TW438819B - (Methyl)acrylic syrup, method of manufacturing the same, and method of manufacturing molding material including the same - Google Patents

Abstract

The present invention provides a (methyl)acrylic syrup which can give a molding material excellent in storage stability and provide a process for producing this (methyl)acrylic syrup within shorter time as compared to the conventional. Furthermore, the present invention provides a molding material which can be cured more quickly, and excellent in resistances to heat, solvents, weather, and water. This (methyl)acrylic syrup is produced, for example, by polymerizing (methyl)acrylic ester monomers with carboxylic vinyl in the presence of thiol compounds and then treating the reaction mixture with maleic anhydride and basic compounds. This molding material contains the (meth)acrylic syrup and it can optionally contains a thickener, a succinic acid derivative, a reinforcement, etc.

Description

TECHNICAL FIELD The present invention relates to a (meth) propionic acid slurry, a method for manufacturing the same, and a manufacturing material for a molding material containing a (meth) acrylic acid slurry. BACKGROUND ART Molding materials containing acrylic slurry have been widely used in the past. The above-mentioned acrylic acid slurry is disclosed in, for example, Japanese Patent Publication No. 64_1 1 652 _ a polymer containing a carboxyl group and a cross-linked propionic acid slurry containing a cross-linked decamonomer containing multiple functional groups, and No. 61_243 5 has not been disclosed in the 7th publication-a propionic acid slurry containing a carboxyl group. Furthermore, for example, in Japanese Patent Publication No. 53-2 2 1989, a slurry obtained by treating a thiol compound remaining in a slurry with maleic anhydride and a basic compound has been disclosed. Since the thiol compound is used as a chain shifting agent of a polymerization reaction or a stabilizer of a slurry, a slurry obtained by polymerization in the presence of a thiol compound contains an unreacted thiol compound. If a thiol compound remains in the slurry, bromine due to the thiol compound may be generated. In addition, the residual slurry of the thiol compound gradually increases in viscosity during storage, and may gelatinize depending on circumstances. Furthermore, a molded product of a molding material containing the slurry was poor in solvent resistance, water resistance, and weather resistance. However, the conventional acrylic slurry has poor storage stability (so-called Shelflife) when used as a molding material. In addition, it takes a long time to harden a molding material containing an acrylic slurry, and a molded product composed of the molding material is inferior in heat resistance and solvent resistance. Further, it takes a long time to produce the acrylic acid slurry in the propionic acid slurry containing no carboxyl group. Therefore, we are very much looking forward to solving these problems with (meth) acrylic acid slurry and its manufacturer-4-This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 mm)!--111: Bu — — II -Γ---II I i, I (Please read the notes on the back before filling this page) Order-438819 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of Invention (2), And a molding material containing the (meth) acrylic acid slurry. Also, the processing method disclosed in Japanese Patent Publication No. 5 3-2 189 is applicable only to a specific slurry and has a narrow application range. Therefore, this treatment method cannot obtain a (meth) acrylic acid slurry which can solve the aforementioned problems. The present invention has been made in view of the above problems, and a first object thereof is to provide a (meth) propionic acid slurry having excellent storage stability when used as a molding material. A second object is to provide a method for producing the (meth) propionic acid slurry in a shorter time than conventionally. A third object is to provide a method for producing a molding material that can be cured in a shorter time than conventionally and can obtain various molded articles having excellent physical properties such as heat resistance, solvent resistance, weather resistance, and water resistance. DISCLOSURE OF THE INVENTION In order to achieve the above-mentioned object, the present inventors have earnestly researched a (meth) propionic acid slurry and a method for producing the same, and a method for producing a forming material containing a (meth) acrylic acid slurry. As a result, it has been found that, for example, a monomer component containing (meth) acrylic acid and a vinyl monomer containing a carboxyl group are polymerized in the presence of a thiol compound, and then the reaction mixture is treated with maleic anhydride and a basic compound ( After the (meth) propionic acid slurry and the monomer component containing the (meth) propionic acid vinegar are polymerized in the presence of a thiol compound, the reaction mixture is treated with maleic anhydride and a basic compound, and The (meth) propionic acid slurry, which is formed by adding a vinyl monomer containing the carboxyl group to the reaction mixture, has excellent storage stability when used as a molding material (so-called Shelflife). Furthermore, by molding a molding material containing the above (meth) acrylic slurry, a molded product having excellent physical properties such as heat resistance, solvent resistance, weather resistance, and water resistance can be obtained, and the present invention has been completed. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) i. ^ — · TM§ ^ — H--I In I i, i (Please read the notes on the back before filling this page)-Order 438819 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (3) That is, 'The manufacturing method of the (meth) acrylic acid slurry of the present invention is to solve the above-mentioned problems, and is characterized by: After the monomer component of the acrylic acid ester and the carboxyl group-containing vinyl monomer are polymerized in the presence of a thiol compound, the reaction mixture is treated with anhydrous maleic acid and a basic compound. In order to solve the above-mentioned problems, the method for producing a (meth) acrylic acid slurry according to the present invention is characterized in that a monomer component containing a (meth) acrylic acid ester is polymerized in the presence of a thiol compound, and then Malay An acid anhydride and a basic compound are used to treat the reaction mixture, and at the same time, an ethylenyl monomer containing several groups is added to the reaction mixture. If the above method is used, a vinyl monomer containing a carboxyl group is used, and the reaction mixture is treated with maleic anhydride and a basic compound at the same time, it can be produced in a relatively short period of time as a molding material with excellent storage stability (methyl ) Acrylic slurry. Further, according to the above method, a (meth) acrylic acid slurry having excellent storage stability when used as a molding material can be provided. Furthermore, in order to solve the above-mentioned problems, the molding material of the present invention is characterized by containing a (meth) acrylic acid slurry obtained by the above-mentioned production method. In order to solve the above-mentioned problems, the molding material of the present invention is characterized by containing a monomer component containing a (meth) acrylate polymerized in the presence of a thiol compound, and then treated with maleic acid liver and a test compound. A (meth) acrylic acid slurry formed by the reaction mixture and a vinyl monomer containing a carboxyl group. According to the above structure, a molding material can be provided, which can be hardened in a shorter time than conventionally known, and obtains a molded product excellent in various physical properties such as heat resistance, solvent resistance, weather resistance, and water resistance. j. -L .-- · ---- (Please read the notes on the back before filling this page)

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4 3 8819 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 Legislation and Description of Invention (4) The invention will be described in more detail below. (1) The (meth) acrylic acid slurry of the invention is a monomer component containing a (meth) acrylic acid ester, and a carboxyl group-containing vinyl monomer is polymerized in the presence of a thiol compound, and then maleic anhydride and an alkali are used. A compound obtained by treating the reaction mixture. Or '(11) The (meth) acrylic acid slurry system of the present invention polymerizes a monomer component containing the (meth) propionic acid vinegar in the presence of a thiol compound, and then treats the component with maleic anhydride and a basic compound. The reaction mixture is formed by adding a vinyl monomer containing the carboxyl group to the reaction mixture to form (iii) the (meth) acrylic acid slurry of the present invention is a monomer containing (meth) acrylate A vinyl ether compound and / or a vinyl thioether compound is added to a reaction mixture in which components are polymerized in the presence of a thiol compound, and is formed. (iv) The (meth) acrylic acid slurry of the present invention is obtained by polymerizing a monomer component containing (meth) acrylic acid vinegar and a vinyl monomer containing a carboxyl group in the presence of a thiol compound, and then adding vinyl ether to the reaction mixture Compounds and / or vinyl sulfide compounds. (v) The (meth) acrylic acid slurry of the present invention polymerizes a monomer component containing a (meth) acrylic acid ester in the presence of a thiol compound, and then adds a vinyl ether compound and / or vinyl sulfur to the reaction mixture. An ether compound is formed by adding a vinyl monomer containing the carboxyl group to the reaction mixture. (vi) The (meth) acrylic acid slurry of the present invention is adapted to the size of the paper containing (meth) acrylic acid in accordance with Chinese National Standard (CNS) A4 (210X297 mm) BW. β · ι ······ aaaiwi MMW ＭΙ ····· 1-_1 ϋ I .. (Please read the notes on the back before filling this page)

1T 438819 A7 B7 Printed by an employee of the Central Standards Bureau of the Ministry of Economic Affairs and a consumer cooperative. 5. Description of the invention (5) Cool monomers 0. Polymerized with a carboxyl-containing acetamyl monomer in the presence of 4 alcohol compounds. The reaction mixture is added with glycidyl (meth) acrylate and / or methyl glycidyl (meth) acrylate before or after the addition of the acetamyl ether compound and / or the vinyl sulfide compound. Glycerol ester, which esterifies a carboxyl group containing a polymer, and is a (meth) acrylic ester polymer that is bonded to the main chain with a side bond containing a polymerizable double bond. (Vii) The (meth) acrylic acid slurry of the present invention is obtained by polymerizing a (meth) acrylic acid ester-containing monomer component and a carboxyl group-containing vinyl monomer in the presence of a thiol compound. Saturated epoxy compounds are esterified in the presence of a metal compound containing at least one element selected from the group consisting of zinc, tin, and chromium, and a side chain with a polymerizable double bond bonded to the main chain (a Based) acrylic polymer. The polymer may contain an oligomer having a polymerization degree of about 2 to 20 or a prepolymer obtained by stopping the polymerization reaction of the monomer in the middle. The monomer component contains a (meth) acrylate and a vinyl compound (monomer) as necessary. Specific examples of the (meth) propionate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) propionate, and isopropyl (meth) acrylate Ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) propionate, dibutyl S (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as 2-ethylhexanoic acid, lauryl (meth) propionate; (meth) propanecylic acid esters such as cyclohexyl (meth) acrylate; ( Methyl) glycidyl propionate; basic (methyl) groups of dimethylaminoethyl (meth) propionate, diethylamino (meth) acrylate, etc. -8- Applicable to China National Standard (CNS) A4 specification (210X29? Mm) IJ ------ ^ ---- t, 1 (Please read the notes on the back before filling this page) Order 438819 A7

V. Description of the invention (6) Acrylate and the like. ϋϋ i —l · — ϋϋ ϋ i 1 (Please read the precautions on the back before filling out this page} Also, in the present invention, (meth) acrylic acid esters can also contain ammonium (meth) acrylate, N • N-alkoxy substituted (meth) acrylic acid fluorenyl methacrylate, N-ethoxymethyl methacrylamine, etc. These (meth) acrylates can also be used alone, Among the compounds exemplified above, methyl methacrylate and (meth) propionic acid vinegar mainly containing methyl propionate feg are preferred. With methyl methacrylate as the main component, the weather resistance, transparency, surface gloss, and other physical properties, or appearance, of a molded product (hardened product) formed from a molding material containing a (meth) acrylic slurry can be further improved. Safety, etc. Also when using a basic (meth) acrylate as the (meth) acrylate, it is desirable to use (relative to the basic (meth) acrylate) i 0.00% by weight or more of neutral (formaldehyde) Based) acrylate. Neutral (meth) acrylic As the acrylate, the above-exemplified alkyl (meth) acrylate, cycloalkyl (meth) propionate, and the like can be used. The ethyl fluorenyl compound may be a compound having no carboxyl group. The ethyl fluorenyl compound is specifically The above examples can be taken from: stilbene, difluorene, and block B; styrene, α-methylstyrene, vinylmethyl, chlorostyrene, etc. printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. Compounds; vinyl esters such as vinyl acetate; allyl alcohol, ethylene glycol monofluorenyl alcohol, propylene glycol monomethyl alcohols, etc .; (methyl) propionitrile; unsaturated test Sex compounds; N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide Fluorenimine, N-phenylmaleimide, Nm-tolylmaleimide, Np-tolylmaleimide, N-from-zylylmaleimide, -9-benzyl Paper size applies Chinese National Standard (CNS) A4 specification (21 × 297 mm) 4 3 88 1 9 A7 __ ,. _ B7 V. Description of the invention (7) N-benzylmaleimide , N_Cyclohexylmaleimide, N, N, _Diethane bismaleimide, N, N'-Tribenzyl bismaleimide, N, N, -m-Extender N-substituted maleimines of phenylbismaleimide, N, N'-p-phenylene maleimine, etc .; (meth) acrylates containing hydroxyl groups, etc., but not particularly In addition, the (meth) acrylic acid ester containing a hydroxyl group is particularly preferably a diol (meth) acrylic acid ester formed by esterifying at least one of the protecting groups having a diol, and specific examples include: 2 · (Meth) acrylates with hydroxyalkyl groups such as ethyl (meth) propionate, 2 # propylpropyl (meth) acrylate; glycerol mono (meth) acrylate, glycerol Poly (meth) propanoate of polyvalent alcohols such as di (meth) acrylate, pentaerythritol mono (meth) propionate, pentaerythritol di (meth) acrylate; polyethylene glycol mono (methyl) ) (Meth) acrylates of high molecular weight diols such as propionate. These ethenyl compounds may be mixed in a single kind, or may be mixed in a combination of two or more kinds as appropriate. The mixing ratio of the two when the vinyl compound is mixed in the (meth) acrylate, that is, the content of the ethyl fluorenyl compound in the above monomer component, although it depends on the type of the ethyl fluorenyl compound or the (methyl) ) The combination of acrylates and the like is determined, but it is more preferably 50% by weight or less. Also printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). When the vinyl compound is N-substituted maleimide, the range is from 5% to 40% by weight. It is more preferably within 10% to 30% by weight, and particularly preferably from 5% to 25% by weight. When the vinyl compound is a (meth) acrylate containing a hydroxyl group, it is preferably within a range of 0.5% to 20% by weight, more preferably 1% to 15% by weight, and particularly preferably 3% to 1%. weight%. -10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs, when the vinyl compound is (meth) propionic acid vinegar containing tritium, when the ratio of the ethyl compound is not; 5% by weight, the monomer component is polymerized A polymer (hereinafter referred to as a polymer containing a hydroxyl group) is introduced, and a (meth) acrylic acid slurry is introduced into a polymerizable double bond by reacting with an unsaturated isocyanate compound or an unsaturated acid (either of which will be described later) (may be Since the number of polymerized double bonds) is limited, a molded product having excellent physical properties such as strength under heat cannot be obtained. The ethylammonium monomer (hereinafter referred to simply as a vinyl monomer) containing the above-mentioned tertiary group, as long as it contains a polymerizable double bond and a compound with a carboxyl group in one molecule. Specific examples of the vinyl monomer include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and vinyl benzoic acid; maleic acid, fumaric acid, decomposed aconitic acid, and aconic acid, etc. Unsaturated dicarboxylic acids; monoesters of such unsaturated dicarboxylic acids, etc., but are not particularly limited. Specific examples of the monoester of the unsaturated dibasic acid include monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, and monomethyl fumarate. , Monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl vinegar, etc. Further, an acid anhydride may be used as a vinyl monomer, and a compound formed by esterifying a (meth) acrylic acid ester containing a hydroxyl group, that is, a half ester of the acid anhydride. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and hexahydrophthalic anhydride. Examples of the (meth) acrylate containing the above-mentioned hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate ε-caprolactone ring-opening adduct, 2 _ Β-butyrolactone ring-opening adducts of hydroxyethyl (meth) acrylic anhydride, etc. Therefore, the half g purpose of acid liver can be exemplified by succinic acid monovinegar, g too acid -11-This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ”· Order &quot;,-^ ί (Please read the precautions on the back before filling this page) 5. Description of the invention (9 Monoesters, Hexahydrophthalic Acid Monoesters, etc. These vinyl monomers can also be used alone, or two or more types can be mixed appropriately. And use it. The ratio (ratio) of the monomer component to the vinyl monomer is 100 weight ❶ / c based on the total of the two, and the monomer component is preferably 80% to 99.5% by weight. In addition, The acetamyl monomer component is preferably from 5 to 20% by weight, and more preferably ΐ · 0% by weight / ❶ to 5% by weight. Further, it is described in the above-mentioned ⑴, (ii), (iv), ⑺ In the (meth) acrylic acid slurry, the vinyl monomer is more preferably 15 to 10% by weight, and the vinyl monomer is described in the (meth) acrylic acid slurry of the above (Vi) and (vii), Furthermore, it is preferably 3% by weight to 10% by weight. Using a vinyl monomer within the above range can be performed in a shorter time than conventionally. (Meth) acrylic acid slurry can be produced, and at the same time, the heat resistance, solvent resistance, weather resistance and water resistance of a molded product formed by molding a molding material containing the (meth) propionic acid slurry can be improved. In addition, the molding material can be cured in a shorter time than conventional, and the average molecular weight of the cured product (molded product) can be increased. Furthermore, a molded product with excellent strength under heat and little coloring can be obtained. Vinyl When the ratio of the monomers is less than 0.5% by weight, the effects and effects expected from the use of vinyl monomers are lacking, that is, the effect of shortening the time taken to produce a (meth) acrylic acid slurry is lacking, and the resulting molding is lacking. Various properties such as heat resistance of the product are not suitable, and the molecular weight of the cured product does not increase. Furthermore, for example, (meth) acrylic acid slurry obtained by polymerizing a monomer component and a vinyl monomer, and unsaturated An epoxy compound (described below) is reacted to obtain -12- This paper size applies to China National Standards (CNS) A4 (2ΐ〇χ297mm) Γ Y --- 1 I clothing-* * ί (please Read the notes on the back and fill in this page),? Τ Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ^ 38819 ____B7 V. Description of the invention (1〇) &lt; In the case of molding materials, the reaction is introduced into (methyl) The number of polymerizable double bonds (polymerizable double bonds) of the propionic acid slurry is limited, so it is impossible to obtain a molded article having excellent physical properties such as thermal strength. When the ratio of the vinyl monomer exceeds 20% by weight, the obtained molding is obtained. The weather resistance and water resistance of the product will be low, so it is not suitable. Vinyl monomers can also be mixed in the monomer component before polymerization, and can also be mixed in the reaction before the added thiol compound is treated, that is, after polymerization. The mixture may further be mixed with the reaction mixture after the added thiol compound is processed. Alternatively, after the added thiol compound is processed to produce a (meth) acrylic acid slurry, the (methacrylic acid slurry and vinyl monomer) may be mixed when producing a molding material. The thiol compound has hydrogen sulfur in its molecule. The chain shifting agent of the base has the function of adjusting the molecular weight of the polymer in the reaction mixture. Specific examples of the thiol compound include: tertiary butyl mercaptan, n-octyl mercaptan; n-dodecyl mercaptan, etc. Aromatic mercaptans such as alkyl mercaptans, thiophenols, and thiophenols; thioglycolic acids; octyl thioglycolate, ethylene glycol dithiodiol esters, trimethylolpropane tri (thioglycolate) , Pentaerythritol tetra (thioglycol ester), etc .: Alkyd = Hydrogenthiopropionic acid (3-hydrothiopropionic acid); Octyl tetrahydropropionate, 1,4-butanediol di (point- Thiopropionate), trimethylolpropane trithiopropionate), pentaerythritol tetra (factory thiopropionate), etc., but not limited to these. These thiol compounds can also be used alone or in combination of two or more kinds ... also can be used together as a bond shifting agent such as methylphenethylammonium dimer or tetragasified carbon. Relative to the mixture of the monomer component and the ethylenic monomer (hereinafter referred to as the monomer group) <addition amount of sulfur compound, or 1_ιϋ- -m ϋϋ — —mmm — I 11 -L ^ n — n ^ i ϋ i 4 (Please read the notes on the back before filling out this page) Order printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

