AU628080B2 - Synthetic stone-forming composition and molded synthetic stone article - Google Patents

Description

6280110 C 0 P LE T SPECIFICATION FOR OFFICE USE Application Number: Lodged: Complete Specification Priority: Class Int. Class Lodged: Accepted: Published: This doci "ent contains the Samendner ailo;ied ainder SSection 83(2) by the Supervising Eximiner on and is correct for printing Related Art: t I TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: Actual Inventors: Address for Service: MITSUI PETROCHEMICAL INDUSTRIES, LTD.

2-5, Kasumigaseki 3-chome, Chiyoda-ku, Tokyo 100, Japan Kakutaro KAUCHI and Yoshiaki KAWAMURA SMITH SHELSTON BEADLE 207 Riversdale Road Box 410) Hawthorn, Victoria, Australia Complete Specification for the invention entitled: SYNTHETIC STONE-FORMING COMPOSITION AND SYNTHETIC STONE ARTICLE

MOLDED

4

C

4s The following statement i- a full description of this invention, including the best method of performing it known to us: Page 1 Our Ref: #4287 JC:WB

I

This invention relates to synthetic stone-forming compositions and molded synthetic stone articles of resinous material, and more particularly, to molded synthetic stone articles having satisfactory chemical resistance, minimized polymerization shrinkage, and high impact strength and compositions therefor.

Molded synthetic stone articles are known in the prior art which are prepared by admixing aggregates or fillers in the form of crushed pieces of natural stone, finely divided stone, o0 various slags, sand, talc, clay or the like with thermosetting unsaturated polyester resins or thermosetting unsaturated acrylic resins and polymerizing and curing the admixture into a predetermined shape.

Japanese Patent Application Kokai No. 61-111953 discloses a molded synthetic stone article comprising polyol-poly(allyl carbonate) and finely divided silica or alumina hydrate. This molded synthetic stone article has improved chemical resistance, but suffers from considerable polymerization shrinkage and low impact strength.

-o Japanese Patent Application Kokai No.63-64948 discloses a synthetic marble-forming composition comprising an inorganic filler, a polymer dispersant and a resinous binder which 4 K comprises monomer and/or oligomer of polyol-poly(allyl carbonate) compound.

The disclosed monomer and/or oligomer of polyolpoly(allyl carbonate) compound are the monomer of diethylene glycol bis(allyl carbonate) compound whose general formula is given below and/or the oligomer obtained by submitting said V X'o ~i.

3T--~U monomer to polymerization reaction in the presence of a polymerization initiator.

0 O

CH

2

=CH-CH

2 -0-C-O-CH 2

-CH

2 -0-CH 2

-CH

2 -0-C-O-CH 2

-CH=CH

2 The synthetic marble-forming composition comprising these g resins has the following disadvantages: The binder resin which includes the high molecular weight polymer described above has high viscosity.

Increased amount of inorganic filler in the synthetic marble-forming composition decreases seriously the fluidity of t/ the composition.

The resulted composition has poor workability such as moldability and shapability.

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems of the prior art and to provide a molded synthetic stone article having satisfactory chemical resistance, minimized polymerization shrinkage, high fluidity and high impact strength and a composition therefor.

The present invention provides a synthetic stone-forming composition comprising 10 to 90% by weight of a dialkyl 0 .compound containing an oligomer of a di- or trihydric alcohol 1 o carbonate as recurring units and 10 to 90% by weight of an S. inorganic filler as well as a molded synthetic stone article comprising a molded and polymerized product of the composition.

Preferably the inorganic filler is at least one member 2 selected from the group consisting of silica, glass, aluminum hydroxide, magnesium hydroxide, and mica.

Also preferably the oligomer of a dihydric alcohol carbonate has the following general formula: _t_

CH

2

=CH-CH

2 O R-O-C-0---CH-H=CH2 0 0 n wherein R is a residue of a dihydric alcohol, and n has a value or an average value in the range of from 2 to More preferably the inorganic filler is a balloon shaped inorganic filler.

DETAILED DESCRIPTION OF THE INVENTION The resinous component which is an essential component of the composition for molding a synthetic stone article according to the present invention is a diallyl compound containing an oligomer of a di- or trihydric alcohol carbonate as recurring /o units.

