marble is filled into a molding die and cured. The molding method is adopted. In addition, inorganic fillers and other extenders are mixed with resin, impregnated into glass fiber, etc., wrapped on both sides with film, and made into a sheet-like SMC (sheet molding compound) or similarly BMC (bulk-like)・ Molding compound) to perform compression molding.

The resin as the matrix is generally an unsaturated polyester resin or an epoxy resin, but the appearance as artificial marble is slightly inferior.For example, those using an unsaturated polyester resin as a matrix are transparent. It has a drawback that a deep appearance based on the transparency unique to marble cannot be obtained due to lack of properties.
Accordingly, proposals have been made to improve this (JP-A-59-66426 and JP-A-61-101552).

Further, those using an unsaturated polyester resin as a matrix have the disadvantage that the surface is not sufficiently scratch-resistant and a gel coat agent must be used.

On the other hand, artificial marble is becoming more and more upscaled in terms of application,
Improvement in appearance, bending strength, mechanical strength such as impact resistance, surface strength, or thermal strength that gives a sense of solidity such as the pattern emerging from the inside of the molded product resulting from transparency is required, Along with this, a methacrylic resin having excellent transparency and mechanical strength has attracted attention as a matrix resin, and there have been many proposals regarding artificial marble compositions or artificial marbles using a methacrylic resin as a matrix. In addition, a patent characterized by a combination with a filler, for example, a method of adding aluminum hydroxide (Japanese Patent Publication No.
Nos. 50-22586 and 55-43422), a method of adding silica (Japanese Patent Application Laid-Open No. 58-4461), a method of adding calcium silicate (Japanese Patent Application Laid-Open No. 59-33308), and the like. Have been. A composition in which the flowability of a methacrylic acid-based resin composition containing a filler is improved at the time of molding (JP-A-60-24)
No. 5609) is also disclosed.

As described above, the resin as the matrix is shifting from unsaturated polyester resins, epoxy resins, and the like to methacrylic resins.

As described above, the resin as a matrix in artificial marble has a deep appearance in the artificial marble molded to be a resin having excellent transparency, and imparts a solid feeling to the resin, so that a methacrylic resin is used. It is generally considered a suitable resin. However, the methacrylic resin and the filler have remarkably different properties from each other, and there is a problem that the affinity and adhesion between the resin and the filler are poor due to the difference in interfacial properties. In addition, when the filler is compounded, the viscosity increases with the compounding, which makes it difficult to uniformly disperse the filler. Therefore, there is also a problem that it is difficult to reduce the cost of improving the properties of artificial marble by increasing the amount of filler.

As a result, the resulting artificial marble has a disadvantage that mechanical strength such as bending strength and impact resistance is not practically sufficient. To remedy this drawback,
For example, artificial marble, in which the surface of a filler is treated with a silane coupling agent and then mixed with a resin, has been proposed, but has not yet achieved a sufficient improvement effect. In addition, an increase in manufacturing costs is inevitable.

In addition, methacrylic resins have a fatal defect that they have low resistance to boiling water and cannot be used in bathtubs.

Means for Solving the Problems The inventors of the present invention have conducted intensive studies for overcoming the drawbacks of a resin used as a matrix constituting a conventionally used artificial marble, and as a result, a specific structure having an allyl group was found. When the polymerizable oligomer represented by the formula is used for a resin as a matrix constituting artificial marble, it is excellent in mechanical strength such as bending strength and impact strength, and has high surface hardness and excellent transparency, so it is molded It has been found that it has an appearance that gives a profound feeling that the pattern emerges from the inside of the product.

The polymerizable oligomer represented by the specific structural formula having an allyl group, which is blended in the composition of the present invention, includes at least one selected from oligomers having the structural formulas represented by the following (1) and (2). One terminal allylic oligomer.

(1) CH ₂ CHCHCH ₂ O (COArCOOBO) _n COArCOOCH ₂ CH ＝ CH _{2 wherein} B is 2 derived from a diol having 2 to 20 carbon atoms
Ar is a 1,4-, 1,3- or 1,2-
Represents an phenylene group, and n is an integer of 1 to 100], wherein the degree of unsaturation represented by an iodine value measured by a wijs method is 20 to 100. Terminal allyl oligomer.

(2) having an allyl ester group at the terminal and having the following repeating unit (COArCOOBO) structure -A (COArCOO) _x Z-O-COArCOO- structure -B wherein x is an integer of 2 or more and 10 or less; Z is an organic residue derived from a polyol having X + 1 hydroxyl groups,
B is a divalent organic residue derived from a diol having 2 to 20 carbon atoms, and Ar represents a 1,4-, 1,3- or 1,2-phenylene group]. An allyl terminal oligomer having a degree of unsaturation represented by an iodine value of 20 to 100 as measured by a wijs method.