438819 A7 B7__ 5. Description of the invention (Μ) J ------- L_ • clothing! j &lt; First (please read the precautions on the back before filling out this page) The amount of compound to be added can be selected according to the type of the thiol compound or the composition of the monomer composition, etc., and is not particularly limited, but It is preferably from 0.01% to 15% by weight, and most preferably from 0.01% to 2% by weight. By adding a thiol compound, the polymerization reaction can be easily controlled. The polymerization method is specifically Various polymerization methods such as bulk polymerization (bulk polymerization), solution polymerization, suspension polymerization, emulsion polymerization, etc. can be used. Among the polymerization methods exemplified above, block polymerization is particularly preferred. In addition, when suspension polymerization is used, for example, A dispersion stabilizer such as polyvinyl alcohol may be a monomer composition (or a monomer component) suspended in a dispersant such as water.

1, 1T Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs When the above monomer composition is polymerized in the presence of a thiol compound, or when the monomer component is polymerized in the presence of a thiol compound, a polymerization initiator should be used. Specific examples of the polymerization initiator include dibenzoic acid peroxide, dilauric acid peroxide, methyl ethyl ketone peroxide, third butyl peroxy_2 ethylhexanoate, and third butyl peroxy caprylic acid. Ester, tert-butylperoxybenzoate, cumene hydroperoxide, dicyclohexanone peroxide, dicumene peroxide, bis (4 · thirdbutylcyclohexyl) peroxydicarbonate , M • bis (third hexylperoxy 3,3,5-dimethylcyclohexyl, etc. organic peracids; 2,2, _azobisisobutylene, 2-phenylazo-2 Azo compounds such as, 4-dimethylmethoxyvaleronitrile and the like, but are not particularly limited thereto. These polymerization initiators may be used alone or in combination of two or more kinds. With respect to the monomer composition The addition amount of the polymerization initiator of the monomer component is not particularly limited. The reaction temperature or the reaction conditions for the reaction time during the above-mentioned polymerization are not particularly limited, and known reaction conditions can be used, for example. The method of stopping polymerization in the middle (so-called partial polymerization), because

A7 438819 ______ B7 5. Description of the invention (12) It is better to obtain (meth) acrylic acid slurry in one stage. Thereby, a reaction mixture containing a polymer (which contains a carboxyl group) can be obtained). Furthermore, by polymerizing (partially polymerizing) the monomer components, a reaction mixture containing a polymer (without a carboxyl group) can be obtained. The average molecular weight of the polymer should preferably be adjusted to a weight average molecular weight (Mw) of about 6,000 to 1,000, 000, more preferably about 30,000 to 1,000,000, and the number average molecular weight (Mη) to be adjusted to 3,000 to 50,000. It is about 10,000, more preferably about 10,000 to 200,000, but it is not particularly limited. The polymerization is preferably performed under a nitrogen atmosphere. Furthermore, at the end of the reaction, the ratio (ratio) of the polymer in the reaction mixture to the unreacted monomer composition (or monomer component) is 100% by weight based on the total of the two, and the polymer is preferably 7 Wt% ~ 80 wt%, the unreacted monomer composition (or monomer component) is preferably 93 wt% ~ 20 wt%. At the end of the reaction, the monomer composition (or Monomer component), or after the polymer is separated from the reaction mixture, a monomer composition (or a monomer component) is further mixed in the polymer. At this time, the monomer composition (or monomer component) to be further mixed may be the same as or different from the monomer composition (or monomer component) used in obtaining the reaction mixture. Alkyl acrylate and styrenic compounds are particularly preferred. In addition, alkyl methacrylate is methyl methacrylate, methacrylic acid ethyl ester, n-propyl methacrylate, n-butyl methacrylate, second butyl methacrylate, methyl Tertiary butyl acrylate is particularly preferred; styrene-based compounds are particularly preferred. This can further improve the weather resistance, transparency, and table of a molded product formed from a molding material containing a (meth) acrylic acid slurry. __15 · This paper size is in accordance with China National Standard (CNS) A4 (210X 297) Mm) (Please read the notes on the back before filling out this page)

1T printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 438819 V. Description of the Invention (13) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of various physical properties such as gloss, appearance, and safety. Furthermore, at the end of the reaction, a maleimide-based compound may be further mixed into the reaction mixture. The above maleimide-based compound refers to an N-substituted maleimide; an oligomer obtained by polymerizing a monomer composition containing N-substituted alimine, and a polymer. These maleimide compounds may be used alone or in combination of two or more kinds. Among the maleimide compounds, N · cyclohexylmaleimide is particularly preferable because it can suppress the coloration of a molded product obtained by press molding and can obtain a molded product having a good appearance. The maleimide-based compound may be a commercially available product or a compound synthesized by a known method. For example, N-cyclohexylmaleimide may be synthesized by reacting maleic anhydride with cyclohexylamine to obtain N-cyclohexylmaleic acid monoimide. The monomer composition used when obtaining the oligomer and polymer described above may contain, in addition to N-substituted maleimine, the vinyl compound exemplified above. When the maleimide imide compound is mixed in the reaction mixture, the amount of the maleimide imide compound used is based on the total amount of the two as 100 wt.% And 5% to 40 wt.%. More preferably, it is more preferably 10% to 30% by weight, and more preferably 15% by weight 2 / ❶ to 25% by weight. When the amount is less than 5 wt%, the moldability of the obtained molding material is lowered, and at the same time, the heat resistance, gloss, and surface smoothness of the molded product are poor, which is not preferable. In addition, when the amount used exceeds 40% by weight, the strength of the obtained molded article is reduced, which is not preferable. The (meth) acrylic acid slurry according to the above (1) is hereinafter referred to as (meth) acrylic acid slurry A when it must be distinguished from others. The (meth) acrylic acid slurry A is suitable as, for example, a flat-shaped molding compound (hereinafter referred to as SMC), a block-shaped molding 11 ^-clothing-(Please read the precautions on the back before filling in this page) -Order • 1 I --!-H!-1 — -16 'Paper size applies Chinese National Standard (CNS) Α4 specification (21Gx297 public meal 438819 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (material) The following is referred to as BMC), pre-mixed materials, or injection molding materials. (Ii) The (meth) propionic acid slurry is described below. When it must be distinguished from others, it is called (meth) acrylic slurry B. The (meth) acrylic acid slurry B is suitable as, for example, a cast material or a pre-mixed material. The (meth) acrylic acid slurry A · B may also contain unreacted monomer components. Moreover, the monomer components are made into a thiol. After the polymerization in the presence of a compound, a (meth) acrylic acid slurry formed by treating the reaction mixture with maleic anhydride and a basic compound, and a vinyl monomer is used as a molding material, which is suitable as, for example, a casting material. Sex Specific examples of the compound include primary amines such as methylamine and ethylamine; secondary amines such as dimethylamine and diethylamine; tertiary amines such as trimethylamine and triethylamine; diazonium compounds and triplet compounds Etc., but it is not particularly limited. These basic compounds are preferably used in the range of 0.001 times mole to 1.5 times mole, and more preferably 3,000 times mole compared to the thiol compound added during polymerization. In the garden of Moore. Maleic acid with the above test compound For the thiol compound added during polymerization, 0.5 times Moore to 3.0 times Moore, and more preferably 07 times Moore to 2 · 8 times Within the range of Moore. When the amount of basic compound is 0.5 mol compared with the thiolated human foot added during polymerization, or when the amount of maleic acid liver is less than 0.5 fold, the amount of thiol compound is: It is not fully processed at the time, so it is not good. If the thiol compound remains in the reaction mixture, that is, (meth) propanoic acid slurry, the stability of the field when using the propionate slurry as the molding material will reduce the plant stability. To harden the forming material containing (meth) acrylic acid slurry, it is necessary to __- 17_ wood paper Standards apply to Chinese National Standards (CNS) Eighty-four Secrets (• ϋ- an ^ i · — I n LI ϋ_ϋ II i · i · (Please read the precautions on the back before filling this page), 1T, • m I-- -n in Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, etc. 18 438819 1 Old · '-丨 · V. Description of the invention (15' Meanwhile, the average molecular weight of the hardened product cannot be increased. The amount of test compound used is relative to that during polymerization When the thiol compound is added more than 1.5 times the mole, the weatherability of the obtained molded article is reduced, which is not good. In addition, the amount of maleic acid used is more than 3.0 times the mole when the thiol compound is added during polymerization. Because the water resistance of the obtained molded product is reduced, it is not good. The processing conditions such as the processing temperature and the processing time when the thiol compound is processed are not particularly limited. For example, the thiol compound can be treated by mixing the maleic acid liver and the basic compound in the reaction mixture. 〇As described above, after the monomer component and the ethylenic monomer are polymerized in the presence of a thiol compound, the reaction mixture is treated with maleic acid and a test compound, and ethylene is added to the reaction mixture. Monomer, a liquid (methyl ^) propionic acid slurry can be obtained. In addition, the (meth) propionic acid liquid solution of the present invention may be a mixture (methacrylic acid slurry A · B, etc.) obtained by the above-mentioned two or three different methods. As long as the ether compound is a compound capable of reacting with a thiol compound (a double bond), specific examples of the ethylenyl bond compound include fluorenyl ethyl ether, ethyl ethyl ether, and n-propyl ethyl. Aliphatic ethylene ethers such as propyl ethyl ether, n-butyl ethyl ether, isobutyl ethylene acid, etc .; cycloalkyl vinyl ethers such as cyclohexyl ethylene ether; 2,3-dihydrosquench, 3,4 · dihydrosquench, 2,3_dihydro_2heart ratio, 3,4-dihydro-2H4an, 3,4_dihydro_2_form Cyclic ethers such as oxygen l-biran, 34_digas_2_ethoxy-2H-late, 3,4_dihydro_4,4_dimethyl_2H_tonan_2_gang, but There is no particular limitation. These ethenyl ether compounds can also be used alone or in combination of two or more types. 'The paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm)

] —LI h — φ! 1 * r (Please read the notes on the back before filling this page), 1T .I- I-II-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 438819 A7 __B7 V. Description of the invention ( 16) The vinyl sulfide compound of the present invention is only a compound having a double bond capable of reacting with a thiol compound. The vinyl sulfide compound may be a compound having a structure in which an oxygen atom in the vinyl ether compound exemplified above can be replaced with a sulfur atom. That is, the acetamyl sulfide compound specifically includes, for example, an aliphatic acetamyl sulfide corresponding to the aliphatic vinyl ether exemplified above; and a cyclamyl ethyl corresponding to the foregoing exemplified cycloalkyl acetamyl ether. Fluorenyl sulfide; cyclic sulfide and the like corresponding to the aforementioned exemplified cyclic ether, but are not particularly limited thereto. These ethionyl sulfide compounds may be used alone or in combination of two or more kinds. The amount of the ethylene acid compound and / or the acetamidine sulfide compound is preferably from 5 times mole to 5 times mole, more preferably 0.8 times mole to 3, relative to the thiol compound added during polymerization. Bemor. When the amount used is less than 0.5 mol, the 'thiol compound is not completely processed, so it is not preferable. If the thiol compound remains in the reaction mixture, that is, the (meth) acrylic acid slurry, the storage stability when the (meth) acrylic acid slurry is used as a molding material is reduced. In addition, in order to harden a molding material containing a (meth) acrylic slurry, it is necessary to have a long time, and meanwhile, the average molecular weight of the hardened material cannot be increased. In addition, if the amount used is more than 5 mols, the weatherability of the obtained molded article is reduced, which is not preferable. The processing conditions such as a processing temperature and a processing time when the thiol compound is processed are not particularly limited as long as they are determined according to the composition of the reaction mixture and the like. The method for adding the vinyl ether compound and / or the vinyl sulfide compound is not particularly limited. For example, these compounds may be added to the reaction mixture, and the reaction mixture may be added to the above compounds. As long as the reaction mixture is mixed and stirred with the vinyl ether compound and / or vinyl sulfide compound —-----—; —------ Order ------ Λ. II: (Please read the back first Note before filling out this page}