Preferred among these diallyl compounds are dihydric alcohol carbonat'e oligomers having the following general formula s0 t 4

CH

2

=CH-CH

2 -O-C-O R-O-C-0--CH 2

-CH=CH

2 (1) 0 0 n wherein R is a residue of a dihydric alcohol, and n has a value or an average value in the range of from 2 to The preferred bisallyl compound is the reaction product of diallyl carbonate and a dihydric alcohol in a molar ratio of 0 4:1 or lower, more preferably in a molar ratio of 2:1.

Preferred examples of the dihydric alcohol include Do ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane- "1 diol, diethylene glycol, polyethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, trimethylpentane diol, cyclohexane dimethanol, bis(hydroxymethyl)tricyclodecane, 2,7-norbornane diol, a,a'-xylene diol, 1,4-bis(hydroxyethoxybenzene), and 2,2-bis [4-(hydroxyethoxy)phenyl]propane alone and mixtures thereof.

LI The diallyl compound which constitutes the composition to be polymerized into the molded synthetic stone article of the present invention is preferably a liquid composition comprising components and shown below. Japanese Patent S Application Kokai No. 59-140214 is incorporated herein by reference.

The preferred composition comprises 10 to 90% by weight of an oligomer of a di(allyl carbonate) of an aliphatic, cycloaliphatic or aromatic dihydric io alcohol having the general formula:

CH

2

=CH-CH

2 -O-C-0 CH 2

-CH=CH

2 II 1I 0 n wherein R is a residue of a dihydric alcohol, and n has a value or an average value in the range of from 1 to 10, preferably from 2 to 10, or a mixture thereof with the proviso that the 15 content of a dihydric alcohol bis(allyl carbonate) monomer 4 optionally present in the oligomer is up to 50% by weight; 0 to 90% by weight of a compound selected from the group consisting of a monomeric di- or tri(allyl carbonate) of an aliphatic, cycloaliphatic or aromatic di- or 2o trihydric alcohol having the general formula: R' O-C-0-CH 2

-CH=CH

2 0 n' wherein R' is a residue of a di- or trihydric alcohol, and n' is equal to 2 or 3, or a mixture thereof, with the proviso that the S.content of an oligomeric di(allyl carbonate) of a di- or 2 trihydric alcohol or a poly(allyl carbonate) of a di- or trihydric alcohol optionally present in the monomer or the mixture is up to 30% by weight, an allyl ester of an.

aliphatic or aromatic di- or tricarboxylic acid having the general formula:

-I

I- 113~~ R" C-O-CH2-CH=CH 2 0 n" wherein R" is a residue of a di- or tricarboxylic acid, and n" is equal to 2 or 3, and triallyl cyanurate and triallyl isocyanurate; and 0 to 30% by weight of an acrylic or vinyl monomer; with the proviso that the total of components ana is more than 0.

The preferred component is the reaction product of diallyl carbonate and a dihydric alcohol in a molar ratio of 4:1 /o or lower, more preferably in a molar ratio of 2:1. The dihydric alcohol is preferably selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, trimethylpentane diol, cyclohexane dimethanol, bis(hydroxymethyl)tricyclodecane, 2,7-norbornane diol, aX,'-xylene diol, 1,4bis(hydroxyethoxybenzene), and 2,2-bis[4-(hydroxyethoxy)phenyl]propane.

The preferred component is the reaction product of a diallyl carbonate and a di- or trihydric alcohol in a molar ratio of 6:1 or higher, more preferably in a molar ratio of 12:1. The di- or trihydric alcohol is preferably selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, trimethylpentane diol, cyclohexane dimethanol, bis(hydroxymethyl)tricyclodecane, 2,7-norbornane diol, a,a'-xylene diol, 1,4-bis(hydroxyethoxybenzene), 2,2-bis[4-(hydroxyethoxy)phenyl]propane, trimethylol propane, and tri(hydroxyethyl) isocyanurate alone and mixtures thereof.

Also included in component are diallyl phthalate, diallyl succinate, diallyl adipate, diallyl chlorendate, diallyl tl: a glycolate, diallyl naphthalene dicarboxylate, and triallyl mellitate.