Examples of the diol having 2 to 20 carbon atoms that induces B include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and 1,3-cyclohexanedimethanol. Butanediol, neopentyl glycol, 1,3-cyclohexanediol, p-
Examples thereof include diols containing an aliphatic or aromatic ring such as xylylene glycol and styrene glycol.

Examples of the polyol having X + 1 hydroxyl groups which induce Z include aliphatic trihydric alcohols such as glycerin and trimethylolpropane, and aliphatic tetrahydric alcohols such as pentaerythritol and sorbitol.

This oligomer is disclosed in Japanese Patent Application No. 63-262217 (Japanese Patent Application Laid-Open No.
No. 1509) can be synthesized by the method described in the gazette.

Here, among B, a particularly preferable one which gives a polymerizable oligomer which is liquid and excellent in transparency is one having a side chain at a position where a hydroxyl group such as 1,2-propylene glycol or 1,3-butanediol is attached. Is what it is.

If the amount of the polymerizable oligomer is too large, the appearance of artificial marble as a molded product is poor, and it is difficult to obtain the desired solid feeling. On the other hand, if the amount is too small, the dispersibility of the inorganic filler is extremely deteriorated. Therefore, it should be used in an actual amount of 15 to 60% by weight, more preferably 20 to 50% by weight.

Further, other reactive monomers can be added for the purpose of improving the polymerizability and the surface hardness.

Such reactive monomers include, for example, unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and derivatives thereof, unsaturated dibasic acids and derivatives thereof, vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof, ) Vinyl cyanide compounds such as acrylonitrile. As unsaturated fatty acid esters, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate , Cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate,
Alkyl (meth) acrylates such as (iso) bornyl (meth) acrylate and adamantyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth)
Acrylate, 1-naphthyl (meth) acrylate, fluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, cyanophenyl (meth) ) Acrylic acid aromatic esters such as acrylate, biphenyl (meth) acrylate and bromobenzyl (meth) acrylate, fluoromethyl (meth) acrylate, chloromethyl (meth) acrylate, bromoethyl (meth) acrylate, trichloromethyl (meth) acrylate Haloalkyl (meth) acrylate, 2-
In addition to hydroxyethyl (meth) acrylate and polyethylene glycol (meth) acrylate, there are (meth) acrylates such as glycidyl (meth) acrylate and alkylamino (meth) acrylate. Further, there are α-substituted acrylates such as α-fluoroacrylate and α-cyanoacrylate.

Examples of the aromatic vinyl compound include styrene or α-substituted styrene such as α-methylstyrene, α-ethylstyrene and α-chlorostyrene, and substituted styrene such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene. There is.

Examples of unsaturated fatty acids and derivatives thereof include (meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and (meth) acrylic acid.

Examples of unsaturated dibasic acids and derivatives thereof include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, There are N-substituted maleimides such as N-carboxyphenylmaleimide, maleic acid, maleic anhydride, fumaric acid and the like.

Vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate, vinyl benzoate and n-vinyl butyrate.

In addition, a crosslinkable polyfunctional monomer can also be used. Examples of such a monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. Acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5
-Pentadiol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyglycol ester di (meth) acrylate, oligoester di (meth) acrylate Acrylate, polybutadiene di (meth) acrylate, 2,2-bis (4-
(Meth) acryloyloxyphenyl) propane, 2,2
-Bis (4-ω- (meth) acryloyloxypolyethoxy) phenyl) propane, 2,2-bis (4-ω- (meth) acryloyloxypolyethoxy) dibromophenyl) propane, 2,2-bis (4 -Ω- (meth) acryloyloxypolypropoxy) phenyl) propane, bis (4-ω- (meth) acryloyloxypolyethoxy)
Di (meth) acrylates such as phenyl) methane, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenene, N,
Bifunctional crosslinkable monomers such as N'-m-phenylenebismaleimide, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) allyl isocyanate Nurate, tri (meth) allyl cyanurate, triallyl trimellitate,
Trifunctional crosslinkable monomers such as diallyl chlorentate,
Examples include tetrafunctional crosslinkable monomers such as pentaerythritol tetra (meth) acrylate.

Among these, aromatic copolyesters such as diallyl phthalate, diallyl isophthalate, and diallyl terephthalate, (meth) acrylates, and vinyl acetate are preferable in consideration of copolymerizability with the allyl group of the polymerizable oligomer. In order to increase the surface hardness, it is particularly desirable to add a crosslinkable polyfunctional monomer.

The mixing ratio of the reactive monomer is 30% by weight of the composition of the present invention.
Or less, more preferably 20% by weight or less. If it exceeds 30% by weight, an unduly slow curing speed and an increase in internal strain of the molded article due to an increase in the curing shrinkage become remarkable, which is not preferable.

