TW209237B - Resin composition for artificial marble - Google Patents

Abstract

To develop an allyl series resin composition for artificial marble which has improvement on hardenability without deteriorating the formability possessing by conventional allyl ester resin, the surface hardness as the resin for artificial marble and the merit of boiling resistance. The object is achievable by the resin composition for artificial marble made from (a) 30-95 wt% of an allyl ester oligomer having the following repeating unit I and II, or I, II and III: -(COACOOBO)- (I); -(CO-CH=CH-COOBO)- (II); -(COYCOO)X-ZO-COYCOO- (III), and having a molar ratio of 0.05s-CH=CH-/As4 and having the allyl ester group at the end of the oligoma, (in which A is a divalent aromatic organic acid or an organic residue derived from saturated organic aliphatic acid having 2 to 20 carbon atoms, B is a divalent organic residue derived from diol having 2 to 30 carbon atoms, Y is above-mentioned A or -CH=CH-, X is an integer of 2 to 10, Z is an organic residue group derived from a polyol having X+1 hydroxy group), (b) 5-70 wt% of a reactive monomer selected from the group consisting of methyl (metha) acrylate, styrene, maleic anhydride, dimethyl maleate, allyl benzoate, diallyl phthalate, dially isophthalate, diallyl terephthala.

Description

The Ministry of Economic Affairs, the Ministry of Economic Affairs, the Pyongyang Bureau of Industry and Commerce cooperated with Du Yin 5i 82 '5, 31 V. Description of the invention (1) The invention is based on a resin composition for artificial marble, especially with the appearance of marble. In addition to its high strength and wear resistance, the moldable resin composition for Rendi marble. The conventional artificial marble competition is used for face-washing and dressing tables, baths, K-equivalent kitchen equipment, and interior and exterior decoration materials for construction. When the artificial marble is used as a resin molded product, the resin that constitutes the artificial marble substrate can be molded by the injection molding method, and a composition obtained by mixing, for example, no eaves filling agent or tweezers-shaped reinforcing material is sufficient for molding. Chess is hardened. Another molding method is to use inorganic fillers mixed with resin and other additives. SMC (sheet molding composition) impregnated with glass male, and the two sides are sandwiched by a film into a sheet, or similarly formed into a block The BMC (block molding composition) is compressed and molded. The resin used as the base material is generally a methacrylate resin, an unsaturated polyester resin, or a gas resin, which is used as a resin for artificial marble, which is improved separately. However, the resin used in the compression molding method cannot be completed without using any system. Even if the most researched 6 and polyester resins are used, the blending system of transparency and gloss is not yet available. In particular, when transparency is emphasized and a low shrinkage agent is not used, it is easy to crack during molding, which is not practical and poses a problem. (Please read the precautions first and then write the hard copy Γ / big, ffi does not need to be formed by someone else. It can be sowed. The turtle and the inferior type have become easy to use, showing a unique form, The perinatal period is filled with sinus, and the type has grown into a film. The previous period of rapid coating industry Zhoujia® Η type test is available in Chengshang. Although the method is attached, the temperature is square and the lack is high. For Wll bil PL, the paper size is used in the B-Ming family's standard (() 肀 4 specifications (210X297 male dragon) 81. 2. 20,000 82. 5. 3,1 by the Ministry of Finance Standards, ^ β 工 消 扑 合作社 印 ft ,, 4 Λ (i I "; _ V. Invention description (2) The intended productivity is the problem. Especially when using unsaturated polyester resins, the surface hardness is not as high as The degree of meaning, once acrylic resin has low viscosity of boiling boilability, so far there is no resin that meets all the physical performance requirements of artificial marble. The inventors have adopted the following allyl ester resin as the substrate resin, and submitted a patent Shen Zhao (Hei 3-339557¾ Description):-(COArCOOB · 0)-Structure- A-(COArCOO) x '-Z' -0-C0ArC00- Structure j fi-B, where the terminal has an allyl ester group, X 'is an integer from 2 to 10, Z' is an organic residue derived from a polyester