Component is preferably selected from vinyl acetate, vinyl benzoate, methyl methacrylate, phenyl methacrylate, methyl acrylate, methyl maleate, maleic anhydride, and vinylidene chloride alone and mixtures thereof.

The specific diallyl compound used herein may contain another monomer in such amounts that the other monomer does not detract from the physical properties of the resulting polymer.

t/o For example, a mono (meth)acrylic compound, di(meth)acrylic compound, or unsaturated carboxylic acid such as maleic anhydride may be added in an amount of up to 30% by weight, or a silane coupling agent such as vinyl triethoxysilane may be added in an amount of up to 10% by weight, based on the weight of the polymer.

The specific diallyl compound used in the synthetic stone-forming composition or molded synthetic stone articles of the present invention has a low polymerization shrinkage of 9- 10% as compared with diethylene glycol bisallyl carbonate monomer having a polymerization shrinkage of 14%, and produces a small amount of heat upon polymerization so that heat generation causes little difference in temperature distribution. Then a mixture of the specific diallyl compound and an inorganic filler can be polymerized into a molded synthetic stone article having high strength without leaving substantial internal strain.

The composition for forming molded synthetic stone articles according to the present invention contains the abovementioned resinous component and the following inorganic filler.

The inorganic filler is not particularly limited, but o0 preferably selected from silica, glass, aluminum hydroxide, magnesium hydroxide, mica, talc, titanium oxide, antimony trioxide, calcium carbonate, or a mixture of two or more of them.

i- 7 When silica and aluminum hydroxide are used, they preferably have a particle size of 1 to 30 p.m, more preferably to 20 p.m. Glass flakes are also advantageously used.

A balloon-shaped inorganic filler is used preferably.

The balloon-shaped inorganic filler is hollow articles of inorganic material, for example, alumina balloons, silica balloons, and glass balloons.

The balloon-shaped inorganic filler preferably has an apparent density of 0.1 to 0.5 g/c.c. and an average particle /o size of 10 to 100 p.m.

The use of glass balloons results in a molded synthetic stone article which has a specific gravity of less than 1 and a low thermal conductivity, exhibiting excellent thermal insulation or lagging when used as bathtubs or the like.

S jThe mixture of balloon-shaped and non-balloon-shaped inorganic filler may be used in this invention.

In this case, the resulted artificial stone article has low specific gravity, low thermal conductivity and high surface ohardness at the surface which contains more amount of nona zo balloon-shaped filler than that of balloon-shaped filler.

o:ao Inorganic fillers such as silica, and glass and aluminum hydroxide may be non-treated products, but preferably be surface o° treated with a coupling agent such as vinyl silane and acryloxysilane before mixing.

1° The synthetic stone-forming composition of the present invention comprises 10 to 90% by weight of the diallyl compound and 10 to 90% by weight of the inorganic filler, preferably a"g, to 40% by weight of the diallyl compound and 80 to 60% by weight aa: of the inorganic filler. When a balloon-shaped inorganic filler 3- is used, the synthetic stone-forming composition comprises more preferably 85 to 60% by weight of the diallyl compound and 15 to by weight of the balloon-shaped inorganic filler. Within this range, dense texture, mechanical strength and hect resistance are satisfactory as artificial stone.

I~ A polymeric dispersant may be added to the synthetic stone-forming composition of the present invention.

The polymeric dispersant is desirably one which is transparently dissolved in the diallyl compound used herein,

V

rC I- assists in evenly dispersing the inorganic filler, and increases the viscosity of the diallyl compound used herein. Preferred with respect to viscosity increase, for example, is the polymeric dispersant which is dissolved in the diallyl compound used herein in a concentration of 10% by weight such that the compound may have an apparent viscosity in the range of 1 to 200 poise as measured at 25 0 C with a B type viscometer. Further, the preferred polymeric dispersant should have useful functions of providing active sites capable of firmly binding to the /o inorganic filler, and assisting in dispersion of the inorganic filler.

The polymeric dispersant which meets these requirements includes homopolymers and copolymers of unsaturated carboxylic acid esters, for example, homopolymers and copolymers of polymethacrylic acid esters and polyacrylic acid esters. These Spolymers may be used in the form of beads having a particle size of about 1 mm or pellets and are commercially readily available.