As the inorganic filler to be contained in the artificial marble composition of the present invention, for example, silica, quartz, titanium oxide, antimony trioxide, aluminum oxide, calcium carbonate, aluminum hydroxide, magnesium hydroxide, talc, clay,
Fine particles of metal or the like are used. In particular, aluminum hydroxide, magnesium hydroxide and the like are suitable for improving the flame retardancy of artificial marble as a molded product. The particle diameter of the fine particles is 1 to 50 µ, preferably 10 to 30 µ.
Furthermore, the inorganic filler is not limited to one type, and two or more types can be used in combination. In addition, those which have been surface-treated for the purpose of improving the dispersibility and adhesion of the inorganic filler can also be used.

The composition for artificial marble of the present invention can be molded into artificial marble by polymerizing and curing.

As the curing agent used in the present invention, any radical polymerization initiator can be used as long as it can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays, and the use and purpose of the curable composition can be used. , The mixing ratio of the components, the method of curing the curable composition, etc.

Examples of radical polymerization initiators that can be used for polymerization by heat, microwaves, and infrared rays include 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, and 2,2'-azobis (2 Azo compounds such as 2,4-dimethylvaleronitrile), ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide, isobutyryl peroxide,
Diacyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobezoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, Hydroperoxides such as cumene hydroperoxide and t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t-
Butyl peroxide, tris (t-butylperoxy)
Dialkyl peroxides such as triazine, 1,1-di-
t-butylperoxycyclohexane, 2,2-di (t-
Peroxyketals such as butylperoxy) butane,
t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy Alkyl peresters such as -3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, diisopropylperoxydicarbonate, di-sec-butylperoxy Percarbonates such as dicarbonate and t-butyl peroxyisopropyl carbonate are exemplified.

Examples of the radical polymerization initiator that can be used in polymerization by ultraviolet light include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 4'-isopropyl-2-hydroxy-
2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis (diethylamino) benzophenone, benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione- 2- (o-ethoxycarbonyl) oxime,
1-phenyl-1,2-propanedione-2 (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoisopropyl ether, benzoisobutyl ether, benzoisooctyl ether, benzyl, benzyldimethyl ketal, benzyldiethyl Ketals, carbonyl compounds such as diacetyl, methylanthraquinone, chloroanthraquinone,
Chlorothioxanthone, 2-methylthioxanthone, 2
-Anthraquinone or thioxanthone derivatives such as isopropylthioxanthone; sulfur compounds such as diphenyldisulphide and dithiocarbamate. These are preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 2 parts by weight, based on the polymerizable oligomer. The polymerization initiator can be used in combination with another polymerization accelerator.

The artificial marble composition of the present invention may contain other known additives, such as a plasticizer, a lubricant, a release agent, a colorant, a flame retardant, and an ultraviolet absorber, if necessary.

After blending each of the above materials, the composition is sufficiently stirred and mixed to obtain a uniform composition. The composition thus obtained is poured into a mold having a desired shape, degassed, and polymerized and cured by heating to obtain a molded article. Further, the SMC or the BMC formed into a sheet by wrapping the homogenized composition with a film can be cured by pressure molding by a usual molding means to form a molded body.

 Hereinafter, the present invention will be described in more detail with reference to examples.

Reference Example 1 In a three-necked flask equipped with a distillation apparatus, 2 mol of diallyl terephthalate, 1 mol of propylene glycol, and 0.1 g of dibutyltin oxide were charged and placed under a nitrogen stream.
The mixture was heated to 180 ° C., and allyl alcohol produced was distilled off. When about 1.8 mol of allyl alcohol was distilled off, the pressure inside the reaction system was reduced to 50 mmHg, and the distillation rate of allyl alcohol was increased. After the theoretical amount of allyl alcohol had distilled off, the reaction was allowed to proceed for an additional hour and the reaction was cooled. The reaction solution contained 22% by weight of diallyl terephthalate monomer, which was used as it was as a raw material for the next artificial marble composition.

Its structure is represented by the following formula, and its iodine value is 103.
The molecular weight by GPC was _Mn = 9.90 × 10 ² , _Mw = 1.67 × 10 ³ , and the viscosity by a rotational viscometer was 7000 cP.

Reference Example 2 Reference Example 1 was repeated except that propylene glycol in Reference Example 1 was changed to 1,3-butanediol to obtain a raw material of artificial marble.

This is represented by the following structural formula, and the DATP monomer is
It contains 20.1%, has an iodine value of 101.6 (75.3 when only an oligomer is used), and has a molecular weight determined by GPC of M _n = 1.23 × 10 ² , M _w
= 2.01 × 10 ³ , and the viscosity by a rotational viscometer was 6,500 P.