having X '+ 1 hydroxyl group, B · represents C2-7 diol Derivative divalent organic residues. Ar is 1,2-, 1,3- or 1,4-phenylene. This article can be compressed and molded, and it is not easy to crack. Low rate. With excellent gloss, it can give artificial marble molded products with special withdrawal. Surface hardness, boiling resistance is also excellent, the physical energy of artificial marble resin is the most balanced. However, the disadvantage is hard; ib speed "slow, below 100 it When the satisfactory hardening speed is not obtained, it must be molded at a high temperature, and the injection wedge molding method that is generally performed cannot be applied. Moreover, compression molding is not used, and it is completely hardened because it does not crack. The purpose of the present invention is not to impair the conventional moldability of allyl sugar resin, the surface hardness of artificial marble resin, excellent boiling resistance and other characteristics. It can improve the hardenability. -4- (Please tell me in advance And remember the matter and then write a wooden outfit-_ _ line-this paper ruler National B-Sample (CNS) Ή Regulations (210x297 public) 81. 2. 20,000 Λ 6 η 6 Ministry of Economic Affairs Central Bureau of Employee Protection &Cooperation; Duinu V. Description of the invention (3) The present invention In order to accelerate the hardening speed, people conducted various research results and found that the combination of an allyl ester resin with a specific structure and an anti-molecular monotene can improve the hardenability and complete the present invention. Is U) the following allyl oligomer 30-95 weight; IX (b) anti-numb monomer 5-70 weight X resin composition for artificial marble; wherein, the allyl oligomer image has the following repeat Unit:-(C0AC00B0)-Structure I-(C0-CH = CH-C00B0)-Structure I S0.05S -CH = CH- / AS 4 (molby), the terminal bat has an allyl ester group, in the formula , A is eaves residue derived from C2_20 divalent aromatic organic acid or saturated organic fatty acid, and B is divalent organic residue derived from C2-30 binary enzyme. The second item of the patent application of the present invention is U) the following allyl ester oligomers 30-95 weight X (b) Reactive monomer 5-570 weight X Resin composition for human entry marble; wherein, allyl The ester oligomer has the following repeating units:-(C0AC00B0)-Structure I-(C0-CH = CH-C00B0)-Structure I-(C0YC00) X -ZO-COYCOO- Configuration and 0.05S-CH = CH -/ AS4 (Cheer tb>, the terminal mites have allyl groups, -5-(please read the precautions before writing this page) This paper scale uses the Chinese National Standard (CNS) A4 specifications ( 210x297 male dragon) 81. 20,000 ～ 1—tmmu—i 丨 丨, — 5. 31 Λ (ί Π (i Printed by the Central Bureau of Economic Affairs, Ministry of Economic Affairs, Mongong Pricing Cooperative Society) V. Description of the invention (4) In the formula, A Eaves residues derived from C2 -20 divalent aromatic organic acids or saturated eaves fatty acids. B is divalent organic residues derived from C2 -30 binary enzymes Y is above A or -CH = CH-, X is an integer from 2 to 10, and Z represents an organic residue derived from a multiplex enzyme having a hydroxyl group of X +〗. The above structure] [medium double bond (-CH = CH-), regardless of cis or trans form, can be derived Beta (: 2-2 Binary leaven has ethane leaven, Malonylase, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentylase, 1,5-pentanediol, adipic enzyme. Pimerolase, octane Glycol, azelaine, sebaceous leaven, dodecane two leaven, twelve master two leaven, thirteen nitrate two leaven, twenty sulfonate two leaven, hydroconcentol-A, 1,4-chen adipose leaven, 2-ethyl-2,5-pentanediol, 2-ethyl-1, 3-hexanediol, benzoethylenediester, etc., containing only saturated diester composed of saccharomyces, as well as diethylenediester, triethylester Di-enzyme • Polyethylene-di-enzyme, di-propane-di-enzyme, Phenol-A-cyclic ethane adducts. Biphenol-A-Chen gas propane adducts and other ether-containing divalent saturated alcohols, or tribromoxin Bromodiols such as glutarase, etc. Among them, when using malonulase, or 1,3-butanedienase, dipropanedienase and other two enzymes, the compatibility with other copolymerizable monomers is good. The transparency is also good. Neoglutarase is excellent in weather resistance and boiling resistance. When using the diphenol-A adduct of bisphenol-A, the refractive index of the hardened product increases and the transparency is good. The derivative Z has X + 1 is a multi-enzyme of hydroxyl group, including ternary enzyme, trimethylolpropane and other aliphatic ternary enzyme; pentaerythritol, sorbic acid enzyme Fatty enzymes with more than four valences such as aliphatics. These uses are very good from the viewpoint of heat resistance, raw -6- (please read the precautions first and then the tips ^) * ΤΛ, · 5 ·