0The composition for forming the molded synthetic stone article according to the present invention may further contain a -o polymerization initiator in advance.

The polymerization initiator used herein may be any of photo polymerization initiators, thermal polymerization initiators, and photo and thermal polymerization initiators, and mixtures thereof.

The photo polymerization initiators include electron beam and radiation polymerization initiators as well as photo polymerization initiators.

A typical example of the photo polymerization initiator is 2-hydroxy-2-methyl-l-phenyl-propan-l-one.

C Examples of the thermal polymerization initiators include peroxydicarbonates such as diisopropyl peroxydicarbonate, disec-butyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and tert-butyl perbenzoate; organic peroxides such as benzoyl peroxide, acetyl peroxide, tert-butyl hydroperoxide, cumene 3 5 hydroperoxide, di-tert-butyl peroxide, tert-butyl L peroxybenzoate, lauroyl peroxide, diisopropyl peroxydicarbonate, dimethyl ethyl ketone peroxide, and diacyl peroxide; and radical initiators such as azobisisobutyronitrile and azobismethylisovaleronitrile.

A typical example of the photo and thermal polymerization initiators is the compound of the following formula: 0 0 0 (t-Bu) -00-C C C-00- (t-Bu) (t-Bu) -00-C C-00- (t-Bu) II II 0 0 Polymerization initiator may be used in an amount of So 0.1 to 10% by weight, preferably 1 to 6% by weight based on the diallyl compound used herein.

In addition to the essential components mentioned above, ,,the synthetic stone-forming composition of the present invention may contain other synthetic resin, natural resin, pigments, flame retardants, ultraviolet absorbers and other additives in amounts not detrimental to the effectiveness of the present invention.

A molded artificial stone article may be prepared from the synthetic stone-forming composition by polymerizing and 2_ curing the composition and any of well-known methods is applicable as the polymerizing and curing method.

One exemplary method involves mixing the diallyl compound, the inorganic filler and optionally, other additives under vacuum or in an inert atmosphere, further admixing the polymerization initiator therewith, casting the composition into a mold, heating the composition, taking off the mold, and further heating the composition to complete polymerization.

When a balloon-shaped inorganic filler is used, the moldedsynthetic stone article of the present invention co preferably has a density in the range of 0.4 to 1 g/cm 3 and a i" z:f~, _i thermal conductivity of up to 0.4 especially up to 0.3 The molded synthetic stone articles of the present invention are used as synthetic marble in various applications including sanitary ware like washstands, bathtubs, and kitchen units, as well as building interiors and exteriors.

Examples Examples of the present invention are given below by way of illustration. The present invention is not limited to these examples.

/o Compositions A and B used in Examples are shown below.

Composition A The reaction product obtained by reacting diallyl carbonate with diethylene glycol in a molar ratio of 2:1 in the presence of sodium ethoxide under the conditions described in Japanese Patent Application KoKai No. 56- 133246 (consisting of 30% by weight of diethylene glycol bisallyl carbonate and 70% by weight of oligo-carbonate, n 3 to 10) 55% by weight Tris(allyl carbonate) of tris(hydroxyethyl) isocyanurate o obtained by reacting diallyl carbonate with tris(hydroxyethyl) isocyanurate in a molar ratio of 12:1 12.4% by weight Diethylene glycol bisallyl carbonate 27.5% by weight Vinyl acetate 5% by weight Composition B The reaction product obtained by reacting diallyl carbonate with diethylene glycol in a molar ratio of 2:1 in the presence of sodium ethoxide under the conditions 3o described in Japanese Patent Application Kokai No. 56- 11 133246 (consisting of 30% by weight of diethylene glycol bisallyl carbonate and 70% by weight of oligo-carbonate, n 3 to 10) 58% by weight Tris(allyl carbonate) of tris(hydroxyethyl) isocyanur.rte obtained by reacting diallyl carbonate with tris(hydroxyethyl) isocyanurate in a molar ratio of 12:1 13% by weight Diethylene glycol bisallyl carbonate 29% by weight c Example 1 43 parts by weight of Composition A of bisallyl compound containing 2.5% by weight of diisopropyl peroxydicarbonate and by weight of triethoxyvinyl silane based on the weight of Composition A was blended with 57 parts by weight of silica having a particle size of 3-30 pLm and a bulk specific gravity of 0.67 g/cm 3 (Crystalite A-A manufactured by Tatsumori Industries under a vacuum of 50 mmHg. The mixture was cast into a mold of glass with a flexible gasket having a cavity demensioned 300 x 400 x 10 mm. The temperature was raised from 400C to 800C oQ over 8 hours. The mold was taken off and then the molding was heated at 1100C for one hour to complete polymerization.