Example 1 100 parts by weight of the polymerizable oligomer obtained in Reference Example 1 were mixed with coarse aluminum hydroxide (manufactured by Showa Denko KK, trade name "Hylide® H-100") and fine aluminum hydroxide (Showa Denko ( Co., Ltd., product name "Heidiland H-32
0 ") was added in an amount of 100 parts by weight, and the mixture was stirred and uniformly dispersed. 1 part by weight of dicumyl peroxide was further added thereto, stirred, and then deaerated under reduced pressure to obtain a compound.

The compound thus obtained was cast into a metal mold of 40mmφ × 40mm and heated and hardened at 170 ° C for 1 hour, and it scattered light beautifully and formed a marble-like molded product that had both depth and concealment. Obtained.

The obtained molded product was measured for Hunter chromaticity using a colorimeter and a hardness measurement using a Rockwell hardness meter.

 The results are shown in Table 1.

Example 2 80 parts by weight of the polymerizable oligomer obtained in Reference Example 1 was mixed with 20 parts by weight of a diallyl terephthalate monomer, and the resulting syrup was mixed with fine aluminum hydroxide (trade name "Hylide" manufactured by Showa Denko KK). H-320 "), 200 parts by weight, and stirred to uniformly disperse. 1 part by weight of dicumyl peroxide was further added thereto, and the mixture was stirred and deaerated under reduced pressure to obtain a compound.

The compound thus obtained was cast into a metal mold of 40mmφ × 40mm and heated and hardened at 170 ° C for 1 hour, and it scattered light beautifully and formed a marble-like molded product that had both depth and concealment. Obtained.

Table 1 also shows the measurement results of the obtained molded product in the same manner as in Example 1.

Example 3 Coarse-grained aluminum hydroxide (manufactured by Showa Denko KK, trade name “Hylide® H-100”) and fine-grained aluminum hydroxide (Showa Denko (100 g) were added to 100 parts by weight of the polymerizable oligomer obtained in Reference Example 2. Co., Ltd., trade name "Heidiride H-32"
0 ") was added in an amount of 100 parts by weight, and the mixture was stirred and uniformly dispersed. 1 part by weight of dicumyl peroxide was further added thereto, and the mixture was stirred and deaerated under reduced pressure to obtain a compound.

The compound thus obtained was cast into a metal mold of 40mmφ × 40mm and heated and hardened at 170 ° C for 1 hour, and it scattered light beautifully and formed a marble-like molded product that had both depth and concealment. Obtained.

[Effects of the Invention] By using the polymerizable oligomer of the present invention as a resin constituting a matrix of artificial marble, it is possible to obtain an artificial marble that has significantly improved boiling resistance, which is a drawback of a methacrylic resin, and can be used in a bathtub. It became possible.

Further, compared with the unsaturated polyester resin, the scratch resistance was greatly improved, and the gel coating agent was not required. In addition, the appearance was full of luxuriousness, and the thermal shock characteristics were significantly improved.

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Mikito Kitayama 8 Ebisu-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside the Showa Denko KK Yokohama Plant (56) References JP-A-52-39785 (JP, A) JP-A-2-75509 (JP, A) JP-A-2-49016 (JP, A) JP-A-2-300220 (JP, A) JP-A-54-68891 (JP, A) JP-A-2-251509 (JP, A) , A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C04B 14/00-41/91 C08F 18/00-18/24 C08F 118/00-118/18 C08F 218/00-218 / 18 C08F 290/00-290/14 C08F 299/00-299/08

Claims (1)

(57) [Claims] (A) 15 to 60 wt% of an allylic terminal oligomer represented by the following (1) and / or (2): (1) CH ₂ CHCHCH ₂ O (COArCOOBO) _n COArCOOCH ₂ CH CHCH _{2 wherein} B is 2 derived from a diol having 2 to 20 carbon atoms
Ar is a 1,4-, 1,3- or 1,2-
Represents a phenylene group, and n is an integer of 1 to 100.] (2) (COArCOOBO) structure —A having an allyl ester group (CH ₂ CHCHCH ₂ OCO—) at the terminal and having the following repeating unit ) _X Z-O-COArCOO- structure -B wherein x is an integer of 2 or more and 10 or less, Z is an organic residue derived from a polyol having X + 1 hydroxyl groups,
B is a divalent organic residue derived from a diol having 2 to 20 carbon atoms, and Ar represents a 1,4-, 1,3- or 1,2-phenylene group.] (B) Inorganic filler 40 A composition for artificial marble comprising about 77 wt% and (c) 0.30 wt% of a reactive monomer.