Printed by the Employees' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 4 3 88 1 9 A7 1 _----—_____________ 5. Description of the Invention (17) ′ can handle thiol compounds. Treated with vinyl ether compound and / or vinyl sulfide compound (methacrylic acid slurry [hereinafter, if it must be distinguished from others, it is referred to as (meth) acrylic acid slurry C]), and can also be used as a coating Etc., but it is particularly suitable as a molding material for 8.0, BMC, pre-mixed materials, injection molding materials, drawing molding materials, injection molding materials, extrusion molding materials, etc. The treatment of thiol compounds can also be used in Lewis acid and amines. Salt, tertiary amine, quaternary ammonium salt, scale salt, metal salt and other catalysts. This can promote the reaction of thiol compounds, ethyl ether compounds and / or vinyl sulfide compounds. Also, When performing the above treatment, a solvent may be used as required. The solvent is preferably water and / or an organic solvent. When a vinyl ether compound and / or an ethyl sulfide compound is added to the reaction mixture, the reaction mixture contains a carboxyl group. In the case of a polymer, before the addition of the above compound, or after the addition, if necessary, glycidyl (meth) acrylate and / or methyl (meth) acrylate are added to the reaction mixture. Water glyceride, it is more preferable to esterify the carboxyl group containing the polymer. By this, a (meth) acrylic acid slurry c containing a polymer having an ester bond can be obtained. The addition amount of the methyl glycidyl (meth) acrylate is not particularly limited as long as it is set according to the composition of the reaction mixture, and the like, but it is 0.5 times mole relative to the vinyl monomer ~ 2 times mole is better, 0. 8 times mole is better;!. 5 times mole is better. When performing the above esterification reaction (hereinafter, when it must be distinguished from others, it is referred to as esterification reaction A), as required Esterification catalyst can be used. The esterification catalyst is only _____- 20 -____ This paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) iT (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 88 1 9 A7 ____B7 V. Description of the invention (18) The compound that promotes the ring-opening reaction between the I group and the epoxy group is not particularly limited. Specific examples of catalysts include: dimethylbenzyl Tertiary amines such as, triethylamine, tetramethylethylene monoamine, di-n-octylamine, etc .; quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, etc .; benzyltriphenyl Fourth-grade phosphonium salts such as base scale chlorine, metal salts, etc. These esterification catalysts can be used alone or in combination of two or more types. The amount of the catalyst added is based on its type, The composition of the reaction mixture, the amount of glycidyl (meth) acrylate and / or the amount of glycidyl (meth) acrylate, these combinations, and the like may be set, and are not particularly limited, but are 'relative to 1 in the reaction mixture. 〇parts by weight, more preferably from 0 parts by weight to 5 parts by weight, and more preferably from 0.1 parts by weight to 3 parts by weight. When the above-mentioned esterification reaction A is performed, a polymerization inhibitor may be coexisted as necessary. Specific examples of the polymerization inhibitor include: · hydroquinone, methylhydroquinone, methylate, second butyl hydrogen, and the like. Furthermore, a solvent can be used when performing the said vinegarization reaction a as needed. The solvent is preferably water and / or an organic solvent. In the present invention, a (meth) acrylic acid slurry [untreated (meth)] is obtained by polymerizing a monomer component containing a (meth) acrylate and a vinyl monomer containing a carboxyl group in the presence of a thiol compound. Acrylic slurry], an esterification reaction with an unsaturated epoxy compound in the presence of a metal compound to be described later (hereinafter, when it must be distinguished from others, it is referred to as esterification reaction B), and a molding material can also be obtained. The unsaturated epoxy compound may be a compound containing an epoxy group capable of reacting with a carboxyl group and a polymerizable double bond in one molecule. Specific examples of this unsaturated soil oxygen compound are: allyl glycidyl ether, glycidyl-21-This paper is suitable for Guancai County (CNS) A4 size (210X297) I ------- --- • Cloths ----- 1T ------, φ (Please read the notes on the back before filling this page) 438819 V. Description of the invention (! 9) Staff consumption of the Central Standards Bureau of the Ministry of Economy and Economy Cooperatives print oil-based (meth) acrylates, methylglycidyl (meth) acrylates, mono (meth) acrylates of epoxy resins, and the like, but are not particularly limited to these. These unsaturated epoxy compounds may be used singly or in combination of two or more kinds. The use amount of the unsaturated epoxy compound is not particularly limited as long as it is set according to the type and the like of the untreated (meth) propionic acid polymer solution, but it is relative to the (meth) acrylic acid. The vinyl monomer used in the manufacture of the slurry is preferably 0.5 times mole to 2 times mole, and more preferably 0.8 times mole to 1.5 times mole. The above-mentioned metal compound contains an esterification catalyst containing at least one element selected from the group consisting of zinc, tin, and zirconium. Since the catalyst activity is high, it can mainly promote the carboxyl group of the untreated (meth) acrylic acid slurry, Esterification reaction B with an epoxy group possessed by an unsaturated epoxy compound. Examples of the metal compound include an inorganic metal compound, a metal oxo acid salt, a polyoxo metal salt, an organic metal compound, an organic acid metal salt, and a gold &amp; salt. In addition, the molding material obtained by using the metal compound has more excellent storage stability. In addition, by using the molding material to a molded article with little coloring. F The inorganic metal compounds include, for example, metal fluorides, Metal bromides, metal chlorides, metal iodides, etc .; metal chalcogenides, such as metal oxides, metal sulfides; metal nitrides; compounds; metal sulfides; metal carbides; metal silicides; Metal cyanides; metal hydroxides; metal gasification oxides, and specific examples include zinc chloride, zirconia, tin sulfide, etc. Huaer III— || ~ ΜII 曹 1 · (Please read the note on the back first Please fill in this page again for the matter} -Order-I-I- -22- "Applicable to the Zhang scale" A4 size (2K) X297 mm_) one 388

V. Description of the invention (20) ----- The above-mentioned metal salt of hydrogen acid printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics can be exemplified by metal sulfate, metal nitrate, phosphorous, phosphinic acid, and phosphonic acid Metal salts, metal metaphosphates, metal acid salts, gas acid metal #, metal bromate :, metal acid salts, silicon salts, etc. Moreover, specifically, for example, tin sulfate, zinc phosphate, nitrate, and Bisi. Also, in the present invention, metal oxo acid salts are also called for those containing hydrogen phosphate of zinc hydrogen phosphate. Examples of human polyoxometalates include: polyphosphate metal salts, polyborate dibasic acid niobate metal salts, polybutton acid metal salts, polymolybdate metal salts, vanadate metal salts, and polytungstate metal salts. Wait. Specific examples include zinc phosphate. The above-mentioned organometallic compound may be, for example, represented by the general formula ⑴ M &quot; (R) n ...... ⑴ （(where M represents zinc, tin, or germanium, R represents a methyl group, an ethyl group, and the like; Or an ethoxy group such as ethoxy, η represents an integer of 1 to 6), and specifically, for example, diethylzinc, tetraethoxy cone, and the like. Examples of the organic acid metal salt include metal clad, metal acetate, metal benzoate, metal salicylate, metal oxalate, metal tartrate, metal salt, and citric acid metal salt. The metal bag may be, for example, a metal salt of lauric acid, a metal salt of myristic acid, a metal salt of palmitic acid, a metal salt of stearic acid, a metal salt of oleic acid, or the like; a metal salt of cyclic acid, a metal salt of caprylic acid , Continuous acid metal salt, sulfuric acid @ Purpose metal salt, phosphoric acid g purpose metal salt, etc. Further, specifically, for example, zinc octoate, tin stearate; zinc acetate, tin salicylate, and the like can be mentioned. The above metal salts can be given, for example, by the general formula (2) —.1 • 丨 contention, 玎 ^! * Second C, please read the precautions on the back before filling out this page) -23- Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printed ^ 388 19 at ____B7 V. Description of the invention (21) M- (L) n… (2) (where M is 7F zinc, tin, or cone, L represents acetone, etc. Position, n represents an integer of 1 to 6). Further, specifically, for example, zinc acetoacetone and the like can be mentioned. These metal compounds may be used alone or in combination of two or more. The use of the metal compound is not particularly limited as long as it is set according to the type thereof, or a combination of an untreated (meth) acrylic acid slurry and an unsaturated epoxy compound, but it is relative to the untreated (meth) acrylic acid slurry. 100 parts by weight is preferably 0.01 parts by weight to 5 parts by weight, and more preferably 0.01 to 3 parts by weight. When the above-mentioned acetation reaction B is carried out, if necessary, for example, the aforementioned polymerization inhibitors can coexist. Furthermore, when the above-mentioned esterification reaction B is carried out, the solvent exemplified above can be used as necessary. When the esterification reaction B is carried out, it is also possible to use the esterification catalyst exemplified above instead of the metal compound. The order or method of mixing the untreated (meth) acrylic acid slurry, the unsaturated epoxy compound, and the metal compound in the above-mentioned esterification reaction B is not particularly limited. In short, the timing of the esterification reaction B of the untreated (meth) acrylic acid slurry and the unsaturated epoxy compound is sufficient as long as the metal compound is present in the reaction system. Thereby, the carboxyl group having an untreated (meth) acrylic acid slurry and the epoxy group having an unsaturated epoxy compound undergo an esterification reaction (ring-opening reaction), and the (meth) acrylic acid slurry [hereinafter, sometimes When it is necessary to distinguish it from others, the polymerizable double bond can be introduced as (meth) acrylic acid slurry E]. That is, 'a side chain with a polymerizable double bond can be obtained through ester bonding and contains — 24 — This paper size applies to Chinese national standards (CNS> M specification (210X297 mm) ϋ ·-ϋ · ^ ^ 1- · Ϋ — ^ ϋ ϋ ^ — ϋ · __ϋ ϋ_ϋ memmmmmmM ϋ · ϋ I Βϋϋ 、 一 「心 nl_— tmtaMme ϋ ^ —— —.I ·· — 一 ·--(Please read the notes on the back before filling this page ) 438819 A7 B7 V. Description of the invention (22) ~ ---; ----------; * ~ r (Please read the notes on the back before filling this page} There is a combination of ( A material of a (meth) acrylic polymer. The molding material contains (meth) acrylic acid slurry E that introduces a polymerizable double bond through an ester bond, and contains at least one element selected from zinc, tin, and Metal compounds in the cone group. The forming material containing (meth) acrylic slurry E is particularly suitable for forming SMc, BMC, pre-mixed materials, injection molding materials, draw molding materials, injection molding materials, and extrusion molding materials. Materials. (Meth) propionic acid slurry E is thermosetting because it has a polymerizable double bond. A polymerizable double bond can also be introduced by esterifying a (meth) acrylic acid ester-based polymer having an epoxy group with a vinyl monomer. The double bond equivalent in the polymer, that is, the weight average molecular weight (Mw) per polymerizable double bond is preferably in the range of 200 to 10,000, and more preferably 10,000 to 8,000. The optimal range is from 2,000 to 5,000. By adjusting the double bond equivalent weight to the above range, the molded product obtained by hardening the molding material can suppress cracks. It is printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. If the double bond equivalent is less than 200, the molded article obtained by curing the molding material may have poor surface smoothness or gloss. In addition, if the double bond equivalent exceeds 10,000, the volume shrinkage of the molding material when it is hardened cannot be sufficiently suppressed. At the same time, the surface smoothness, gloss, and other surface properties of the molded product obtained by hardening the molding material, or the strength under heat may be reduced. Also, when a polymerizable double bond is introduced, the (meth) acrylate polymer The weight average molecular weight is preferably 3,000 to 500,000, more preferably 5,000 to 10,000, and most preferably in the range of 10,000 to 40,000. If the weight average molecular weight is less than 3,000, the physical properties of the obtained molded product In addition, if the weight averages 8-25- d 3 8 8 1 9 A7 B7 5 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, and the description of the invention (23) The volume is more than 500,000, (meth) propionic acid slurry The viscosity of E will be too high, and the workability of the molding operation will be reduced. A molding material containing (meth) acrylic slurry E and a metal compound, or a molding material containing the aforementioned (meth) acrylic slurry C, as required, It may contain at least one thermoplastic polymer selected from the group consisting of a thermoplastic elastomer, a thermoplastic resin, and a rubber. At this time, if the thermoplastic polymer is dispersed in the (meth) acrylic acid slurry C and E, if the thermoplastic 咼 molecules are dispersed, the thermal expansion of the thermoplastic polymer during heating and curing can effectively suppress the forming material, that is, the hardened material. shrink. In a third aspect, since the volume shrinkage of the molding material is low when it is hardened, by molding the hardening of the molding material, a molded product having superior surface properties such as surface smoothness and gloss can be obtained. Here, the term "dispersion of the thermoplastic polymer Γ" in the (meth) acrylic acid slurry c ', E means that the thermoplastic polymer (dispersed phase) is dispersed in the form of fine particles in the (meth) acrylic acid slurry C, E. status. More specifically, the thermoplastic polymer is dispersed in the (meth) acrylic acid slurry C ', E in the form of fine particles having a particle diameter of 1 mm or less, and the molding material is in an opaque state. The term "dissolved" refers to a state in which the dispersed phase is dispersed to a particle size of the size of molecules or ions, and the molding material is transparent. The "thermosetting property" refers to the property that the dryness is increased by heating, and that a product insoluble in a solvent is formed by a crosslinking reaction. By "thermoplastic" is meant that the viscosity is reduced by heating and is soluble in at least one solvent. In addition, by using a low-shrinkage agent described later in combination with a thermoplastic polymer described herein, the shrinkage can be reduced more efficiently. 26- Common Chinese National Standard (CNS) A4 specification (21 × X 297 mm) as far as possible paper size IJ, | ~ ^ ^ &quot; I ♦ II: (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 438819 A7 _ ^ B7 V. Description of the Invention (24) In the present invention, the so-called thermoplastic elastic system is expressed in the molecule and has a rubber component (soft component) with elastic structure. A resin component (hard component) that prevents plastic deformation structure, a thermoplastic polymer that exhibits rubber elasticity at room temperature and exhibits plasticity at high temperature. The so-called thermoplastic resin is a thermoplastic polymer that has only a resin component (hard component) that prevents plastic deformation in the molecule and does not exhibit rubber elasticity at room temperature. The rubbers indicated are high molecules that show rubber elasticity at room temperature or even south temperature. &quot; Specific examples of the above thermoplastic elastomers include: styrene / ethylene / propylene / styrene copolymer (SEP S), styrene / ethylene / butene / phenylethyl fluorene copolymer (SEBS), anhydrous malay Acid-denatured stilbene / acetamidine / butadiene / phenylethylidene copolymer (MA denatured SEBS), styrene / isoprene / phenylethyl hydrazone copolymer (SIS), styrene / butadiene / styrene Copolymers (SBS), styrene / ethylene / propylene copolymers (SEP), styrene-based thermoplastic elastomers; polyester-based thermoplastic elastomers; polybutadiene-based thermoplastic elastomers, etc., but there is no special Limited to these. These thermoplastic elastomers may be used alone or in combination of two or more. The thermoplastic elastomer may be appropriately selected in accordance with the type of the (meth) acrylic slurry C ', E, but, among the thermoplastic elastomers exemplified above, a styrene-based thermoplastic elastomer is particularly preferred. In addition, the styrene-based thermoplastic elastomer may be linear or radial. The styrene content of the above styrene-based thermoplastic elastomer is (meth) propionic acid slurry C, E. The unreacted ethylammonium monomer contained in methyl methacrylate, or unreacted ethylene When the base compound is phenethyl, ______ -27- This paper size applies the Zhongguanjia Standard (CNS) M specification (training; 7 meals) _ —; ---: ---- — · *: (Please read the notes on the back before filling in this page) Order 4388 1 9 A7 _______ ____B7 V. Description of the invention (25) Weight% ~ 25% by weight 'more preferably 丨 3% by weight / ❶ ~ 20% by weight. When the (meth) propionic acid polymer liquids C 'and e contain methyl methacrylate or styrene other than unreacted compounds such as third butyl methacrylate, the styrene content is preferably 10 The weight% to 40 weight% / c, more preferably 13 weight weight /% to 30 weight weight / 0. By setting the styrene content within the above range, it is possible to more effectively suppress shrinkage of the hardened material, which is a molding material. Specific examples of the thermoplastic resin include acid-denatured polyvinyl acetate (acid-denatured PVAc), vaporized ethylene-vinyl acetate copolymer (vcl_VAc), ethylene / vinyl acetate copolymer (EVA), and cellulose acetate. Butyrate (CAB), acrylonitrile, ethylene propylene diene rubber / styrene copolymer (AES), propionate rubber / acrylonitrile / styrene (AAS), and the like are not particularly limited. These thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin may be appropriately selected in accordance with the type of the (meth) acrylic slurry c, E, and the like. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ~ -------- Cao II / *: (Please read the precautions on the back before filling out this page) L »The above rubber can be specifically exemplified: styrene / Butadiene rubber (SBR), hydrogen-added styrene / butadiene rubber (HSBR), nitrile / butadiene rubber (nbr), butadiene rubber (BR), natural rubber, isoprene rubber, etc. Diene rubber; chloroprene rubber; butyl rubber; ethylene / propylene rubber; acrylic rubber (ACM), urethane rubber, etc., but it is not particularly limited thereto. These rubbers may be used alone or in combination of two or more. The rubber may be appropriately selected depending on the type of the (meth) acrylic slurry C, E, and the like. The above-mentioned thermoplastic polymer glass transition temperature (hereinafter referred to as Tg) is preferably -100 ° C to 80 ° C, more preferably -70 ° c to 30 ° c, and most preferably _60. (: ~ 01. If the Tg is lower than the above -100 ° C, the table of the molded product obtained by hardening the molding material _____________- 28-This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) ) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 8 8 1 9 A7 ———____ B7_ V. Description of the Invention (26) The gloss of the surface will decrease. In addition, if the above Tg exceeds S (rc, the thermoplastic polymer is very It is difficult to swell, and the shrinking effect of the molding material, that is, the hardened material, becomes insufficient. In the present invention, the Tg of the thermoplastic polymer is, for example, the T of the rubber component when the thermoplastic polymer is a thermoplastic elastomer. g is the low temperature side T g. The amount of the thermoplastic polymer added is 100% by weight based on the total of (meth) acrylic acid slurry C, £ and thermoplastic polymer, preferably 2% by weight. ~ 50% by weight, more preferably 5% by weight ❶ / ❶ ~ 30% by weight, and most preferably 10% by weight to 20% by weight. When the added amount is less than 2% by weight, the shrinkage effect of the molding material, that is, the hardened material, becomes Not good, so when hardened The product shrinkage rate will increase, and a molded product with excellent surface properties will not be obtained. In addition, if the added amount exceeds 50% by weight, the viscosity of the (meth) acrylic acid slurry c, e will increase too much, making it difficult to make ingredients. As long as it is stably dispersed in the (meth) propionic acid slurry c,, E, it is preferable to form a dispersed phase having a particle diameter of 5 nm to 800 m, and more preferably to form a particle diameter of 50 nm to 500 a. The dispersed phase of 111 is particularly suitable to form a dispersed phase having a particle diameter of 100 nm to 100 &quot; m. A molding material containing (meth) acrylic slurry E and a metal compound, or a molding material containing (meth) acrylic slurry C, In order to stabilize the dispersed state of the thermoplastic polymer, a dispersion stabilizer may be further contained as required. This can further increase the appropriate combination of the (meth) acrylic slurry c, E, and the thermoplastic polymer. As long as the stabilizer is in the molecule, it has a high affinity with (meth) acrylic acid slurry C and E, and an affinity with thermoplastic polymers. 29- This paper is based on Chinese standards (CNS) Α4 regulation (210X297 public shame) (Note, please read the back of this page and then fill -W)