The molded article had the physical properties shown in Table 1. Chemical resistance was determined by immersing molded samples in 10% sulfuric acid, 10% acetic acid, 10% nitric acid, 10% hydrochloric acid, methanol, isopropyl alcohol, acetone, MEK, butyl acetate, dimethylformamide, nitrobenzene, xylene, cyclohexane, and trichloroethylene for 60 days, finding no defects.

A lit cigaret was allowed to stand on the molded article, o resulting in neither depression nor deformation.

Examples 2. 3, 5 6 Molded articles were prepared by the same procedure as in Example 1 except that the silica was replaced by the inorganic lll~rcr I~I fillers shown in Table 1 (the detail data of the fillers are shown in Table The molded articles obtained were tested, with the results shown in Table 1.

Example 4 s A molded article was prepared by the same procedure as in Example 1 except that the silica was replaced by glass flakes and Composition A was replaced by Composition B. The molded article was similarly tested, with the results shown in Table 1.

Example 7 /o A molded article was prepared by the same procedure as in Example 1 except that the silica was replaced by vinyl silane treated Al fOH)3 and composition A was replaced by Composition B.

The molded article was similarly tested, with the results shown in Table 1, (S Chemical resistance was determined by immersing the molded samples of Examples 2-6 in 10% sdlfuric acid, 10% acetic acid, 10% nitric acid, 10% hydrochloric acid, methanol, isopropyl alcohol, acetone, MEK, butyl acetate, dimethylformamide, nitrobenzene, xylene, cyclohexane, and L_ trichloroethylene for 60 days, finding defects in none of the samples.

A lit cigaret was allowed to stand on each of the molded articles of Examples 2-6, finding depression or deformation in none of the samples.

5 CLmparative Example 1 A molded article was prepared by the same procedure as in S'Example 1 except that diethylene glycol diallyl carbonate monomer containing 5% by weight of diisopropyl peroxydicarbonate was used as the resinous component. The molded article was similarly tested, with the results shown in Table 1.

Cs Cs C Tabele 1 Example I Example 2 Example 3 Example 4 Example 5 Example 6 Rlesin Composition Composition Composition Composition Composition Composition A A A B A Filler S10 2 Glass flakes Al (011)3 Glass flakes CaC0 3 Mica (Amount) -A GB731-M 11-32 GO-All #200 #100 wt 5)(63) (57) (68) (50) (2b/ Density g/cm 1.81 1.91 1. 7 8 1.99 1.64 Flexural modulus kg/mm 2 353 195 2 5 2 174 115 173 Flexural strength k g/mm 2 3.03 1.87 2. 1 6 1.11 1.30 1.73 Compression strength hg/mm 2 588 282 6 6 1 221 468 348 impact st.-ength kg. cm/cm 1.7 1.68 1 6 1.74 1.7 (notched) Rockwell hardness M-scale 90 82 8 9 81 81 Shore hardness D-scale 85 77 8 4 74 74 (3 mimT) Pencil hardness 511 411 4 If 511 311 311 'rilermal conductivity W/ (m 0.9809 0.4784 0. 9 988 0.4562 0.4728 0.4040 -7 Table 1 con't Example 7 Comparative Example 1 Resin Compositicn diethylene glycol diallyl B carbonate monomer Filler Vinyl silane Si02 Amount treated A(01I) 3

A-A

wt% 11-32 (57) (68) Density g/cm 1.92 1.82 Flexural modulus kg/mm 2 955 265 Flexural strength kg/mm 2 8.1 2.2 Compression strength kg/mm 2 1368 490 ISOD impact strength kg.cm/cm 1.91 1.2 (notched) Rockwell hardness M-scale 88 Shore hardness D-scale 92 81 (3 mmT) Pencil hardness 5H1 411 Thermal conductivity 0.9820 1 ~1 111 Table 2 Glass flakes A .9 (O0H 3 SiO 2 CaC0 3 Mica Toshiba Toshiba Toshiba 1lijilite Crystalite Escaron Indian Mica GB731- I11301- GB-All 11-32 A-A #1200 #1100 Manuf acturer T o s h 1 ba G I a ss s K X Showa Denko. Ta tsumori Sankyc Yamada K.K. Industries K.K. Flour ILK. Industries K.K.