T% This paper scale uses the China® National Standard (CNS) * f 4 gauge (210x297 g) 81. 2. 20,000 _Λ! | _ V. Description of the invention (5) Allyl ester oligomer viscosity To increase, it is appropriate to use a small amount. The divalent aromatic organic acids or saturated organic fatty acids (hereinafter referred to as "saturated carboxylic acid J") shown in A are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 々-methylhexane Diacid, pimelic acid, suberic acid, azelaic acid, sebacic acid. Undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, 1,2- or 1, 3- or 1,4-Adipic acid, phthalic acid, isophthalic acid. Terephthalic acid, diphenyl-ρ, ρ'-dicarboxylic acid, diphenyl-, m'-dicarboxylic acid , 1,4- or 1,5- or 2,6- or 2,7-naphthalenedicarboxylic acid. Diphenylmethane-ρ, ρ · -di · dipic acid, diphenylmethane- *, * · -di Carboxylic acid, benzophenone-4,4'-dicarboxylic acid, terephthalic acid, p-carboxyphenylacetic acid, methyl terephthalic acid, tetrahydrophthalic acid, etc. Among them, terephthalic acid or isophthalic acid Divalent saturated carboxylic acids containing benzene such as phthalic acid are particularly good in improving heat resistance and boilability. Divalent unsaturated carboxylic acids with cis or trans-CH = CH-, maleic ether and rich Ma acid. (Please read ^ Backward notes 孥 塥 Write this tile "装 装-线 线-Ministry of Economic Affairs, Bureau of Standards, CX, Gongxian, Cooperation, Du Yin 3i's enke h). Acid Z. The order is 5 to make horses and make up, U controls B-rich esters of moles (* Yihesheng and propionidine acid derivative should be different in proportion and inverse, shrinking in the ear horses with esters, inexplicable, shrinking When the raw material is formed by the conversion of propyl ester ester fcb into methyl propylene, and the conversion of the carboxylic acid ester into the carboxypropyl ester is possible. , Oligomeric and deene than polydiallyl with Π, making this ester W, storage structure. Propylene, ^ in the Communist Party, should be suspected ester, Yelu I is equal to propanol Η over C to create this ene in Alcohol-formed garden two-polypropylene template paper size side use China National Standard (CNS) A 4 specifications (2 丨 0X297; it) 81, 2. 20,000 V. Description of the invention (6 Λ 6 B 6 These allyl The ratio of each component in the structure of the ester oligomer can be determined according to the molar ratio of its raw material, and it is preferably limited to the ratio range shown in the following formula. In the following model garden: φ 0.05 ^ -CH = CH- / A ^ 4 The invention claims the patent model _ Item 2 allyl ester oligomeric structure, in the following formula 1 to 3 model garden: Φ 0, 0 5 S-CH = C Η-/ A forget 4② B = 0, Z is off 0, and Z = 0, B # 0 ③ 1.005 < (A + -CH = CH-) X2 / {BX2 + ZX (X +}} < 3 divalent with double bond The ratio of unsaturated carboxylic acid to divalent saturated carboxylic acid. As shown in formula (1), the molar ratio of -CH = CH- / A is 0.05-4, preferably within the range of 0.1-2. This ratio is too When it is low, the sulfonation property of the allyl acid oligomer cannot be improved. However, when it is too far away, the good moldability of the allyl oligomer will be lost. What's the use of too 0 Μ, so that ζ ZO and 'Β again. Solution one yuan its multi-purpose and make yeast must be less than two (please read the precautions of the poor and then fill out this page; install. * 可. 线The Ministry of Economic Affairs, Central Bureau of Standards, M Industry, Consumer Cooperation, Du Printing and A. The use of it avoids avoiding the use of ο. ③ The ratio of the total rate to the total rate of the total enzyme is more than two enzymes and the value of the propylene volatilization method is not too low. The rate is lower than the value of C 1 in the case of ester propylene. Poly C This paper uses the Chinese National Standard B (CNS) specifications (2 丨 0X297 public: «:) 81. 2. 