438819 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (27) Aggregates of high-performance parts are sufficient. As the dispersion stabilizer, for example, when the thermoplastic polymer is a styrene-based thermoplastic elastomer, a styrene / vinyl acetate copolymer or a styrene / methyl methacrylate copolymer is preferable. The method for dispersing a thermoplastic polymer in a (meth) acrylic acid slurry may include, for example: ① a method of adding a stirring thermoplastic polymer to (meth) acrylic acid slurry C, E; ② the monomer composition A method of adding a thermoplastic polymer after stirring and polymerizing it; ③ A method of adding a stirring thermoplastic polymer to the aforementioned vinyl monomer and then adding a (meth) acrylic polymer; ④ in a vinyl monomer After adding a thermoplastic polymer, the method of adding (meth) acrylic acid slurry C, E, etc. is added. In these methods, the stirring system may be performed using, for example, a high-speed stirrer at a stirring speed of about 10,000 rpm. The stirring time may be appropriately selected depending on the stirring speed and the like, but is preferably 1 minute or more, and more preferably 10 minutes or more. Among the methods exemplified above, the method of adding a thermoplastic polymer to the (meth) acrylic acid slurry C ', E is the easiest in manufacturing and can obtain a molding material efficiently. Therefore, the molding of the present invention is particularly preferable. The material contains a monomer component comprising the (meth) acrylate-containing monomer and a carboxyl-containing vinyl monomer after polymerization in the presence of a thiol compound, and then treating the reaction mixture with maleic anhydride and a basic compound. Composition of (meth) acrylic acid slurry A. The molding material of the present invention includes a (meth) group obtained by polymerizing a monomer component containing a (meth) acrylate in the presence of a thiol compound, and treating the reaction mixture with maleic anhydride and a basic compound. Acrylic slurry B, and vinyl monomer. -30 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling this page)-Order 438819 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Explanation (28) Furthermore, the molding material of the present invention includes a reaction mixture obtained by polymerizing a monomer component containing (meth) acrylate in the presence of a thiol compound, and adding a vinyl ether compound and / or ethylene (Meth) acrylic acid slurry C consisting of a sulfide compound. The above-mentioned (meth) acrylic acid slurry C may be a reaction mixture obtained by polymerizing a monomer component containing a (meth) acrylate and a vinyl monomer component containing a carboxyl group in the presence of a thiol compound. In this case, a vinyl ether compound and / or a vinyl sulfide compound are added. The molding material of the present invention contains a (meth) acrylic acid slurry C, which is a reaction mixture (which is a monomer component containing a (meth) acrylate ester and a carboxyl group-containing vinyl monomer in a thiol compound Formed by the following polymerization) adding (meth) acrylic acid glyceride and / or (meth) acrylic acid to the reaction mixture 'as needed' before or after adding the vinyl ether compound and / or vinyl sulfide compound Methyl glycidyl ester esterifies a carboxyl group containing a polymer, and fluorene contains a (meth) acrylate polymer having a side chain having a polymerizable double bond bonded to a main chain. Furthermore, the molding material of the present invention includes a (meth) acrylic acid slurry E, which is obtained by polymerizing a monomer component containing a (meth) acrylate and an ethylenic monomer containing a carboxyl group in the presence of a thiol compound. The reaction mixture and the unsaturated epoxide are subjected to esterification in the presence of a metal compound containing at least one element selected from the group consisting of zinc, tin and cone, and fluorene has a side chain with a polymerizable double bond bound to (Meth) acrylate polymer of main chain. Another forming material of the present invention includes a (meth) acrylic acid slurry D, which is a monomer component containing (meth) acrylic acid ester in the presence of a thiol compound -31-Winter paper scale applies Chinese National Standard (CNS) A4 specification (210'〆297mm) 1—: ^ — — *; (Please read the precautions on the back before filling this page) Order 4388 1 9

V. Explanation of the invention (29): After the combination, the reaction mixture is added with an ethylamidine compound 2 ether compound, and at the same time, a vinyl monomer is added to the reaction mixture. ^ Another forming material according to the invention of the present invention includes _ double-bond meth) acrylic acid slurry E with an acetic acid bond, and at least one element selected from the group consisting of zinc, tin, and cone. Metal compounds. Further, the molding material of the present invention further contains a granulating agent, a succinic acid derivative, a reinforcing material, and the like, as necessary. This molding material can be hardened in a shorter time than conventionally. In addition, by molding the molding material, a molded product excellent in various physical properties such as heat resistance, solvent resistance, weather resistance, and water resistance can be obtained. In the following description, components other than the reinforcing material in the molding material are referred to as ingredients. Specific examples of the above-mentioned thickening agent include: alkaline earth metal oxides such as magnesium oxide and calcium oxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; and the like, but are not particularly limited thereto. These bulking agents may be used alone or in combination of two or more kinds. Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs ---: -I — ΙΦ! V-^ (Please read the precautions on the back before filling this page) Although the amount of tackifier used depends on its type, or ( The combination of the (meth) acrylic slurry, the use of the molding material, and the like depend on 100 parts by weight of the (meth) acrylic slurry, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. By using the tackifier within the above range, the viscosity of the ingredients after tackifying can be set to a predetermined value suitable for a molding operation or the like. When the amount of the tackifier is more than i 0 parts by weight, the viscosity after the ingredients are thickened may be too high, and when the molding operation is reduced, the weather resistance and water resistance of the obtained molded product may decrease. 32- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 4388 19 A7 V. Description of the invention (30) The above succinic acid derivatives are capable of inhibiting excess drowning caused by thickeners , Especially the function of the initial thickening behavior. The succinic acid derivative is only a compound having a succinic acid skeleton or a succinic anhydride skeleton in the molecule and a substituent having an alkyl group, an alkenyl group, an alicyclic hydroxyl group, or an aromatic hydroxyl group in the ethylene portion of the skeleton. It is not particularly limited, but it is preferably a compound having a total carbon number of 8 to 30. A succinic acid derivative having a total carbon number of 7 or less is not good because it has poor solubility in a (meth) acrylic acid slurry. Further, a succinic acid derivative having a total carbon number of 31 or more lacks the action and effect expected from using the succinic acid derivative. That is, the effect of suppressing the excess viscosity-increasing behavior caused by the viscosity-increasing agent is low, so it is not good. Specific examples of the succinic acid derivative include: hexylsuccinic acid, heptylsuccinic acid, octylsuccinic acid, nonylsuccinic acid, decylsuccinic acid, dodecyl succinic acid, myristyl octyl succinic acid, fifteen Hexenylsuccinic acid, hexadecyl succinic acid, heptyl succinic acid, octadecyl succinic acid, nonadecyl succinic acid, eicosyl succinic acid, etc. compounds having an alkyl group having a carbon number of 4 or more; Cylic acid, heptenyl succinic acid, octenyl succinic acid, nonanyl succinic acid, decenyl succinic acid, dodecenyl succinic acid, tetradecenyl succinic acid, pentaenyl succinic acid, hexadecyl Alkenyl succinic acid, heptenyl succinic acid, octadecenyl succinic acid, printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs J --- 1II ^ -I • 衣 II: I. (Please read the note on the back first Please fill in this page for more details) Compounds with alkenyl groups such as undecylenyl succinic acid and eicosyl succinic acid; cyclododecyl succinic acid and cyclododecenyl succinic acid with aliphatic ^ Compounds; aromatic compounds such as diphenylbutenyl succinic acid; and, It is not particularly limited only two other acid derivative may be used alone, but also by the force J Xin two or more kinds. There is no particular limitation on the method for preparing the carboxylic acid derivative. ____- 33-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 × 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 43 88 1 9 A7 ____B7_ V. Description of the invention (31) Addition of succinic acid derivatives The amount depends on the type, the combination of (meth) acrylic acid slurry and granulating agent, and the use of the molding material. However, it is more preferably 0.001 part by weight relative to 100 parts by weight of (meth) acrylic acid slurry. ~ 10 parts by weight. When the addition amount of the succinic acid derivative is less than 0.01 part by weight, the action and effect expected from the use of the succinic acid derivative are lacking. That is, there is a fear that the effect of suppressing excess viscosity-increasing behavior due to the viscosity-increasing agent may be lacking. When the added amount of the succinic acid derivative is more than 10 parts by weight, the viscosity of the ingredients after thickening does not reach a predetermined value suitable for forming operations, or it may take a long time to reach it. Specific examples of the above-mentioned reinforcing material include inorganic fibers such as glass fibers, metal fibers, ceramics (such as silicon nitride or silicon carbide), and organic fibers such as aramide, polyester, and carbon fiber. ; Natural fiber, etc., but it is not particularly limited. The shape of the fibers may be, for example, bundled, interlaced, tufted, woven, cut, or shredded, but is not particularly limited. These reinforcing materials may be used alone or in combination of two or more types. A forming material containing a reinforcing material is suitable as, for example, SMC or BMC. In addition, when the shape of the fiber is shredded, the length of the reinforcing material is particularly preferably 1 mm or more and 6 mm or less: This can further improve the strength, surface smoothness, and gloss of the molded product obtained by molding the molding material. The amount of the reinforcing material is preferably in the range of more than 0% to 40% by weight relative to the total weight of the molding material, but it is not particularly limited as long as it is in accordance with its type or combination with (meth) acrylic slurry, etc. The use, desired physical properties, etc. may be set. For example, when a molding material is used as the smc, the amount of the reinforcing material is more preferably from 0% to 40% by weight relative to the total weight. In addition, when the forming material is used as the BMC, the amount of reinforcing material used is relative to _________- 34-This paper size is applicable to the China National County (CNS) cell (21GX297 mm) ------------- —; --- r-, ---- ί *: (Please read the notes on the back before filling out this page} -Order 1 438819 Α7 Β7 V. Description of the invention (32) The full weight is more preferably 2 weight % ~ 3G% by weight. When the reinforcing material is used within the above range, a molded article having excellent strength such as tensile strength or elasticity can be obtained. When the shape of the fiber is Choppedstrand, the amount of the reinforcing material used is relative to The total weight of the molding material should preferably be in the range of 5% to 9% by weight. In this way, it can be transferred to a molding material with excellent handling, productivity, or formability, and at the same time, the molding product obtained by molding the molding material can be further improved. Strength, surface smoothness, and gloss. X can prevent cracking of the molded product. There is no particular limitation on the method of mixing the reinforcing material and ingredients, as long as it is appropriately set according to the form of the reinforcing material. For example, when the form of reinforcement is wrong or cross, just immerse the ingredients in the reinforcement In addition, for example, in the case of a reinforcing material (in the form of a bundle or a shred, etc.), it is only necessary to mix the reinforcing material with the ingredients, or to impregnate the reinforcing material with the ingredients. The staff of the Central Standards Bureau of the Ministry of Economy The molding material printed by the cooperative according to the present invention preferably contains a hardener (polymerization initiator), and may further be impregnated with a filler and a crosslinkable monomer (crosslinker) as needed. The j hardener may be produced, for example, by manufacturing The aforementioned example polymerization initiator used for the (meth) acrylic acid slurry is not particularly limited. The addition of the hardener may be set according to the type or the combination of the (meth) acrylic acid slurry. None It is particularly limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid slurry. Specific examples of the filler include aluminum hydroxide, calcium carbonate, sulfuric acid, and oxidation. Inorganic fillers for aluminum, clay, talc, milled fiber, silica (silica sand), chuan sand, diatomite, mica powder, gypsum, chilled stone (sand), asbestos powder, glass powder, glass ball, etc. Organic fillers such as plastic granules, etc., but are specially limited. These fillers can also be used alone, and also 35- (Please read the precautions on the back before filling this page) This paper is suitable for standard ((21 〇χ297mm) 438819 A7 ------- «&lt;-_B7_ V. Description of the invention (33) Two or more types can be used together. Moreover, the average particle size of the filler and other forms are not limited. The dosing amount may be set in accordance with the type or combination with the (meth) acrylic slurry, the use of the molding material, desired physical properties, and the like, and is particularly limited. However, it is relative to the (meth) acrylic slurry. 〇〇 重量 份 'is preferably 10 parts by weight to 600 parts by weight. Further, when a molding material is used as the sMC, the amount of the filler to be formulated is more than 100 parts by weight, and more preferably 30 to 300 parts by weight relative to the (meth) acrylic acid slurry. When a molding material is used as the BMC, the blending amount of the filler is more preferably 150 to 600 parts by weight relative to 100 parts by weight of the (meth) acrylic acid slurry. When a molding material is used as the injection molding material, the amount of the filler is relative to 100 parts by weight of the (meth) propionic acid slurry, and more preferably 30 to 350 parts by weight. When a molding material is used as the drawing material, the blending amount of the filler is more preferably 100 parts by weight to 200 parts by weight relative to 1,000 parts by weight of the (meth) acrylic acid slurry. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs II ---- ΦΤΙ m ^ i (Please read the notes on the back before filling this page) The above-mentioned crosslinkable single system has the function of increasing the crosslink density of hardened materials. The crosslinkable single system may be any compound containing a plurality of functional groups capable of reacting with the functional groups contained in the (meth) acrylic acid slurry. Specific examples of the crosslinkable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) propionate, and dipropylene glycol di (formaldehyde). Polyfunctional (meth) acrylates such as methacrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) propionate, etc. ; Epoxy (meth) propionates; Divinylbenzene, diallyl g tarate, diallyl isophthalate, triallyl cyanide-36- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) '' Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 s ----------_ B7 V. Description of the invention (34) Isocyanate and the like are not particularly limited. The crosslinkable single plate &lt; added amount is set according to its type or combination with (meth) acrylic slurry, etc., the use of the molding material, desired physical properties, etc., and the blood is particularly limited. It is used in the presence of thiol compounds. When the monomer composition is polymerized, or when the monomer component is polymerized in the presence of a sulfur compound, the human-based monomer may be added as necessary. In this case, the addition amount of the crosslinkable monomer is not particularly limited as long as it is set in accordance with its type or combination with the monomer composition (or monomer component), the use of the molding material, or desired physical properties. The above-mentioned additives can be various additives generally used, and are not particularly limited. Examples include: low shrinkage agents, (internal) release agents, colorants, polymerization inhibitors, and the like. These additives may be appropriately added depending on the use of the molding material, desired physical properties, and the like. In addition, the amount of the additive to be added may be determined in accordance with the type of the additive, a combination with the (meth) acrylic acid slurry, and the like, and is not particularly limited. Specific examples of the low shrinkage agent include: polymethyl methacrylate, polyethylene, polypropylene, polystyrene, polyethylene glycol, polypropylene glycol, cellulose butyrate, acetate, polyvinyl chloride, poly Thermoplastic polymers having no carboxyl group such as vinyl acetate, polycaprolactone, and saturated polyester, but are not limited thereto. By adding a low shrinkage agent, the hardening shrinkage of the molding material can be suppressed, so that the dimensional stability of the molded product can be further improved. The weight-average molecular I of the aforementioned low-shrinkage agent, that is, a thermoplastic polymer, is preferably 1,000 or more and 20000 or less. As a result, the low shrinkage agent is more uniformly dispersed in the forming material, so the line of the forming material can be effectively suppressed _________ -37- This paper size applies to the Chinese National Standard (CNS) 8-4 specification (2 297 mm) ^ M — -r; (Please read the notes on the back before filling this page) Order 4388 19 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 __ 5. Description of the invention (35) Shrinkage. In addition, the dimensional stability, surface smoothness, and gloss of the molded product can be further improved. The addition amount of the low-shrinking agent may be set depending on the type or combination with the (meth) acrylic slurry, the use of the molding material, or desired physical properties, and it is not particularly limited. It is relative to the (meth) acrylic slurry 100 parts by weight, preferably 5 to 50 parts by weight. Examples of the releasing agent include stearic acid, zinc stearate, aluminum stearate, calcium stearate, barium stearate, ammonium stearate, triphenylphosphonate, alkylphosphonate ; Release agents such as waxes and silicone oils generally used. The colorant may be a known inorganic pigment or organic pigment. The above-mentioned forming materials are suitable as SMC, BMC, injection molding materials, etc. The SMC can be easily manufactured using a so-called SMC manufacturing apparatus. The BMC series is easily manufactured using a kneading machine such as a double wrist kneader. The SMC or BMC is, for example, 6 (TC ~ 16 (TC, more preferably 70. (: ~ 140X :, most preferably 80 C ~ 130 C), heating and press forming (press forming) to form a molded product.) The injection material is injected (injected) into the mold at room temperature to 701 to form a molded product. Furthermore, the method of hardening the molding material, that is, the manufacturing of the molded product is not particularly limited. Related to the present invention The molding material can be applied to various molding methods such as compression molding method, injection molding method, and transfer molding method, but the compression molding method is particularly suitable. The molding pressure can be set according to the shape or size of the molded product to be manufactured. There is no particular limitation, but it should preferably be about 0.1MPa to 20MPa. The molding pressure within the above-mentioned range can be used to form a molded article with better surface smoothness. The molding time only needs to consider the molding temperature and molding pressure! I Tube-(Please read the notes on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 438819 A7 __B7 V. The description of the molding conditions (36) and the hardening speed of the molding materials can be set as appropriate, and there is no particular limitation. As described above, the method for producing (meth) acrylic acid slurry A of the present invention is to polymerize a monomer component and a vinyl monomer in the presence of a thiol compound, and then treat the reaction mixture with maleic anhydride and a basic compound. . Moreover, the manufacturing method of the (meth) acrylic acid slurry B of this invention is after polymerizing a monomer component in the presence of a thiol compound, and treating this reaction mixture with maleic anhydride and a basic compound, and in this reaction mixture Add vinyl monomer. Furthermore, the manufacturing method of the (meth) acrylic acid slurry C of this invention is a reaction mixture which polymerized the monomer component containing a (meth) acrylate in the presence of a thiol compound, and adds a vinyl ether compound and / Or vinyl sulfide compounds. Furthermore, the method for producing a (meth) acrylic acid slurry c according to the present invention is a reaction obtained by polymerizing a monomer component containing a (meth) acrylic acid ester and a vinyl monomer containing a carboxyl group in the presence of a thiol compound. A vinyl ether compound and / or an ethyl sulfide compound may be added to the mixture. In the method for producing a (meth) acrylic acid slurry C1 of the present invention, after polymerizing a (meth) acrylic acid-containing monomer component and a carboxyl group-containing vinyl monomer in the presence of a thiol compound, the reaction mixture is subjected to Before or after adding the vinyl ether compound and / or the ethylene sulfate compound, glycidyl (meth) acrylate and / or methyl glycidyl (meth) acrylate are added to the reaction mixture to contain a polymer. The carboxyl group is esterified, and a side chain having a polymerizable double bond is bonded to the main chain. -39- This paper size is applicable to China National Standard (CNS) A4 (210X297mm) (Please read the precautions on the back before filling this page)