Chemical composition SiO,/Na 2

O/K

2 0/CaO/Al 2 0 3 soda glass A.9 (OH) 3 S i 02 C a CO0 3 Si0 2

/A-Q

2 00/ 2 0 Density. g/cc 2. 5 2. r 2. 6 2. 8 ~Specific surface area in 2 /g 2. 0 1. 8 2. 1 Apparent density g/cc 0. 7 0. 6 7 0. 01 7 Average particle size in 1 8 3. 5 0. 4 0 Particle size 565i .100% 180'-75 i 90'-45g ji ;40g .0.05% 530 g *100?% 44 74 g .31.5% distribution 33g.t 8% Z 80% >50% 0 9 7% 74 '-149 g .45 :519 M. 5% 5g.~t 85% 149 '-297 it 20.5% ;513 g. 2% 10Ig 69% 297 '-'710 2 i8g. 1% :1 5 5g, 16 Example 8 parts by weight of a composition containging Composition B, 2.5% by weight of diisopropyl peroxydicarbonate, and 1.0% by weight of triethoxyvinyl silane based on the weight of Composition A was blended with 25 parts by weight of glass balloons having an average particle size of 40 Lm (Kalloon manufactured by Japan Galss under a vacuum of 50 mmHg.

The mixture was cast into a mold of glass with a flexible gasket having a cavity demensioned 300 x 400 x 10 mm. The temperature /o was raised from 40 0 C to 80 0 C over 8 hours. The mold was taken off and then the molding was heated at 110 0 C for one hour to complete polymerization.

The molded article had a tensil strength of 1.7 kg/mm 2 a flexural strength of 2.5 kg/mm 2 an Izod impact strength of 0.8 kg-cm/cm, a Rockwell hardness (M scale) of 80, and a pencil hardness of H. It was lighweight as demonstrated by a density of 0.79? g/cm 3 and had a thermal conductivity of 0.162 W/(m.k) which was markedly lower than the existing synthetic mable (Koryan available from E.I. duPont) having a thermal Io conductivity of 1.2 Chemical resistance was determined by immersing molded samples in 10% sulfuric acid, 10% acetic acid, 10% nitric acid, 10% hydrochloric acid, methanol, isopropyl alcohol, acetone, MEK, butyl acetate, dimethylformamide, nitrobenzene, xylene, cyclohexane, and trichloroethylene for 60 days, finding no defects. A lit cigaret was allowed to lay on the molded article, resulting in S;neither depression nor deformation.

Examples 9 and Molded articles were prepared by the same procedure as in 1o Example 8 except that the glass balloons were replaced by the glass balloons shown in Table 3 (the detail data of the glass balloons are shown in Table 4) and Composition B was replaced by Composition A. The molded articles obtained were tested, with the results shown in Table 3.

I C 17 Comparative Example 2 For comparison purposes, a molded article was prepared by the same procedure as in Example 8 except that a composition containing diethylene glycol bisallyl carbonate monomer as a g resinous component and 5% by weight of diisopropyl peroxydicarbonate was used and the type of filler was changed.

The molded article was similarly tested, with the results shown in Table 3.