20,000 Λ (i η (ί η (ί Central Ministry of Economic Affairs, Central Bureau of Standards, β-consumer work, cooperation, cooperation, duin ¾ V. Inventions Description (7) Although the allyl ester oligomer used in the present invention contains unreversed residual allyl ester monomers such as diallyl terephthalate, diallyl maleate, etc., but As long as it meets the above-mentioned range, it doesn't matter. However, when the above value is too large, the residual monomer concentration will be too high and must be separated from the monomer, otherwise the problem of too high shrinkage will occur. The molecular weight of the allyl ester oligomer used in the present invention is determined by GPC (Condensation Permeation Color Analysis) method, and the average molecular weight (Mn) of polystyrene-converted JR is more than 500, preferably 800 or more. When the molecular weight is too high, the viscosity will be too high, or it will become solid, making handling difficult. . The molecular weight of the oligomer described by GPC is determined by the following method. One SH0DEX column AC-80P, 802, 804, 806 each was connected in series, using chloroform as the solvent, the column temperature was 2513, and measured at the flow rate I.ObI/b i η. ① First, at least 10 types of commercially available standard polystyrene with a known average molecular S are used, and the retention time together with the DAT monomer is determined. The average molecular weight and the retention time are pseudo-curved to form a cubic curve, or a calibration curve that approximates a broken line. ② Take 20 mg of the sample and dissolve it in 20 ml of the human-made atmosphere, and use the Naruto ejector. • Inject 0.5 ml through the linear filter into the column. Based on the calibration curve created by ®, the obtained dissolution curve data is automatically calculated in the Shimadzu CR-3A2_ data processor to obtain sum > 4 *. The peaks are separated at 10 second intervals, and the molecular director at two points is Mi, and the height of the peak is Hi -9- (please read the backing notes first # 蜞 写 木 一 本 paper scale using Chinese music standards (CNS) A4 specification (210X297 male dragon) 81. 20,000 2 The Ministry of Economic Affairs Central Bureau of Labor and Welfare employees cooperated to print the fifth, invention description (8, calculated by the following formula: Σ 11

Mw = Σ i Other reactive monomers can also be added in the present invention to improve viscosity, polymerizability, or surface hardness. Anti-negative monomers such as unsaturated fatty acid esters, such as unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and their derivatives, unsaturated dibasic acids and their derivatives, abalone and lipid or aromatic carboxyl Vinyl acid esters or allyl esters, and their derivatives, (meth) acrylonitrile and other cyanide vinyl compounds and other acid esters < ¥ 3 base methene vinyl, {metha / 1 / 6J § JXS ( Yin Yin β,, > 丨 _ Benzene _ ', _ ylyl phenyl ester _ methyl bromobenzene methyl propionate. _Ίί} ene three bis aryl ester ene, such as propionyl _ propyl aryl acrylate > Suspected acidity- > butylhexyl propyl allyl propionate ring-meth) > propene > methacrylate < yl} yl methacrylic acid, methylmethyl methyl: > propanyl_ester {< metholyl group} nil ,, ί isopropyl methyl propan-1-ester ester and other esters methacrylic acid phenyl ester oil fat, yl ethyl bromide methyl glycolate, methyl propionic acid gas benzene water and Ethyl ethyl methyl ethyl hexanoate, propyl propionic acid __ not allyl ester methyl, > allyl allyl ethyl yl propyl propyl propylene This paper standard is used in the HS home standard (CNS) T4 specification (210X297 Public; ¢) 81. 2. 20,000 (please read the backnote first Please fill in this page again. J tzrl A 6 n 6 V. Description of the invention (9 IS of the Ministry of Economic Affairs, Bureau of Standards, IS: industrial and consumer cooperation, du printed, gas-based Ν'amine Ν 膯 Ν vest acid-rich acid CS) two three Ethylene, gas, acetone. Lai, Daidi, horse cheese, etc. Fermentation, propylene divinyl methyl ester enamine, amine, and acetic acid esters and esters ® {二 _i) zygyl, propylene subunit N-Lysin, its, malondiacetoxydiyl styrene S) Maleic acid such as acetyl hexamethylene and acrylonitrile triene pentyl methionyl propionate melamine, acid propionate enoic acid di, Benzene 5-I takes benzene. Equine N-maleic acid to isopropyl methyl acetic acid} yeast 1, αι group and other groups, such as carboxylic acid benzene, such as acid group two, α · methyl methyl acetic acid methylamine benzene, acid or A, for example, butyl methyl esters are similar to diene buylene, phenyl esters of butyl esters have propylene 3-acrylic acid, with