1T 438819 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

A7 B7 V. Description materials of the invention (38), etc .; exterior materials such as roofs and walls; suitable artificial marbles such as bathtubs, cooking tables (kitchen ceilings), various countertops, vanity vanities, etc .; electrical appliances, etc. But it is not limited to these. The molded product is beautiful and suitable for various applications that require beautiful appearance. In addition, a molded article formed by molding a molding material containing a filler has a beautiful marble shape, and is therefore suitable as an artificial marble. Further objects, features, and advantages of the present invention will be fully understood from the description below. The advantages of the present invention will be apparent from the following description. BEST MODE FOR IMPLEMENTING THE INVENTION The present invention will be described in further detail by way of examples and comparative examples, but the present invention is not limited to these. The "part" described in the examples and comparative examples means "parts by weight", and "%" means "% by weight". [Example 1] In a reactor equipped with a thermometer, a cooler, a nitrogen introduction pipe, and a stirrer, 196 parts of methacrylate as a (meth) acrylate was fed, and vinyl monomer was used as a monomer. After 4 parts of methacrylic acid, the reactor was purged with nitrogen. Next, while stirring the mixture, the temperature was raised to 80 ° C, and then 0.1 parts of 2,2, -azobisisobutyronitrile (hereinafter referred to as AIBN) as a polymerization initiator was added, and as a normal thiol compound. Dodecyl mercaptan started to polymerize. 420 minutes after the start of the polymerization, the particle size of the reaction solution was 30 to 35 poise (25 ° C), so the reaction was ended at this point (that is, the reaction time was 420 minutes), and methacrylic acid was further added to the reaction solution. After 35 parts of methyl ester, it is cooled (quenched) -41-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative 438819 A7 B7 V. Description of Invention (39) The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed to 40 ° C. Then, 07 parts of maleic acid liver and 0.04 parts of triethylamine as a test compound were added to the obtained reaction mixture, and the reaction mixture was added to the reaction mixture for 15 minutes (also That is, the remaining) n-dodecyl sulfur #. The maleic acid mentioned above is added 14 times more moles than the added n-dodecyl mercaptan. It is to be noted that the triethylamine is added in an amount of 0.88 moles relative to the added n-dodecyl mercaptan. &amp; Thereby, the (meth) acrylic acid slurry A of the present invention is obtained. The particle size of the (meth> acrylic acid slurry A is 7 poise (2rc), polymerization in (meth) acrylic acid slurry A The weight ratio of the (meth) acrylic acid slurry a as measured by the gel permeation chromatography (GPC) was 61%, which was 61%. Then, 100 parts of the above (meth) acrylic acid slurry A was added with 2 parts of benzamidine peroxide as a hardener I to dissolve it, thereby obtaining a casting material as a molding material. The obtained molding material is degassed by decompression. This injection molding material, that is, the ingredients have excellent storage stability. Then, use an elastic gasket to lock around two glass plates arranged oppositely (3mm apart from each other) and The formed mold chamber is filled with the injection molding material, that is, after the injection molding material is injected into the mold chamber, it is heated to harden. The gel time at 60 ° C is based on JIS κ 69〇1. Measurement .... Immediately after placing the cast-in-place material into a test tube with a diameter of 18 mm, the depth is 100 mm. Keep it in a constant temperature tank adjusted to 6 (rc), and then, the temperature of the measuring / king-type material is raised from 45t to the time of 651 by the heat of reaction. This is a mold and it should be I. I ----- ί- (Please read the Note # &quot; Matters before filling out this page} -Order · -42- 4 3 881 9 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. The description of the invention (40) is regarded as the gel time As a result, the gelation time at 60 ° C was 45 minutes. Next, after demolding, post-curing (so-called after cure) was performed in the lot to obtain a resin plate, which is a molded product. The obtained resin plate was neutralized with chlorine, and 'Crystalline is placed under the price for 24 hours == two, that is, the solvent resistance of the resin plate is good. Therefore, the resin, which is an injection-molded material, cannot be measured using GPC, which can be regarded as a high molecular weight (three-dimensional). The main reaction conditions and results are summarized in Table 1. [Example 2] Except changing the usage amount (feed amount) of methylpropionic acid methyl I in Example 1 from 196 parts to 184 parts, and Except changing the amount of methylpropionate from 4 parts to 16 parts, the rest was subjected to the same reaction, treatment, etc. as in Example 1, and adjusted ( (Meth) acrylic acid slurry A. The reaction time was 300 minutes. The viscosity of the obtained (meth) acrylic acid slurry A was 8 poisep c), the solid concentration was 22 3%, and the weight average molecular weight was 64,000. The same operation as in Example 丨 was performed to obtain the injection molding material. The obtained injection molding material had excellent storage stability. Secondly, the injection molding was performed in the same manner as in Example 1 to obtain a resin plate. The gelation time was 30 minutes. The obtained resin plate was insoluble in THF and acetone and had good solvent resistance. The main reaction conditions and results are summarized in Table 1. [Comparative Example 1] In Example 1, except that maleic anhydride and triethylamine were not used, the same reaction as in Example 1 was performed to prepare a (meth) acrylic acid slurry for comparison, that is, The added n-dodecyl mercaptan was treated to prepare a (meth) propionic acid slurry for comparison. The viscosity of the obtained (meth) acrylic slurry for comparison is 7 -43- non-heterogeneous standard common f family standard (CNS) A4 specification (2 Shu 297 male (will read the precautions on the back before filling this page) Order [3 88 1 9 A7 __B7 V. Description of the invention (41) poise (25 ° C), solid concentration is about 24.1%, weight average molecular weight is 620,000, and then the same operation as in Example 1 is performed to obtain Comparative injection molding material. Next, using the obtained comparative injection molding material, the same injection molding as in Example 1 was performed to obtain a comparative resin plate. The gelation time was 58 minutes. Also, everything was done The comparative resin plate is insoluble in THF and acrylic acid, and has good solvent resistance. However, the comparative injection molding material has poor storage stability. The above main reaction conditions and results are summarized in Table 1. [Comparative Example 2] Except for Examples The amount (feed amount) of methyl methacrylate in 1 was changed from 196 parts to 200 parts, and the same reaction and treatment as in Example 1 were performed without using methacrylic acid. Methyl) propanoic acid slurry. The reaction time is 500 minutes. Also, The obtained comparative (meth) propionic acid slurry had a viscosity of 6 poise (25 ° C), a solid attitude of 21.9%, and a weight average molecular weight of 61,000. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please First read the precautions on the back of the gas and then fill out this page.) Then, perform the same operation as in Example 1 to obtain the comparative injection molding material. The obtained comparative injection molding material has excellent storage stability. Secondly, the same implementation is performed. The injection molding of Example 1 resulted in a comparative resin plate. The gelation time was 69 minutes. However, the obtained comparative resin plate was soluble in THF and acetone and had poor solvent resistance. The main reaction conditions and results mentioned above are summarized. In table i.-丨 丨 — ..-44 ~ _ This paper rule standard (CNS) A4 specification (210 × 297 mm) — ~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 88 1 9 A7 B7 V. Invention Explanation (42) Table 1 Example 1 2 Methyl methacrylate (parts) 196 184 (+ 35) (+ 35) Methacrylic acid (parts) 4 16 Reaction time (minutes) 420 3 00 n-dodecyl mercaptan Processed with weight average molecular weight (Mw) 61,000 64,0 00 Gelation time (minutes) 4 5 3 0 Poor storage stability Good solvent resistance THF Insoluble Insoluble Acetone Insoluble Insoluble Comparative Example 1 2 Methyl methacrylate (parts) 196 200 (+ 35) (+ 35) methacrylic acid (Parts) 4 0 reaction time (minutes) 420 500 n-dodecyl mercaptan treatment without weight average molecular weight (Mw) 62,000 61,000 gelation time (minutes) 58 6 9 poor storage stability good solvent resistance THF insoluble soluble Acetone is insoluble and soluble (read the precautions on the back of the chain first and then fill out this page)-夤 · 45-45- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) A7 438819 _ B7 V. Invention Explanation (43) [Example 3] First, the same reaction and treatment as in Example 1 were carried out to prepare a (meth) propanone slurry A. Next, 1 part of the (meth) propionic acid slurry a 100% of osmium oxide as a thickening agent, 1 part of pentaenylsuccinic acid as a succinic acid derivative, and a third part as a hardener 1 part of butylperoxy_2_ethylhexanoate, 4 parts of zinc stearate as a release agent, and a hydroxide hydroxide as a filler (manufactured by Showa Denko Corporation, 4 yoyotsubu HS 320) 150 parts to obtain ingredients. Then, after coating the ingredients on the surface of the polyethylene film to a certain thickness, glass fibers (shreds of 1 inch in length) as a reinforcing material are uniformly spread on the coating. Next, a coating material (which is formed by coating ingredients on the surface of a polyethylene film to a certain thickness) is laminated thereon. That is, the glass fiber is held by the ingredients. Thereby, S μ C was obtained as a molding material. The proportion of the glass fiber in the SMC is adjusted to 25%. Thereafter, the obtained S M C was packaged in cellophane, and matured at 40 ° C for 1 day. After ripening, the ingredients, namely SMC, do not harden, and the surface of the SMC is not sticky. Next, the above-mentioned SMC is formed by pressure heating. That is, a mold of a predetermined size is used to set the temperature of the upper mold to u ° C, and the temperature of the lower mold to 100 ° C. Then, the SMc cut into a predetermined size was filled in the above mold, and the mold was clamped at a pressure of 6 MPa, and then heated and press-molded for 10 minutes to form a molded product, that is, a plate having a thickness of 3 mm. The gelation time at 110 ° C was measured using Niugong Yugaibu / Yiyichiyi V-type (manufactured by Tofang Technology Co., Ltd.) as a measuring device. That is, the test granules, that is, the SMC, are heated to 110 ° C, and from the point when the temperature is reached (the point when the heating starts) ---------- -46- This paper size applies; Standard (CNS) Αϋ ( 2ΐ () χ297 public envy) — — mlllljti J j: (Please read the notes on the back before filling in this page) Order printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 438819 A7 B7 V. Description of the invention (44) Central of the Ministry of Economic Affairs The standard bureau staff consumer cooperative prints the back measuring device to measure the time when the measured torque rises, and this time is used as the gelation time. As a result, the gelation time in 110 r was 200 seconds. The surface of the obtained molded product has gloss and excellent smoothness. In addition, the molded product is insoluble in THF and Lai, and has good solvent resistance. Furthermore, in accordance with A 1415, a weather resistance test was performed using a climatometer for 1,000 hours. As a result, no substantial discoloration or chalking was observed in the molded product. A hot water resistance test was performed at 90 ° C for 100 hours to evaluate the water resistance. As a result, after the test, the surface of the molded article had gloss and no substantial change was observed. Furthermore, when the molded product was placed in a furnace set at 170 ° C, heat resistance was evaluated. As a result, the molded product did not show any change in appearance such as yellowing, and did not lose the surface gloss. The above main reaction conditions and results are summarized in Table 2. [Example 4] First, the same reaction and treatment as in Example 2 were performed to prepare (meth) acrylic acid slurry A. Next, using this (meth) acrylic acid slurry A, except that the amount of magnesium oxide used in Example 3 was changed from 1 part to 2 parts, and the amount of pentaenyl succinic acid was changed from 1 part to 3 parts. The rest are implemented by congruence; 3 operations, molding, etc., to make a molded product. The gelation time was 165 seconds. The surface of the obtained molded article was glossy and excellent in smoothness. Table 2 shows the main reaction conditions for obtaining the molded products and the measurement results of the molded products. [Comparative Example 3] First, the same reaction and treatment as in Comparative Example 1 were performed to prepare a (meth) acrylic acid slurry for comparison. Next, the comparative (meth) propionic acid polymer solution was used, and the same operations as in Example 3 were performed to obtain a comparative SMC. Notes for reading and reading the first page ί-47 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 438819 V. Description of the invention (45) The comparison SMC obtained at 40X: Xia Chengcheng] π,

Γ ..., the wind is 1st. However, the comparative SMC will harden. The above main reaction conditions are summarized in Table 3. [Comparative Example 4] First, the same reaction, treatment, and the like as in Comparative Example 2 were performed to prepare a (meth) acrylic acid slurry for comparison. Next, using the (meth) acrylic acid slurry for comparison, the same operation as in Example 3 and the like were performed to obtain 2Smc for comparison. The obtained comparative SMC was matured at 4 ° C. for 1 day. However, the comparative SMC did not increase withering. The surface of the comparative SMC was dull. Next, the comparison SMC was used in the same manner as in Example 3. Operation, molding, etc., to produce a comparative molded product. The gelation time was 25 seconds. However, the obtained comparative molded product was soluble in THF and acetone and had poor solvent resistance. Further, the heat resistance was evaluated and the results Compared with molded products, changes in appearance such as yellowing can be seen, and the surface gloss has also been lost, resulting in streaks. The above main reaction conditions and results are summarized in Table 3. [Comparative Example 5] Except for those in Example 1, The amount of methyl methacrylate used (feed amount) was changed from 196 to 199.4 parts, and the amount of methylpropionic acid used was changed from 4 to 0.6. The rest was the same as in Example 1. (Meth) acrylic acid slurry for comparison and treatment was prepared. The reaction time was 48 minutes. In addition, the viscosity of the obtained (meth) acrylic acid slurry for comparison was 6 poise (25 ° C), solid The concentration was 22.8%, and the weight average molecular weight was 66,000. The same operation and injection molding as in Example 1 were performed to obtain a comparative resin plate. The gelation time was 65 minutes. However, the obtained comparative resin plate was soluble in THF and acetone and had poor solvent resistance.- 48- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

T Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention Operation, etc., to obtain a comparative SMC. The obtained comparisons were matured with SMC at 40 CT for 1 day. However, the surface of the comparison SMC is slightly withered. Then, a comparative SMC was used to perform the same operations, molding, and the like as in Example 3 to prepare a comparative molded article. The gelation time was 23 seconds. However, the obtained comparative molded product was slowly dissolved in THF and acetone, and the solvent resistance was poor. Furthermore, heat resistance was evaluated, and as a result, a comparative molded article showed slight changes in appearance such as yellowing. The main reaction conditions and results are summarized in Table 3. [Comparative Example 6] In addition to changing the usage amount (feed amount) of methyl methacrylate in Example 1 from 196 to 150 parts, and changing the usage amount of methacrylic acid from 4 to 50 parts Other than that, the same reaction and treatment as in Example 1 were performed, and a (meth) acrylic acid slurry for comparison was prepared. The reaction time was 24 minutes. The viscosity of the obtained (meth) acrylic acid slurry for comparison was 8 poise (2yc), the solid concentration was 23.9%, and the weight-average molecular weight was 68,000. Then, the same operation and injection molding as in Example 1 were performed to obtain a comparative molded product. The gelation time was 17 minutes. The obtained comparative molded product was insoluble in THF and acetone, and had good solvent resistance. Next, using the aforementioned (meth) propionic acid beam liquid for comparison, the same operations as in Example 3, molding, etc. were performed to prepare a comparative molded product. In addition, the surface of the ingredients, i.e., the SMC used for comparison, was non-sticky after ripening. The gelation time was 120 seconds. The obtained comparative molded product was insoluble in THF and acetone, and had good solvent resistance. Furthermore, the molded article has excellent heat resistance. However, the comparative moldings have poor weather resistance and water resistance. The above main reaction conditions and results are summarized -49- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 丨 ^ _ — (Please read the precautions on the back before filling this page)