0 00 0 0 0 0 0 0 0 4 0 C 0 0 0 0 4 0 00 0 0 0 0 00 0 40 0 000 00 0 0 0 0 00 0 0 -4 40 *40 0 004 0 0 0 C~ S 0 0 0 0 0Q 0 0 040 TablIe 3 Example 8 Example 9 Comparative Example 2 Resin Composition Composition Diethylene glycol A A diallyl carbonate monomer Filler Glass balloon, Glass bailoon, Glass flake, amut M I croceIlI 35 Hal loon C 1 0 G B7 3 1 -M 25 2 5) 63) Dens!ity /c M 1.0 1.0 1.9 1 Tensile strength kg/mm 2 1 7 5 1 .6 1 1 .1 6 Flexural modulus kg/mm 2 1 6 4 1 8 7 1 9 Flexural strength k g/mm 2 2 7 9 2 .5 2 1 8 7 Comipression strength k g/mm 2 4 0 3 4 1 6 2 8 2 1Z 0D I m p act kg -cm/cm 0 7 6 0 4 8 1 .6 8 strength (notched) Rockwell hardness li-scale 8 0 7 0 8 2 Shore hardness D-scale 7 1 7 0 7 7 (3 minT) Pencil hardness 11 H B 4 H Thermal conductivity 0 .1 8 2 7 0 1 6 1 9 0 4 7 13 4 r Table 4 Glass balloon ?Aicrocell 3 5 Glass balloon Kalloon C 1 0 Manufacturer Chemical composition Asahi Glass K.K.

borosilcate glass Nihon Glass L..

Glass flake Toshiba G B 7 3 1 -M Toshiba GlassK.K.

Si0 2 /Na 2

O/K

2 0/ CaO/A. soda glass Density g/cc 0. 3 5 0. 3 8 2. Specific heat. KJ/kg K 0. 8 0. 2 8 Apparent density. g/cc 0. 1 9 Average particle size, g m 6 0 8 0 4 0 1 8 Particle dize :5250 g 100% 0 g, 90% ;565 g 100% distribution ;:55 g 95- ;540 g 50% ;533 g, 8% 100% ;:55 g. 10% ;5 Isg 5 g' 0- ::53 g, 2% ;58 g 1% Surface treating agent vinyl silane The synthetic stone-forming composition of the present invention which comprises a resinous component in the form of a diallyl compound containing an oligomer of a di- or trihydric alcohol carbonate as recurring units can be polymerized into a molded synthetic stone article having satisfactory chemical resistance and heat resistance, minimized polymerization shrinkage, and high impact strength.

The claims form part of the disclosure of this specification.

I

Claims (9)

1. A synthetic stone-forming composition comprising to 90% by weight of a diallyl compound containing an oligomer of a di- or trihydric alcohol carbonate as recurring units and tu 90% by weight of an inorganic filler.

2. The synthetic stone-forning composition as set forth in claim 1 wherein said inorganic filler comprises at least one member selected from the group consisting of silica, glass, aluminum hydroxide, magnesium hydroxide, and mica. /o

3. The synthetic stone-forming composition as set forth in claim 1, wherein said oligomer of a dihydric alcohol carbonate has the following general formula: CH2=CH-CH 2 R- -CH=CH 2 II II 0 O n rt wherein R is a residue of a dihydric alcohol, and n has a value /S or an average value in the range of from 2 to

4. A synthetic stone-forming composition as set forth in claim 1 wherein said inorganic filler is a balloon shaped S: inorganic filler. oa a 0,

5. A moulded synthetic stone article comprising a moulded and 2 1 polymerized product of a composition comprising to 90% by weight of a diallyl compound containing an oligomer of a di- or trihydric alcohol carbonate as recurring Sunits and to 90% by weight of an inorganic filler.

6. A moulded synthetic stone article as set forth in claim wherein said inorganic filler comprises at least one member selected cJ"6~ y 22 from the group consisting of silica, glass, aluminum hydroxide, magnesium hydroxide, and mica.

7. A moulded synthetic stone article as set forth in claim wherein said oligomer of a dihydric alcohol carbonate has the following general formula: CH2=CH-CH2-O-C-O--R-O-C-O--CH 2 -CH=CH 2 II II 0 O n wherein R is a residue of a dihydric alcohol, and n has a value or an average value in the range of from 2 to

8. A moulded synthetic stone article as set forth in claim /o wherein said inorganic filler is a balloon shaped inorganic filler.

9. A composition substantially as herein described with reference to any one of the examples. A moulded synthetic ston article substantially as herein described with reference to any one of the examples. DATED THIS 22nd May, 1992 CARTER SMITH BEADLE Fellows Institute of Patent Attorneys of Australia. Patent Attorneys for the Applicant MITSUI PETROCHEMICAL INDUSTRIES, LTD. CT