N-propyl: butyrene, methacrylic acid, butadiene, propylene,} 2,1, ene styrene , «, ^ There are lenbenben, ethyl ethyl vinyl body enzyme. Propyl: styrene, fumar, ramarate. Acid enoic acid monomethyl diester i) cyanobenzene. Aminoamines Aminoamines Carboxylic acid from water and other carboxyethylpropylene acetic acid «Compound I bromoene derivative, butylene N- no horse diester family _, official ditetraene (¥ combined α, ethylene Its N-acyl ,,, propyl acid octanoate multi-enzyme, malonization. Enbenzene and propylamine and, maleate esters of maleic acid, propionate diester 丨 Enzymatic acetoacetic acid &) amine acid malayl Acetoic acid or ester vinylacetate diacetoxyethylbenzene is a fatty acid ethylidene subunit amide, oxalic acid cross-diene methyl butyl ethyl benzonitrile ribopropylene benzene, __ Selenium ethyl Use, propylene 4-group group-equivalent group «) and to N-maleimide, fatty acid, ester} di 1 fenvinene saturated ΦΙΙ full horse, kiyama diester and ethyl ester _ Basic fermentation, aromatic I, ethyl, ethyl, amine, benzoyl, acid, butene, methacrylic acid, alpha, phenyl, N-, etc., ethylchloride, methyl chloride, ethylpropyl, propionic acid (please read the back And the precautions # 塡 写 此 page "Binding · The size of the paper is used in the Chinese National Standard (CNS) A 4 specifications (210x297; ¢) 81. 2. 20,000 Λ 6 B 6 Employee consumption of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative. 5. Description of the invention (10) (meth) acrylic acid, 1 , 6-hexamethylene diacrylic acid di (meth)> Acrylic pain, neopentyl diacid di (meth) acrylate, hydroxypivalic acid neopentyl diacrylic acid ester di (meth) acrylic acid oligoester di (methyl) Acrylate, polybutadiene di (meth) acrylate, 2,2-bis (4-methyl) acryloylphenyl) propane, 2.2- «(4- (ω- (methyl> propylene Acetyl-based polyethylene) phenyl) propane, 2.2-bis (4- (〇 ;-( meth) acrylic acetyl-based polyethylene) dibromophenyl) propane, 2,2-bis (4 -(ω- (meth) acryloyloxypolypropylene gas> phenyl) propane, bis (4- (ω- (methyl> acryloylpolyethylene gas) phenyl) methane and other di ( Methyl> Acrylic ester, or diallyl phthalate, diallyl isophthalate, diallyl terephthalic acid, diallyl 2,6-dicarboxylic acid Ester, diallyl adipate, 1,4- or 1,3- or 1,2-cycloadipate diallyl, _ diallyl surface, diallyl ethanedisulfonate_ , Divinylbenzene, Ν, Ν'-m-phenylene bismaleimide and other difunctional cross-linkable monoamine, trimethylolethane tri (methyl> Enoate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate_, trifmethyl) allyl isocyanate, tri (methyl> allyl cyanate Ester. Triallyl phthalate, Diallyl Chlorendate, diallyl maleate, diallyl fumarate and other trifunctional crosslinking monomers, Pentaerythritol four (meth) acrylate and other four-functional cross-linking monobloc, etc. In addition, unsaturated polyacid resin or vinyl ester tree can also be used as these copolymerizable monomers. Which takes into account the copolymerization of allyl groups in polymerizable oligomers, above -1 2-(please read the precautions before writing this page) Sample standard (CNS) 〒 4 specifications (2〗 0 father 297 male dragon) 81. 2. 20,000 da- o Ministry of Economic Affairs 3-Central Standards Bureau employee consumption cooperation to produce Λ 6 _ V. Description of invention Cli) Aromatic allyl esters such as propyl phthalate, diallyl isophthalate, diallyl terephthalic acid, etc. (meth> acrylates, vinyl acetate are preferred. In addition, In order to increase the reactive monomer, there are 2,6-dicarboxylic acid diallyl, and in order to improve the surface hardness, it is better to add a cross-linkable multifunctional monomer. The mixing ratio, if the amount is more, the collection rate will be increased, and the good moldability of the allyl ester oligomer will be lost, so it is better to use 70% of the organic component S! Or less, and more preferably 50% by weight or less . However, if the weight is less than 5 3 !, it is inconvenient to mix aluminum hydride, Bo Ji, etc., as mentioned above, and as mentioned above, depending on the feeder ratio of diallyl monohydrazine When synthesizing the reaction, it will be left unreacted monohydrate. It is better to coexist in the original state during molding. The inorganic compounds contained in the resin composition for artificial marble of the present invention can be used, for example, vaporized silicon, quartz, digas Titanium trioxide, antimony trioxide, aluminum vapor, calcium sulfonate, aluminum hydride, hydrogen hydride powder, clay, gold