, 1T 438819

In Table 3. [Comparative Example 7] Except that the amount of maleic anhydride added in Example 1 was changed from 07 parts to 02 parts, and the amount of triethylamine added was also changed from 0.004 parts to 0.004 parts. The rest is the same as the implementation of your jl for reaction, processing, etc., compared with (meth) acrylic acid slurry. One of the above-mentioned maleic anhydride is added to the n-dodecyl mercaptan system in an amount of 0.4 times mole. In addition, triethylamine was added in an amount of 0.008 times the mole of n-dodecyl mercaptan. The obtained comparison (meth) propionic acid slurry had a dryness of 7 poise (25C), a solid concentration of 211%, and a yield average molecular weight of 630,000. ) The acrylic slurry was subjected to the same operations as in Example 3 to obtain a comparative SMC. The obtained comparative sMc was matured at 40 ° C for 1 day. However, the comparison 8] ^ (: will harden. The above main reaction conditions are summarized in Table 3. [Example 5] Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs First, the same reaction and treatment as in Example 2 were performed. To prepare (meth) acrylic acid slurry A. Next, using this (meth) acrylic acid slurry A, except that the amount of magnesium oxide used in Example 3 was changed from 1 part to 2 parts, and the pentadecyl group was broken The amount of Yasushi acid was changed from 1 part to 3 parts, and 100 parts of aluminum hydroxide was mixed with 50 parts of calcium carbonate (manufactured by Toyo Fine Chemical Co., Ltd., water 74 4 &gt; P-70) as a filler to replace Except for 150 parts of aluminum hydroxide, the rest is the same as the operation, forming, etc. of Example 3 to form a molded product. Also, the surface of the SMC, that is, the surface of the SMC is not sticky after curing. The gelation time is 160 seconds. __- 50- The paper size is suitable for financial standards (CNS) A4 (210X297). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Has gloss and excellent smoothness. The main reaction of the above-mentioned molded products The conditions and results are summarized in Table 2. Furthermore, the molded product has excellent heat resistance. The weather resistance and water resistance were evaluated. As a result, the molded product was slightly discolored compared with the molded product of Example 4, and Gloss is slightly reduced, but its physical properties are excellent. [Example 6] First, the same reaction, treatment, etc. as in Example 2 were performed to prepare (meth) acrylic acid slurry A. Next, this (meth) acrylic acid slurry A was used, In addition to changing the amount of magnesium oxide used in Example 3 to 2 parts, while changing the amount of pentaenyl succinic acid used from 1 part to 3 parts, and mixing 100 parts of hydroxide hydroxide with The filler was filled with 50 parts of glass powder (manufactured by Tobo Industries Co., Ltd., fmb 30W-001) in place of 150 parts of aluminum hydroxide, and the same operations as in Example 3 were performed, forming, and the like to form a molded article. The ingredients, that is, the surface of the SMC is not sticky. The gelation time is 170 seconds. The surface of the obtained molded product has gloss and excellent smoothness. The main reaction conditions and results of the above molded products are summarized in Table 2. [Implementation Example 7] In Example 1, except for adding In addition to 25 parts of methyl methacrylate and 10 parts of trimethylmethylpropanetrimethylpropionate as crosslinkable monomers, in addition to 35 parts of methyl methacrylate added after the polymerization reaction is completed, The rest were subjected to the same reaction and treatment as in Example 1 to prepare (meth) acrylic acid slurry A. The viscosity of the obtained (meth) acrylic acid slurry A was 8 poise (25 ° C), and the solid concentration was 21.7%, weight The average molecular weight is 62,000. Secondly, using this (meth) acrylic acid slurry A, the same as in Example 3 -51-This paper size applies the Chinese National Standard (CNS) A4 specification (210'〆297 mm) --- ： --- ： ------- --- (Please read the notes on the back before filling in this page) Order A7 4388 1 9 B7 V. Description of the invention (49) (Please read the notes on the back before (Fill in this page). The gelation time was 180 seconds. The obtained molded product has a glossy surface and excellent smoothness. The main reaction conditions and results of the above molded products are summarized in Table 2. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 2 Example 3 4 5 6 7 Magnesium oxide (parts) 1 2 2 2 1 Pentadecyl succinate (repair) 1 3 3 3 1 Aluminum hydroxide (parts) ) 150 150 100 100 150 Calcium carbonate (parts) _ — 50 — One glass fiber (parts) _ 110 — The forming material after curing is good Good Good Good Good gelation time (seconds) 200 165 160 170 180 Solvent resistance THF insoluble, insoluble, insoluble, insoluble, acetone, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, insoluble, and insoluble (210X297 mm) 4 3 8 8 19 V. Description of the invention (50) Table 3 Comparative Example 3 4 5 6 7 Magnesium oxide (parts) 1 1 1 1 1 Pentaenyl succinic acid (parts) 1 1 1 1 1 Aluminum hydroxide (parts) 150 150 150 150 150 After curing, the molding material is hardened without thickening and thickening. Good hardening and gelling time (seconds) — 250 230 120 __ Solvent resistance THF — Soluble and insoluble-Acetone-Soluble and insoluble-Heat resistance-Bad and good-Weather resistance-Poor-Water resistance-_-Bad-[Example 8] (Please read the precautions on the back before filling in this Page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs First, the same reaction and treatment as in Example 1 were performed to prepare (meth) acrylic acid slurry A. Next, in this (meth) acrylic acid slurry, 1 part of magnesium oxide, 2 parts of pentaenyl succinic acid, 1 part of tert-butylperoxy-2-ethylhexanoate, and stearin were mixed. 4 parts of zinc acid, 350 parts of aluminum hydroxide ('44b H_320 manufactured by Showa Denko Corporation), and glass fiber (shear of 1/4 inch in length) as a reinforcing material, then use a double-wrist kneader Knead this blend. Thereby, BMC was obtained as a molding material. The proportion of the glass fiber in the BMC is adjusted to 5%. Thereafter, the BMC obtained was packaged in Vinylon (manufactured by Yuki K. Co., Ltd.) and matured at 40 ° C for 1 day. After ripening, the ingredients, namely BMC, will not harden, and the surface of BMC is not -53- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (51) Sticky. Next, the above-mentioned B c is formed by heating and pressing in a predetermined method to form a molded product. The gelation time was 190 seconds. The surface of the obtained molded article was glossy and smooth. The main reaction conditions and results of the above molded products are summarized in Table 4. [Comparative Example 8] First, the same reaction, treatment, and the like as in Comparative Example 2 were performed to prepare a (meth) acrylic acid slurry for comparison. Next, the comparative (meth) acrylic acid slurry 'was used to perform the same operations as in Example 8 to obtain a comparative bmC. The obtained comparison was made at 40 ° C; 6] ^ &lt;: matured for 1 day. However, the comparative BMC does not increase viscosity. In addition, the surface of the comparative BMC is sticky. Next, using this BMC for comparison, the same molding as in Example 8 was performed to prepare a molded product for comparison. The gelation time was 260 seconds. However, the obtained comparative molded product was soluble in THF and acetone and had poor solvent resistance. Furthermore, the comparison of the molded article for the "result" of the heat resistance and the appearance of the molded article showed changes in appearance such as yellowing. The above main reaction conditions and results are summarized in Table 5. [Example 9] First, the same reaction, treatment and the like as in Example 2 were performed to prepare (meth) acrylic acid slurry A. Next, 100 parts of the (meth) acrylic acid slurry a was mixed with 1 part of bis (4-tert-butylcyclohexyl) peroxydicarbonate and aluminum hydroxide (manufactured by Showa Denko Corporation, (4,7 ,, this &lt; BU H 32〇ST) after 200 parts, the mixture was kneaded and defoamed. Thereby, a cast material was obtained as a molding material. Secondly, use the glass mold room to inject the obtained injection molding materials. 54- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) IJ:-(Please read the precautions on the back before (Fill in this page) Order 4388 1 9 A7 B7 5. Description of the invention (52). That is, after the injection molding material is injected into the mold cavity, it is at 60. 〇 Harden for i hours. Next, after demolding, it is post-cured at 10 ° C for 2 hours to obtain an artificial marble slab, which is a molded article. The obtained artificial marble slab has gloss, smoothness, and so-called high-quality and texture. The main reaction conditions and results of the plate are summarized in Table 4. [Comparative Example 9] First, the same reaction, treatment, and the like as in Comparative Example 2 were performed to prepare a (meth) acrylic acid slurry for comparison. Second, this comparison was used ( The (meth) acrylic acid slurry was subjected to the same operation, forming, and the like as in Example 9 to prepare an artificial marble board for comparison. However, 'the obtained artificial marble board for comparison was soluble in TjjF and acetone' and had poor solvent resistance. The heat resistance was evaluated. As a result, when using artificial marble slabs to compare the appearance changes such as yellowing, it also lost the surface gloss and caused streaks. The above main reaction conditions and results are summarized in Table 5. [Example 1 0] in In the same reactor as in Example 1, after 200 parts of methyl methacrylate was fed, the inside of the reaction vessel was replaced with nitrogen. Next, the methyl group was stirred while After the methyl enoate was heated to 80 ° C, 0.1 parts of AIBN and 1.0 part of n-dodecyl mercaptan were added to start the polymerization reaction. After the polymerization reaction was started, the viscosity of the reaction solution was 30 to 35 poise (25 ° C) The reaction was terminated at

After 35 parts of methyl methacrylate was added to the reaction solution, it was cooled (quenched) to 40 ° C. Then, to the obtained reaction mixture, 0.7 parts of maleic anhydride was added. (CNS) 8 specifications (210X297 mm) 1 .-., | _ ^ ---- JmwII -I: (Please read the precautions on the back before filling this page) Order-Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, printed 4388 1 9 V. Description of the Invention (0.04 parts of triethylamine, stirred for 15 minutes, treated n-dodecyl mercaptan added to the reaction mixture. The above maleic anhydride is relatively To the added n-dodecanol system, the added force was 1.4 times the mole. The triethylamine was added 0.08 times to the added dodecyl alcohol system. Then, the reaction compound after the above treatment was added. 5 parts of methacrylic acid was added to 95 parts to obtain 1 acrylic bromide acid slurry B of the present invention. Next, 100 parts of the (meth) acrylic acid slurry B was mixed with bis (4-third-butyl ring). Hexyl) Peroxydicarbonate 丨 Aluminum hydroxide (Showa Denko Corporation) After making 200 parts of H / 32, ST, and 200 parts, the mixture is kneaded and defoamed. Thereby, a molding material is obtained as a molding material. This molding material, that is, the storage stability of the ingredients is excellent. Next The obtained injection molding material was injection-molded using a glass mold chamber. That is, after the injection molding material was injected into the mold chamber, it was hardened at 6 ° C for 1 hour. Then, 'after demolding, at 100 ° C After curing for 2 hours, the artificial marble slab is obtained as a molded product. The surface of the obtained artificial marble slab has gloss, excellent smoothness, and high-quality and texture. The main reaction conditions and results of the artificial marble slab are summarized in Table 4. [Example 11] In the same reactor as in Example 1, after feeding 200 parts of methyl methacrylate, the reactor was purged with nitrogen. Next, the temperature of the methyl methacrylate was raised to 80 ° while stirring. After C, polymerization was started by adding AIBN 0.1 part and 1.0 part of n-dodecyl mercaptan. After the polymerization reaction was started, the reaction solution was terminated at a point of 30 to 35 poise (25 ° C). Medium to reaction liquid -56 This paper is suitable for National Standard (CNS) A4 specification (210X297 mm)! 1 丨 &quot; &quot; &quot; ^ Φ II II: (Please read the precautions on the back before filling this page) Order 438819 A7 B7 V. Description of the invention (54 A consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed a step of adding 25 parts of methyl methacrylate and 10 parts of methacrylic acid, and then cooled to 40 ° C. Then in the reaction mixture obtained, add 07 parts of maleic acid and 0.04 parts of triethylamine were stirred for 15 minutes, and n-dodecyl mercaptan added to the reaction mixture was treated. The maleic anhydride is added 1.4 times moles to the n-dodecyl mercaptan system. In addition, triethylamine was added in an amount of 0.08 times mole relative to the added n-dodecyl mercaptan. Thereby, the (meth) acrylic acid slurry b of this invention is obtained. The person / person 'used the (meth) acrylic acid slurry B to perform operations, molding, and the like similar to those in Example j0 to prepare an artificial marble slab. In addition, the injection molding material, that is, the ingredients, has excellent storage stability. The known artificial marble slabs have a glossy surface, excellent smoothness, and a southern feel and texture. The main reaction conditions and results of the above artificial marble slabs are summarized in Table 4. [Example 1 2] In the same reactor as in Example 1, after feeding 200 parts of methyl methacrylate, the reactor was purged with nitrogen. Next, while stirring the methyl methacrylate vinegar ', the temperature was raised to 8 (rc), and AIBNO. And 1.0 parts of n-dodecyl mercaptan were added to start the polymerization reaction. After the polymerization reaction was started, the reaction solution dried The reaction was completed at a temperature of 30 to 35 poise (25X :). After 35 parts of methyl methacrylate was added to the reaction solution, it was cooled (quenched) to 40 ° C. Then, 'the obtained reaction mixture After 0.7 parts of maleic anhydride and 0.04 parts of triethylamine were added to the mixture, the mixture was stirred for 15 minutes, and the n-dodecyl alcohol added to the reaction mixture was processed. Ear 4 (Please read the notes on the back before filling out this page) 蝼 ·

、 1T 57- This paper size applies the Ningguanjia standard (cnsu ^ (210x297 ^) 438819 A7 B7 V. Description of the invention (55) In addition, the above-mentioned diethylamine is added to the n-dodecyl mercaptan added 0.0 8 (Meth) propionic acid slurry was obtained by adding 5 parts of mol. Then, 5 parts of methacrylic acid was added to 95 parts of (meth) propionic acid slurry, and then the same operation as in Example 10 was performed. Artificial marble slab. Also, the injection molding material, that is, the stability of the ingredients is excellent. So the artificial marble slab has a glossy surface, excellent smoothness, and has the so-called high-quality and texture. The main reaction of artificial marble slab The conditions and results are summarized in Table 5. I:-丨 丨 Hr — *-!:: 1 (Please read the precautions on the back before filling out this page}

1T Table 4 Example 8 9 10 11 Magnesium oxide (parts) 1 — — — Pentaenylsuccinic acid (parts) 2 — — — Aluminum hydroxide (parts) 3 50 200 200 200 — — Gelation time (seconds) 190 I — __ Solvent resistance THF Insoluble Insoluble Insoluble Insoluble Acetone Insoluble Insoluble Insoluble --------- Insoluble Good for good heat resistance Good Good Good weather resistance Good Good Good Good Water resistance Good, use moderate ruled paper

438819 A7 B7 V. Description of the invention (56)

(Please read the precautions on the back before filling in this page] Order-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs It is obvious from Tables 1 to 5 that when it is expected, it can be installed and stored in a shorter time than usual. Excellent storage stability The (meth) acrylic slurry A · B. In addition, the molding material of this embodiment is suitable for heating and pressure molding, and can be cured in a relatively short time. Furthermore, the obtained molded product has excellent heat resistance and solvent resistance. Various physical properties such as weather resistance, water resistance, etc. [Example 1 3] In a reactor equipped with a thermometer, a cooler, a nitrogen introduction pipe, and a stirrer, 94 parts of methyl methacrylate and 6 parts of methacrylic acid were fed. After the serving, nitrogen Xiaxi is carried out in the reactor. Secondly, the above-mentioned 皋 -59 is covered. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210'〆297 mm). It is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 438819 A7 B7 V. Description of the invention (57) &quot; ~ After heating up to 80 ° C, 0.1 parts of AIBN and 2 parts of n-dodecyl mercaptan were added for copolymerization reaction for 6 hours, thereby obtaining a reaction mixture. The acid value of the obtained reaction mixture was 19. Next, after adding isobutyl vinyl ether as a vinyl ether compound to the above reaction mixture, the temperature was raised to 100 ° C and stirred for 30 minutes, and the residue remained in the reaction mixture for processing. N-dodecyl mercaptan. The above isobutyl ethyl sulfenyl ether is added to the n-dodecyl mercaptan added at the time of polymerization by 2.0 times moles. Then, methyl propionate is added as glycidyl vinegar, as g 0.4 g of triphenylphosphine as a catalyst, and 0.01 part of hydroquinone as a polymerization inhibitor, and then stirred at 1000 c for 10 hours to perform an esterification reaction. The above glycidyl methacrylate The ester was added 0.5 times moles to the methacrylic acid. As a result, a (meth) acrylic acid slurry C was obtained. The (meth) acrylic acid slurry C had a solid concentration of 42%, a viscosity of 28 poise, and an acid value of 11. The weight average molecular weight was 42,000. Further, the number of double bonds per molecule of the (meth) acrylic polymer in (meth) acrylic acid slurry C · was measured. That is, first, the reaction of glycidyl methacrylate was measured. Before and after (methyl) The difference in the acid value of the enoic acid polymer is used to calculate the number of moles of the carboxyl group per gram of the (meth) acrylic polymer, and this is used as the mole of the polymerizable double bond in 1 gram of the (meth) acrylic polymer. The number of ears is calculated from the weight average molecular weight of the (meth) acrylic polymer. The number of moles per gram of (meth) acrylic polymer is calculated. The number of moles of polymerizable double bond in 1 g of (meth) acrylic polymer is calculated. And the molar number of 1 gram of the (meth) acrylic polymer to calculate the number of double bonds per molecule of the (meth) acrylic polymer. As a result, the number of double bonds per molecule was 5 to 3. Then, in Peroxide is added to 100 parts of the above (meth) acrylic acid slurry C-60. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

, 1T 438819 Economic Central Standards are printed for member fees. 5. Invention Description (58) 2 copies of benzamidine are dissolved. Thereby, a cast material as a molding material was obtained. The obtained cast material was degassed by decompressing. This injection-molded material has excellent storage stability. Then, the injection molding material was poured into the same mold chamber as in Example 丨, and then heated to 60 C to harden it. The gelation time was measured in the same manner as in Example i. As a result, the gelation time in 60 × X: was 30 minutes. Next, after demolding, after-ureing was performed at 100 ° C to obtain a resin plate which is a molded article. The obtained resin plate was insoluble in THF or acetone. That is, the above-mentioned resin plate has excellent solvent resistance. The main reaction conditions are shown in Table 6, and the results are shown in Table 7. [Example 1 4] Except that 3,4-dihydro_2H-pyran was used as the ether-based ether compound to replace the isobutyl vinyl ether in Example 13, the rest were reacted and treated in the same manner as in the example. A (meth) acrylic acid slurry c was obtained. The obtained (meth) propionic acid slurry C had a solid concentration of 43%, a particle size of 31 poise, and an acid value of 11 'and a weight average molecular weight of 39,000. Then, the same operation as in Example 3 was performed to obtain an injection-molded material. The obtained cast material has excellent storage stability. Then, the same procedure as in Example 13 was carried out to obtain a resin plate. The gelation time at 60 ×: is w minutes. The obtained resin plate had good solvent resistance. The main reaction conditions are shown in Table 6 '. The results are shown in Table 7. [Comparative Example 1] Example 1 was repeated, except that reaction and treatment of Example 1 and 3 were performed. As a result, the viscosity slowly rises during esterification.