hurricane, etc. skimming. Especially shaped products such as aluminum hydride, magnesium hydroxide, etc. The marble is more suitable for flame retardancy. In addition, the vaporized silicon (glass glass) is a transparent, inorganic material with excellent boiling resistance. The grain size of the grain is l-80w, preferably 3-50 households Λ. In addition , Inorganic materials are not limited to one type, but the chief can also be used in combination of two or more types. For the purpose of improving the dispersion and adhesion of inorganic materials, surface treatment is applied to the official window, -1 3- (please read the notes first ^ 项 再 塥 写 本 -fj This paper size is used in the SS home sample standard (CNS) TM specification (210χ2ί) 7 male; ":) 81. 2. 20,000 2〇α Η 6 5. Description of the invention (12) The invention The resin composition for artificial marble can be cured by polymerization to form artificial marble. The hardener used here is only The use of heat, wave cancellation, infrared, or ultraviolet light can generate residues, any residue polymerization initiator can be used, the purpose of the hardening composition, the purpose, the mixing ratio of the ingredients, and the hardening method of the hardening composition Wait for it to be properly selected. If the use case is advantageous, it can be used occasionally in the '0 wave micro-fat and other applications to synthesize pentamethylene double residues.-Yes, 2 o'clock. Β9 Gas ketone methyl 4 butyl 2 0 f base gas met, acetoxy ketone ketones, gas qualities »combined _ chemical and other gas 0 0 Yu Tiaoji Zhuo met acetyl toluene 0 2 (please read the back first Please pay attention to it and fill in this shell.) Gas-based perpentyl 11-yl laurel month three I »4 gas 4, * 2 type gas 0 base 0 second-class gas encounter 0 Toluocyanide is used to kill Ghide hydrogen and meet cumene hydrogen Oxygen Encounter «Gas, Ventilation, etc. a Gas-based wait / κDibutylidene 1-two 1 '· f Gas-based meet air-based peroxiyl alkane butadiene wait, azine gas pass through 丨 cumene 2 Base 2, 2-ester 2 acid, pentane gas has met the base gas, but the total gas of butyl tetraxide Isobutane \ / Oxybutyrylbutyryl ester hexyl ethyl-2 I gas-peroxybutyrate 0 acid methylenedibenzene, 5 pairs, 5 hydrogen-3 hexaoxygen peroxide »Gylbutyrate, diacetate, acid ester Decanoic acid diacid encounters oxybutyrate T dioctane, carbamide III, Ministry of Economic Affairs, Pyongyang Bureau of Standards, KX industrial and consumer cooperation to produce duo gas, glyceryl propionate isoxadiene, oxygen Ester group meets butyl ketane, etc. Ester esters, acid, ethylene, gas, decyl, methyl, butane, tert, gas, ^ 0, acid, hexyl, propane, isobutyl, benzene. Sulfonyl disulfide gas encounter. The butyl ester can be used in combination with butyl ester when it is hypoacidic, and over-poly_isosteric acid ester exophosphoric acid purple diorate. This paper is used as a standard (CNS) A 4 specification (210X297 ;; :) 81. 2. 20,000 The Ministry of Economic Affairs, Bureau of Standards, Mongong Consumers cooperated in the production of Du. Fifth, the description of the invention (13) 2,2-dimethylamino-2-phenylacetophenone, 2.2-diethylaminobenzene Acetone, 4'-isopropyl-2-hydroxy-2-methylbenzeneacetone, 2-hydroxy-2-methylphenylpropane 4,4'-bis (diethylamino) benzophenone, diphenyl Formazan, methyl (o-benzoyl enzyme > benzoate, 1-phenyl-1,2-benzenedien-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1 , 2-malonyl-1- (o-toluoyl) oxime, benzoyl, benzoin methyl ether, benzoyl cyanide, benzyl isopropyl ether, benzoin isobutyl ether, benzene Carboxylic acid octyl ether, benzyl, benzyl methyl acetal, benzyl ethyl acetal, diethyl acetal and other acyl compounds, methyl awakening, atmosphere diuresis. Chlorodioxanone, 2-Methyldioxanone, 2-isopropyldioxanone, etc. or dioxanone derivatives, diphenyl disulfide, dithiocarbamate, etc. For polymerizable allyl oligomers, 0.1-10 parts by weight is a companion, and 0.5-3 parts by weight is more preferred. Of course, the polymerization initiator can be used in combination with other polymerization accelerators. The resin composition for artificial marble may contain other well-known additives such as plasticizer, slip agent, type, colorant, flammable, ultraviolet absorption, etc., if necessary, in a blend of non-destructive transparency and physical properties. After mixing the materials described above, fully stir and mix them to form a composition. The composition thus obtained can be poured into a yung-shaped shape of the desired shape, degassed, heated, polymerized and hardened into a molded body. The homogenized composition is wrapped into an N material with a film Shaped SMC or bulk BMC, which is formed by pressure molding according to the usual molding methods, and then hardened to form a tattoo. -1 5- (please read back to the precautions #fill in this 1®) Binding · Order _ Line · The paper size is common China National Standards (CNS) T4 specifications (210X297 public goods) 81. 