210X297 mm) 4388 1 9 A7 B7 V. Description of the invention (59, the solid, viscosity, and weight-average molecular weight are all increased (metapropionic acid slurry. &Amp; Then, the same operation as in Example U is performed To obtain a comparative injection molding material. Then, using the obtained comparative injection molding material, the same injection molding as in Example 13 was performed to obtain a comparative resin. The gelation time in 6 (Γ (: 60 points. The obtained comparative injection molding material has poor storage stability. In addition, the obtained comparative resin plate swells in THF and acetone. The main reaction conditions of the second description are shown in Table 6, and the results are shown in Table 7. [Example 15] Except that the order of thiol treatment and esterification in Example 13 was changed, the same reaction and treatment as in Example 13 were performed to obtain a (meth) acrylic acid slurry c. The (meth) acrylic acid slurry c had a solid concentration of 50%, a viscosity of 150 poise, an acid value of u, and a weight average molecular weight of 5800. Then, the same operation as in Example 13 was performed, and the injection was obtained. Material. The obtained injection material has Excellent storage stability. Then, a core / king type was performed in the same manner as in Example 1 to obtain a resin plate. The gelation time at 6 (Γ (:) was π minutes. In addition, the obtained resin plate had good solvent resistance. The main reaction conditions are shown in Table 6, and the results are shown in Table 7. 9 1-8 8 3 4

7 B V. Description of the invention (60) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 6 Implementation 4 column Comparative Example I 3 14 15 10 Methyl methacrylate (parts) 194 194 194 194 Polymethacrylic acid (parts) 6 6 6 6 N-dodecyl mercaptan (parts) 2 2 2 2 Anti-AIBN (parts) 0.1 0. 1 0. 1 0 „1 Reaction temperature (° c) 80 80 80 80 Reaction time (hr) 6 6 6 6 Acid value 19 20 19 19 Isobutyl vinyl ether (bemolle) 2.0-2.0; — place 3,4-dihydro-2 !!-pyran (bemolle) — 2.0 — rational reaction Temperature (° C) 100 100 100 One reaction time (hr) 0.5 0.5 0.5 — glycidyl methacrylate (bemol) 0.5 0.5 0.5 0.5 ester triphenylphosphine (parts) 0.4 0.4 0.4 0.4 hydroquinone (parts) ) 0.01 0.01 0.01 0.01 Reaction temperature (° c) 100 100 100 100 Response time (hr) 10 10 10 10 (Please read the precautions on the back before filling out this page) -63-This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) 4 3 881 9 A7 B7 V. Description of the invention (61) Table 7 13 Example 4 15 Comparison 10 Poise Solid concentration (%) Acid value Weight average molecular weight (Mw; Number of double bonds per molecule Gelation time (minutes) 28 42 43 150 170 50 11 42,000 39? 000.00 08,000 2 30 30 30 5 1 13 60,000 7.4 60 — ^^ ------— ·-1 (Please read the precautions on the back before filling out this page) Good storage stability Good Good Poor Solvent resistance Insoluble Insoluble Insoluble Swelling [ Example 16] In the same reactor as in Example 13, 180 parts of methyl methacrylate and 20 parts of methacrylic acid were fed, and then the reactor was purged with nitrogen. Next, while stirring the above mixture, After raising the temperature to 80 t, 0.1 part of Aibn and 10 parts of pentaerythritol tetrathioglycolate as a thiol compound were added, and a copolymerization reaction was performed for 4 hours. Thereby, a reaction mixture was obtained. Then, in the reaction mixture, After isobutyl vinyl ether was added, the temperature was raised to 100 ° C. and stirred for 30 minutes, and the n-dodecyl mercaptan remaining in the reaction mixture was treated with the isobutyl vinyl ether. Undecyl sulfide add 2.0 times Ear. Next, glycidyl methacrylate, triphenylphosphine 0.1 part, and hydroquinone 0.01 part were added, and it stirred at 100 ° C for 8 hours, and then esterified. The above glycidyl methacrylate is added 10 times as much as methacrylic acid. -64 Order printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Thousand You ί, J /---

r one I ¾ y Z 438819

T. Thereby, a (meth) acrylic acid slurry c 'is obtained. The obtained (meth) acrylic acid slurry c had a solid concentration of 52%, a viscosity of 39 poise, an acid value of ", and a weight-average molecular weight of 14.00. Then, the same operation as in Example 13 was performed. An injection-molded material was obtained. The obtained / king-shaped material had excellent storage stability. Then, the injection molding was performed in the same manner as in Example 13 to obtain a resin plate. The gelation time in 60 ×: was obtained. The resin plate had good solvent resistance. The above main reaction conditions are shown in Table 8, and the results are shown in Table 9. [Example 17] Except the amount of methyl methacrylate used in Example 16 (feed The amount was changed from 180 parts to 6 parts for J 9 and the amount of methacrylic acid used was changed from μ parts to 4 parts. The rest was reacted and treated in the same manner as in Example 16 to prepare (meth) acrylic acid.棉 · 酸 浆液 C. Then, the same operation as in Example 13 was performed to obtain a cast material. The obtained cast material had excellent storage stability. Then, the same "King type" as in Example 13 was performed to obtain a resin. Plate. Gelation time at 60 ° C is 40 minutes. The tree obtained The grease plate has good solvent resistance. The main reaction conditions are shown in Table 8. The results are shown in Table 9. [Example 18] In a reactor equipped with a thermometer, a cooler, a nitrogen introduction tube, and a stirrer, feed After 196 parts of methyl methacrylate and 4 parts of methacrylic acid, nitrogen was substituted in the reactor. Next, the mixture was heated to 80X while stirring the mixture: After that, AIBN 0 ″ parts and n-dodecyl mercaptan were added and The copolymerization reaction was carried out for 6 hours. Thereby, a reaction mixture was obtained. -------- 65- This paper size applies to China National Standard (CNS) A4 (210 &gt; &lt; 297mm) 43 ^ 8 1 9

5. Description of the invention (63) Then, after adding isobutyl vinyl ether to the above reaction mixture, the temperature was raised to 100 C and stirred for 1 hour, and the n-dodecyl mercaptan remaining in the reaction mixture was treated. The isobutyl vinyl ether is added 2.0 times moles to the n-undecyl mercaptan added during polymerization. Thereby, a (meth) acrylic acid slurry C 'is obtained. The obtained (meth) acrylic acid slurry c had a solid concentration of 24%, a viscosity of 7 poise, an acid value of 12, and a weight average molecular weight of 61,000. Then, the same operation as in Example 13 was performed to obtain a cast material. The resulting cast material has excellent field stability. Then, the same injection molding as in Example 13 was performed to obtain a resin plate. The gelation time in 60 t was 40 minutes. Further, the obtained resin plate has good solvent resistance. The main reaction conditions are shown in Table 8, and the results are shown in Table 9. [Comparative Example 11] In Example 18, except that isobutyl vinyl ether was not used, the same reaction and treatment as in Example 18 were performed to obtain a (meth) acrylic acid slurry. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs—II ---- Φ! A comparative injection molding material was obtained. Then, using the obtained injection molding material for comparison, the same injection molding as in Example 13 was performed to obtain a comparative resin plate. The gelation time in 60 π is 60 minutes. The obtained comparative injection-molded material was stable in sound. In comparison, the comparative resin plate is swollen in THF or acetone. The main reaction conditions are shown in Table 8, and the results are shown in Table 9. -66-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 9 ^-8 8 3 4

A

7 B V. Description of the invention (64) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 8 Examples Comparative Example 16 17 18 11 Methyl methacrylate (parts) 180 196 196 196 Methacrylic acid (parts) 20 4 4 4 Poly-n-dodecyl mercaptan (parts) — one 1 1 pentaerythritol tetrathioglycolate (parts) 10 10 one — anti-AIBN (parts) 0.1 0.1 0.1 0.1 reaction temperature rc) 80 80 80 80 reaction time ( hr) 4 4 6 6 Acid value 58 11 12 12 Isobutyl vinyl ether (Bemol) 2.0 2.0 2.0 One reaction temperature (° c) 100 100 100 One reaction time (hr) 0.5 0.5 0.5 1. 0 Glycidyl monomethylpropionate (Bemol) 1.0 1.0 — Triphenylphosphine (parts) 0.1 0.1 — Hydroquinone (parts) 0.01 0.01 — — Reaction temperature (° c) 100 100 — One response time (hr) 8 8 one one! -II ---- J9II two-V (Please read the precautions on the back before filling this page)

、 1T -67- This paper size applies to Chinese National Standard (CNS) A4 (210X 297mm) 4 3 8819 * A7 B7 V. Description of invention (65 Printed in Table 9 by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Comparative Example 16 17 18 11 Particle size (poise) 39 40 7 8 Solid concentration (%) 52 51 24 24 Acid value 27 5 12 12 Weight average molecular weight (Mw) 14,000 13,000 61,000 60,000 Number of double bonds per molecule 7.6 1 · 8 — — Gelation time (minutes) 15 40 40 60 Good storage stability Good Good Poor Solvent resistance Insoluble Insoluble Insoluble Swelling [Example 1 9] In a reactor equipped with a thermometer, a cooler, a nitrogen introduction tube, and a stirrer The solution was fed with an aqueous solution [consisting of dissolving 0.2 parts of polyvinyl alcohol (PVA-205, manufactured by Yuki K. Co., Ltd.) as a dispersing stabilizer in 180 parts of deionized water as a dispersing agent (solvent)]. In addition, in another container, 8 parts of methyl methacrylate, 8 parts of styrene as an ethynyl compound, 4 parts of trimethyl methacrylate trimethacrylate, and n-dodecyl mercaptan were mixed. 0.5 copies, and, ΑΙΒ 0.2 parts of N to obtain a mixture. The above mixture was added to the reactor and stirred at 500 rpm to form a homogeneous suspension. Then, the temperature was raised to 75 ° C while blowing nitrogen gas, and the stirring was continued at this temperature for 5 hours. Suspension polymerization was performed. Then, after adding isobutyl vinyl ether to the suspension (reaction mixture) after polymerization, the temperature was raised to 90 ° C and stirred for 1 hour to treat the remaining -68- paper. Standards apply Chinese National Standard (CNS) A4 specifications (21〇 &lt; 297 mm) (Please read the precautions on the back before filling this page),?!-^ 38819 V. Description of the invention (66 Dodecyl mercaptan. The isobutyl vinyl ether described above is added to the n-dodecyl mercaptan added at the time of polymerization by 30 times the mole. Then, from the treated suspension [(meth) acrylic acid slurry] The polymer was filtered, washed, and dried. Thereby, a granular polymer was obtained. The obtained granular polymer was extruded with a sleeve diameter of 30 mm (made by the Institute of Plastics Engineering) at 240 C, 20 A strand with a diameter of 5 mm was extruded under mmHg, and was cut by a granulator

I ', granulated. At this time, no carbide was observed on the screw. In addition, when granulated, there was no odor due to the thiol compound. The above main reaction conditions and results are summarized in Table 10. [Example 20] In Example 19, except that isobutyl vinyl ether was used, the reaction and treatment were the same as in Example 19 to obtain a bead polymer. Then, the obtained bead polymer was heated to 24 ° C. and isobutyl vinyl ether was added to treat the n-dodecyl mercaptan remaining in the bead polymer. The isobutyl vinyl group described above Ether was added 3.0 times moles to the n-dodecyl mercaptan added during the polymerization. Then, the same operation as in Example 19 was performed to form particles. At this time, no carbides were adhered to the screw. Further, particles were formed. No odor was caused by the thiol compound I. The above main reaction conditions and results are shown in Table 10. [Comparative Example 12] First, the same reaction and treatment as in Example 20 were performed to obtain a compound. Except for the addition of isobutyl ethylene ether, the rest is the same as the operation of ㈣ to make granules for comparison. At this time, when many carbides are attached to the screw ° and 'formed into granules', the thiol compound is generated. Paper scale Shicaiguan -69- ^ 88 19 Μ B7, invention description (67) Economy, Ministry of Standards Bureau staff odors printed by cooperatives. The above main reaction conditions and results are shown in Table 10 Table 10-- __________ Examples Comparative example 19 20 12 Methyl methacrylate (parts) 8 8 8 Polystyrene (parts) 8 8 8 Trimethylolpropane trimethacrylate (parts) 4 4 4 Dodecyl mercaptan (parts) ) 0.5 0.5 0.5 Acetyl alcohol (parts) 0.2 0.2 0.2 Deionized water (parts) 180 180 180 ΑΙΒΝ 0.2 0.2 0.2 Reaction temperature (° c) 75 75 75 Reaction time (hr) 5 5 5 Ether (Bemol) 3.0 3.0 — Physical reaction temperature (° c) 90 240 —Reaction time (hr) 1.0 — —- ^ Carbide on the screw is present or not Caused by the odor of mercaptan or not [ Example 2 1 First, the same reaction, treatment, and the like as in Example 13 were performed to prepare (meth) acrylic acid slurry c. Secondly, 100 parts of (meth) acrylic acid slurry CV was mixed with 1 part of magnesium oxide and pentadecene 1 part of succinic acid, 1 part of third butyl peroxyethylhexanoate, 4 parts of zinc stearate, and oxidized inscriptions (Showa Denko Corporation -70-: Standards apply to Chinese National Standard (CNS) A4 Specifications (210X297 public celebration)! 1 ----- Read II -Μ: (Please read the precautions on the back before filling (This page), 1T 438819 A7 B7 V. Description of the invention (68) Company, ... 4 ^ 4 Bu HS_320) 150 parts, to obtain ingredients. Then, the ingredients are coated on the surface of the polyethylene film to a certain thickness, and then coated on the coating Evenly spread the glass fiber as a reinforcing material (a 1-inch-long cut bundle). On top of that, a coating (a coating made by coating ingredients with a certain thickness on the surface of the polyethylene film) is superposed. That is, the glass fiber is held by the ingredients. Thereby, SMC was obtained as a molding material. The proportion of glass fibers in the SMC was adjusted to 25%. Thereafter, the obtained s μ C was packaged in cellophane, and matured at 40 ° C. for 1 day. Next, the SMC is formed by heating and pressing. That is, a mold of 200 mm × 200 mm was used, and the mold temperature on the upper side was set to U (rc, and the mold temperature on the lower side was set to 100 ° C. Further, the SMC cut into a predetermined size was filled in the mold. The mold is clamped at a pressure of 6 MPa, and heated and pressed for 5 minutes to form a molded product, that is, a molded plate with a thickness of 3 mm. The gelation time in 110 C is based on the use of Feng Gongyi y — Xi _ V type (East Technology Co., Ltd.) measures it as a measuring device. That is, the SMC, which is a raw material, is heated to HOT, and the time at which the measured torque rises is measured by the measuring device from the time when the temperature reaches the temperature (the heating start point). , This time is used as the gelation time. As a result, the gelation time in 11 (rc is a leap second. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