2, 20,000 AG B6 V. Description of the invention (14) Η is further detailed in the following examples, but it is not limited to the examples as long as it does not violate the gist of the present invention. Preparation method of allyl ester oligomer Reference Example 1 Equipped with distillation device 10 male pressure booster, 4.0 kg of diallyl terephthalate (hereinafter referred to as DAT), 1.062 kg of diallyl maleate (hereinafter referred to as DAM), 1.236 kg of propylene glycol (hereinafter referred to as PG), Dibutyl tin oxide (hereinafter referred to as DB0) 8 grams, heated to 180 = 0 under radon gas flow, the resulting allyl alcohol was distilled off. When the allyl alcohol was distilled out of about 1.8 kg, the reaction pressure was reduced to 50mnHg, Increase the leaching rate of allyl fermentation. After distilling out the theoretical amount of allyl fermentation, reduce the pressure in the reaction mixture to 2mniHg, react for another hour, and cool the reactant. The residual monomer content in the reaction liquid was 9.2% by weight, and it was used as it is as the allyl oligomer for the artificial resin composition for artificial marble described below. Reference Example 2 The raw material of Reference Example 1 was changed to the composition shown in Table 1, and the rest was reacted in the same manner as Reference Example 1 to obtain an allyl ester oligomer. The analysis value of this allyl ester oligomer is shown in Table 1. (Please fill in the note t on the back and then fill out this page.) Printed by S Industry and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs -1 G-This paper size is applicable to raw 訂 樂 准 irNjq. CΛ r / r

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Printed by the S Industry and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (16) Example 1 The allyl ester oligomer of #Examination Example 1 was mixed with styrene monomer to become the resin composition for the inventor's Di marble . Example 2-15 The allyl ester oligomer of Reference Examples 2-6 and the reactive monomers shown in Table 2 were mixed at the ratio shown in Table 2 to form the resin composition for Dimarble of the present invention. Comparative Example 1 The allyl ester oligomer of Reference Example 7 not containing Structure I was mixed with styrene monomer to obtain a resin composition of Comparative Example. 100 parts by weight of the resin composition for artificial marble described above was taken, and 200 parts by weight of aluminum hydroxide (removed by Showa Kiko Engineering Co., Ltd., Higilite H-320ST) was removed, and the mixture was heated and mixed uniformly. Then add two parts by weight of perOyl TCP, after mixing, degassed under reduced pressure to obtain a composition. The composition thus obtained was injected into a 40mra ≦ Xπππ metal mold, and was hardened at 601: heating for 1 hour. In Example 1-6, a beautiful light-scattering marble shaped product with both depth and obscurity was obtained, but only in Comparative Example 1. At this time, the semi-hardened molded product that is not soft enough under the above conditions. The resulting molded product was measured for Hunter color using a color-measuring color difference meter, and the hardness was measured using a Barcol (B a r c ο 1) hardness meter. The above results are listed in Table 2. -1 8--------: ----------------- installed ------ ordered ------ line (please read it first Matters needing attention on this page) This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 public dreams) Five instructions issued (17 ι§ ^, 〇 >

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V. Description of the invention (18) Example 1 G-3 1 The allyl ester oligomer of Reference Example 1-6 and the reactive monomer shown in Table 3 are mixed in the ratio shown in Table 3 to become the present invention Resin composition for artificial marble. Inorganic fillers use glass "material (product of Japan FERRO company, SHEI GLASS FIRST M-50S), instead of the above-mentioned grain aluminum hydroxide, and the rest are heated and hardened in the same manner as in the above example, to obtain scattered beautiful light, both depth and shielding A marble-shaped molding. The resulting molded product was measured for Hunteri color using a colorimetric color difference meter, and hardness was measured using a Barcol hardness meter. The above results are listed in Table 3. (Please read the notes on the page first and then write this page) 丨 Installed. Ordered-. Line. Printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs of the Ministry of Economy, Industry and Commerce Cooperative Cooperative -20- This paper scale is applicable to the Chinese National Standard (CNS > A4 Specifications (210 X 297 mm) V. Description of the invention (19 〇

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i 28V 3E ^ «< D W- '« NEE—' 313 ^ 21-Various paper sizes are subject to China National Standard (CNS) A 4 specifications (210 X 297 public dreams) 1 Λ 6 Π 6 9 ο Ministry of Economic Affairs Printed by the Bureau of Standards and Technology of China Consumer Industry Co., Ltd. ii 5. Description of the invention (20) The allyl oligomer with a double-bond molecular structure is used as the oligomer of the eaves into an artificial marble substrate, which is combined with the reactive ray The resulting resin composition for artificial marble of the present invention can greatly improve the hardenability without compromising the good moldability of the conventional allyl ester resin, and the characteristics of the resin for artificial marble, such as the degree and excellent boiling resistance. The resin composition for artificial marble of the present invention can be used for Fan Ou, who requires the transparency of artificial chrysotile, especially when injection molding or eaves molding can accelerate the ploughing cycle, and has great industrial utilization value. (Please read the back first-Attentions # Fill in this page j Outfit-This paper is used in the standard a Η home sample standard (CNS) Yu 4 specifications (210x297 male dragon) 81. 2. 20,000

Claims (1)

Seven A7 I B7 j C7 L D7 VI. Patent Application Group No. 81102356 "Resin Compositions for Artificial Marble" Patented (amended in May 1982) 1. A resin composition for human Di marbles, which is presumed by the following (a ) And (b), (a) an allyl ester oligomer with the following repeating units 30 -95 reset%-(COACOOBO)-Structure I-(C0-CH = CH-C00B0)-Carrying Π and 0.05 forget-CH = CH- / A guest 4 (Chile ratio), with an allyl ester group at the end, where A is an organic residue derived from a C2_u divalent aromatic organic acid or saturated organic fatty acid, and B is C2- 30 divalent organic residues derived from diol; (b) reactive monoamines selected from the group consisting of 5-70 weight X methyl (meth) acrylate, styrene, maleic acid, maleic acid Dimethyl ester, allyl benzoate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl fumarate Ester, triallyl trimellitate. 2. A resin composition for artificial marble, consisting of the following (a) and (b), (a) an allyl oligomer with the following repeating units 30-95% by weight-(COACOOBO)-( C0-CH = CH-C00B0)-(C0YC00) x-ZO-COYCOO 1 This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) ----------- ------------- installed ------, 玎 ----- ^ 丨 line ,, _-(please read the notes on the back before writing this page) Ministry of Economic Affairs Printed by the Central Standards Bureau Beigong Consumer Cooperative I. Structure I. Structure H-AT B7 Dream ❼_ ^ 6. Apply for a patent park S and 0.05S -CH = CH- / A; S 4 (molby), with alkene at the end Propyl group, where A is an organic residue derived from a C2-2C divalent aromatic organic acid or a saturated organic fatty acid, B is a divalent organic residue derived from a C2_3c binary enzyme, and Y is the above A or -CH = CH-, X is an integer from 2 to 10, and Z represents an organic residue derived from a multi-enzyme with X + 1 hydroxyl group; (b) Reactive single fishes 5-70 weight 3 from the following groups! (甲Base) methyl acrylate, styrene, maleic acid, dimethyl maleate, allyl benzoate, benzene Acid, diallyl isophthalate diallyl for stupid diallyl maleate, diallyl fumarate, diallyl, triallyl trimellitic acid was poured.丨 (please read the notes on the back before filling in this page). Xiang. · &Quot; The printed paper size of the Employees ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The paper size is suitable for WW Family Standard (CNS) specifications (210 father 297 mm )