The surface of the obtained molded plate has gloss and excellent smoothness. In addition, the template is insoluble and has good solvent resistance. Furthermore, according to JIS 2 1415, a weather resistance promotion test was conducted for 1,000 hours using a sun weather meter. As a result, no substantial discoloration or chalking was observed on the molded plate. In addition, a boiling test was performed at 90 C to evaluate the water resistance of the 100 Xiaoling, and the surface of the molded plate had a gloss, and the change in quality after seeing a: r. Furthermore, the paper size standard for financial rewards (CNS) A4 specifications -71-printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economy 4388 1 9 A7 B7 V. Description of the invention (69) The molding plate is set at 1 7 0 In the furnace of C, the heat resistance was evaluated for 1 hour. As a result, no appearance change such as yellowing was observed in the molded plate, and the surface gloss was not lost. The above main reaction conditions and results are summarized in Table 11. [Example 22] First, the same reaction, treatment and the like as in Example 11 were performed to prepare a (meth) acrylic acid slurry C '. Next, using this (meth) acrylic acid slurry C, except that the amount of magnesium oxide used in Example 21 was changed from 1 part to 2 parts, and the amount of pentadecylsuccinic acid used was changed from 1 part to 3 parts Except for the rest, the same operations, forming, and the like as in Example 21 were performed to form a molded plate. The gelation time in U (rc) is 100 seconds. The surface of the obtained molded plate has gloss and excellent smoothness. The main reaction conditions and results of the above molded plate are shown in Table n. [Comparative Example 1 3] First The same reaction and treatment as in Comparative Example 10 were performed to prepare a (meth) acrylic acid slurry for comparison. Next, using the (meth) acrylic acid slurry for comparison, the same operation as in Example 21 was performed to prepare a comparative iSM. (&gt; After that, the comparative SMC obtained was matured at 40 ° C for 1 day. However, the comparative SMC was cured after ripening. The above main reaction conditions are shown in Table ^ 丨. [Comparative Example 1 4] In Example 13 except that the addition amount of isobutyl vinyl ether relative to n-dodecyl mercaptan was changed from 2.0 times mole to 0.05 times mole, the rest were carried out in the same manner as in Example. Reaction and treatment of 13. As a result, during the esterification, the viscosity gradually rises, and a (meth) acrylic acid slurry with an increased solid content, viscosity, and weight average molecular weight is obtained. Next, this (meth) acrylic acid slurry for comparison is used. , The same as the implementation (read first Note on the back, please fill out this page) J #. Order

A7 B7! 438819 V. Description of the invention (70 cases 21, 1 operation, etc. 'to obtain sMc for comparison. Thereafter, the obtained comparison SMC was matured at 40 ° C for 1 hour. However, the comparison sMc would Hardening. The above main reaction conditions are summarized in Table 1. [Comparative Example 15] In Example 15, the addition amount of isobutyl vinyl ether relative to n-dodecyl mercaptan was changed from 2.0 times mole. It was changed to 0.05 moles, and the rest was the same as the reaction and treatment of Example 15. As a result, the viscosity will gradually increase during the esterification, and the solid content, viscosity, and weight average molecular weight can be increased ( Methyl) propionate: liquid. Next, 'use the (meth) acrylic acid slurry for comparison and perform the same operation as in Example 21, etc.' to obtain s μ C for comparison. Thereafter, use the obtained comparison for The SMC is matured at 40 ° C for 1 day. However, the comparative SMC is hardened. The above main reaction conditions are shown in Table 11. [Example 2 3] First, the same reaction and treatment as in Example 15 were performed. Prepare (meth) acrylic slurry C '. Next, use this (meth) acrylic slurry Liquid c, except that the amount of magnesium oxide used in Example 21 was changed from 1 part to 2 parts, the amount of pentaenylsuccinic acid used was changed from 1 part to 3 parts, and aluminum hydroxide was mixed with 100%. Except for 50 parts of calcium carbonate (Toyo 7 7 4 y 亇 々 Co., Ltd., Shi 74 4 &gt; P-70) as a filler instead of 150 parts of aluminum hydroxide, the rest were the same as in Example 21 Operation, molding, etc., to form a molded plate. The gelation time in 丨 丨 0C is 80 seconds. The obtained molded plate has a glossy surface and excellent smoothness. Moreover, the molded plate has excellent heat resistance. Furthermore, Assessing weather resistance and water resistance, the result is ____ 173: _____ This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page), 11 Central Standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 4 3 B8 1 9 A7 _ B7 V. Description of the invention (71) Compared with the molded plate of Example 21, although a little discoloration and slight reduction in gloss can be seen, these physical properties are superior. The above main reaction conditions and results are shown in Table 11. [Example 2 4 ] First, the same reaction and treatment as in Example 16 were performed to prepare (meth) propanoic acid slurry C. Second, this (meth) acrylic acid slurry was used, except that the amount of magnesium oxide used in Example 21 was changed. 1 part was changed to 2 parts, the amount of pentaenyl succinic acid was changed from 1 part to 3 parts, and 100 parts of aluminum hydroxide was mixed with glass powder as a filler (manufactured by Tobo Industries Co., Ltd., FMB 30W-001) 50 parts were replaced by 150 parts of aluminum hydroxide, and the rest were the same as those in Example 21, and the forming and forming were performed. The gelation time at 120 ° C was 120 seconds. The surface of the obtained molded plate has gloss and excellent smoothness. In addition, the molded board has excellent heat resistance, weather resistance, and water resistance. The above main reaction conditions and results are shown in Table 11. [Example 2 5] Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 ._, | _; ---- AWI—:; (Please read the precautions on the back before filling this page) First, perform the same as The reaction, treatment, and the like of Example 17 prepared (meth) acrylic acid slurry C ,. Next, the same operation as in Example 21 was performed except that the amount of the (meth) acrylic acid slurry π in Example 21 was changed from 100 parts to 85 parts, and 15 parts of trimethylolpropane trimethacrylate was added. , Forming, etc. 'to make a forming plate. At 110. The gelation time in 〇 was 75 seconds. The surface of the &lt; formed board is shiny and smooth. In addition, the molded board has excellent heat resistance, weather resistance, and water resistance. The main reaction conditions and results are shown in Table 11.

4388 1 9 A7 B7 Five invention description (72 Table 1 1 Example 21 22 23 24 25 Magnesium oxide (parts) 1 2 2 2 1 Pentaenyl succinic acid (parts) 1 3 3 3 —---- 1 Hydrogen Oxidation name (parts) 15 0 15 0 100 100 — 1 5 0 Calcium carbonate (parts) One — 50 __ —---- Glass powder (parts) — — — 50 -_ Gelation time (seconds) 100 100 80 120 —— _ 75 The forming material after maturity is good Good Good Good Good Heat resistance Good Good Good Good Good weather resistance Good Good Good Good Water resistance Good Good Good Good Comparative Example 13 14 15 Magnesium oxide (parts) 1 1 1 15 Fluorenylsuccinic acid (parts) 1 1 1 Aluminum hydroxide (parts) 150 150 150 The forming material after curing has been hardened and hardened [Example 2 6] ---:-: ----- Φ- -II-V (Please read the notes on the back before filling in this page)-Order and print the printed paper by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs First, perform the same reaction and treatment as in Example 13 and prepare ( Methyl) acrylic slurry C '. Second, in ( In 100 parts of meth) acrylic acid slurry, 1 part of mixed magnesium oxide, 2 parts of pentaenyl succinic acid, 1 part of tert-butylperoxy-2_ethylhexanoate, and 4 parts of zinc stearate Aluminium hydroxide (manufactured by Showa Denko Co., Ltd., 4 ^ 4 ^ H-3 20) 3 50 parts and glass -75- as a reinforcing material The standard applies to Chinese National Standard (CNS) A4 (210'〆297 Mm) 438819. A7 __ B7 V. Description of the Invention (73) (Please read the precautions on the back before filling this page) Glass fiber (1/4 inch long shred), then use a double wrist kneader This mixture is kneaded. In this way, BMC is obtained as a molding material. The proportion of glass-breaking fibers in the BMC is adjusted to 5%. Thereafter, the obtained BMC is packaged in a vinylon film (manufactured by Yuki 7k Co., Ltd.). 40. (: mature to 1 next. Second, the above-mentioned BMC is heated and press-molded by a predetermined method to form a molded plate (molded product). The gelation time in 1 10X: is 110 seconds. The obtained The surface of the molded board has gloss and excellent smoothness. The molded board has excellent heat resistance, weather resistance and water resistance. The above main reaction conditions The results are shown in Table 12. [Comparative Example 16] First, the same reaction, treatment, and the like as in Comparative Example 10 were performed to prepare a (meth) acrylic acid slurry for comparison. Second, this (meth) acrylic acid slurry was used. The same operation as in Example 26 was performed to obtain a BMC for comparison. The obtained comparative BMC was matured at 40 ° C. for 1 day. However, after maturation, BMC will harden. The main reaction conditions and results are shown in Table 12. [Example 2 7] Printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economy First, the same reaction, treatment, and the like as in Example 14 were performed to prepare a (meth) acrylic acid slurry Cf. Next, 1 part of (meth) acrylic acid slurry C, 100 parts of bis (4-third-butylcyclohexyl) peroxycarbonate as a hardener, and aluminum hydroxide (manufactured by Showa Denko Corporation) were mixed. (,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ~ B), 200 parts, knead the mixture, and defoam. Thereby, a cast material was obtained as a molding material. Secondly, the obtained injection molding material is injection-molded using a glass mold chamber, that is, after the injection molding material is injected into the mold chamber, it is hardened at 60 ° C for 1 hour -76- This paper standard applies Chinese national standards ( CNS) A4 specification (210X297 mm) 438819 A7 B7 5. Invention description (74). After demolding, post-curing was performed at 100 ° C for 2 hours to obtain an artificial marble slab, which is a molded article. The surface of the obtained artificial marble slab has luster, excellent smoothness, and high-quality and texture at the door. Artificial marble has excellent heat resistance, weather resistance and water resistance. The main reaction conditions and results are shown in Table 12. [Comparative Example 17] First, the same reaction, treatment and the like as in Comparative Example 10 were performed to prepare a (meth) acrylic acid slurry for comparison. Next, this comparative (meth) acrylic acid 1 solution was used to perform the same operation, molding, and the like as in Example 27 to prepare an artificial marble slab for comparison. However, the heat resistance, weather resistance, and water resistance of the comparative artificial marble slabs obtained by the evaluation were evaluated. As a result, changes in appearance such as yellowing were seen, and the surface gloss was also lost, causing streaks. The main reaction conditions and results are shown in Table 12 [Example 2 8] Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 丨 ._ ^^ ---- AW | 丨 ''-·· (Please read the note on the back first Please fill in this page again.) First, the same reaction and treatment as in Example i 5 were performed to prepare (meth) acrylic acid slurry C '. Next, to 100 parts of this (meth) acrylic acid slurry c, 100 parts of bis (4 · third butyl cyclohexyl) peroxycarbonate and 3 parts of third butyl peroxybenzoate (Japanese Manufactured by Oils and Fats Co., Ltd., 〆 一, 千 小 2) 1 part, aluminum hydroxide (manufactured by Showa Denko Co., Ltd., Hiroshi Nakimoto H-npoO parts, and as a release agent VII, k (trade name (Made by DuPont, USA) 7 parts to form a drawn forming material. Next, using a mold with a total length of 800 mm and a hole size of 113 mm x 3 "mm", the obtained drawn forming material was drawn together with 75 glass bundles to form t. (cns) A7 B7 438819 ----------- 5. Explanation of the invention (%) The mold temperature is 90 ° C and the drawing speed is 0.8 m / min. In this way, a molded plate (molded product) is obtained. The surface of the obtained molded plate has gloss and smoothness. The molded plate has excellent heat resistance, weather resistance, and water resistance. The main reaction conditions and results are shown in Table 12. [Comparative Example 18] First, In the same manner as the reaction and treatment of Comparative Example 10, a (meth) acrylic acid τ acid slurry was prepared for comparison. Next, it was used The (meth) propionic acid slurry for comparison was subjected to the same operations and molding as in Example 28 to prepare a comparative molded plate (molded article). However, the heat resistance and weather resistance of the obtained comparative molded plate were evaluated. And water resistance. As a result, changes in appearance such as yellowing can be seen, and the gloss of the surface is also lost, resulting in markings. The above main reaction conditions and results are shown in Table 12 II —: ----- ΦI— »— * »(Please read the precautions on the back before filling this page)-Order printed by the Central Consumers' Cooperative of the Ministry of Economic Affairs-78-! 4388 19 A7 __________B7 V. Invention Description (76) Employee Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Print Table 12 Example 26 27 28 Magnesium oxide (parts) 1 _ Pentaenyl succinic acid (parts) 2 —— ——Aluminum hydroxide (parts) 3 50 200 200 Gelation time (parts) 110 —— — Good forming material after maturity — — Good heat resistance Good Good Weather resistance Good Good Water resistance Good Good Comparative Example 16 17 18 Magnesium oxide (parts) 1 — — Pentadecyl succinic acid (parts) 2 — — Aluminium hydroxide (parts) 3 50 200 200 After curing, the molding material has hardened — _ Heat resistance — Poor weather resistance-Poor ---- --- Poor water resistance — Poor From Tables 6 to 12 It is obvious that the molding material can be obtained by using the manufacturing method of this example. That is, regarding the molding material of Example 19 or 20: no odor due to a thiol compound is generated during molding, and No carbides adhere to the mold. Regarding the actual travel records 1 3 ～ 丨 8 and 21 ～ 28 (the molding material can be hardened in a relatively short time. Furthermore, it becomes ^ _____________________- 79-This paper standard is applicable to China National Standard (CNS) 8-4 specifications (21〇 &gt; &lt; 297 mm) 2f Read the notes on the back ^ before filling in this page j

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 8 8 19 A7 —-B7 V. Description of the invention (77) The molded products obtained from the above-mentioned molding materials have excellent heat resistance, weather resistance, solvent resistance and water resistance. And other physical properties. [Example 2 9] In a reactor equipped with a thermometer, a cooler, a nitrogen introduction pipe, and a stirrer, 130 parts of methyl methacrylate and 40 parts of cyclohexylmaleimide as a vinyl compound were fed. After 30 parts of styrene, the reactor was purged with nitrogen. Next, the mixture was stirred while the temperature was raised to 85t, then 0.006 parts of AIBN and 03 parts of n-dodecyl mercaptan were added to start the polymerization reaction. 5 hours after the start of the polymerization reaction, the viscosity of the reaction solution became 30 ~ 3 5 poise (25 ° C), so at this point the reaction was terminated (that is, the reaction time was 5 hours), and further formazan was added to the reaction solution. After 35 parts of methyl methacrylate, cool (quench) to 40 ° C. Next, after adding isobutyl vinyl ether to the above reaction mixture, the temperature was raised to 100 C and stirred; stirred for 30 minutes' to treat the n-dodecyl mercaptan remaining in the reaction mixture. The isobutyl vinyl ether is added at 2.0 times moles to the n-dodecyl mercaptan added during polymerization. Thereby, (meth) acrylic acid slurry C was obtained. (Meth) acrylic acid slurry c has a solid concentration of 29%, a dryness of 8.5 poise, and a weight average molecular weight of 103,000 °. Next, 100 parts of the (meth) acrylic acid slurry C is mixed with a third butyl per milk-2. · Ethyl hexane, 4 parts of hard fat, and 400 parts of oxychloride (manufactured by Showa Denko Co., Ltd., HS-320) 400 parts, to obtain the compound J ^ a---------- ------------------------ 々 ·. Τ ............ ......................................................... Then, add glass fiber (1/4 inch long shred) to the ingredients, double-80-this paper size applies Chinese National Standard (CNS) A4 specification (210x297 mm) I ------ ----- Μ. ^ I (Please read the notes on the back before filling this page) Order 438819 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (78) Wrist-type kneader . Thereby, BMC was obtained as a molding material. The proportion of the glass fiber in the BMC is adjusted to 5%. Thereafter, the obtained BMC was placed in a metal container and matured at 40 t. After ripening, the ingredients, namely BMC, will not harden, and the surface of BMC will not be sticky. Next, the BMC is formed by heating and pressing. That is, a mold of a predetermined size is used, and the temperature of the upper mold is set to 12 (rc, and the temperature of the lower mold is set to 110C.) The BMC cut into a predetermined size is filled in the mold, and the mold is locked at a pressure of 6 MPa, Press molding for 7 minutes to make a molded product, that is, a plate with a thickness of 3 mm. The gelation time in 120X: is 70 seconds. The obtained molded product has a gloss (60.0 gioss ^ 85, which is good, In addition, the X chromaticity (YI) was 2.31, which was low in colorability. Furthermore, the surface of the molded product did not show mesh-like floating caused by glass fibers, and the surface was excellent in smoothness. It was also promoted for 1,000 hours. As a result of the weather resistance test, substantially no discoloration or powdering was observed in the molded product. Furthermore, the molded product was placed in a furnace set at 150 C for 1 hour to evaluate the heat resistance. As a result, the molded product was not visible. The appearance of yellowing and the like changes without losing the surface gloss. Moreover, the above-mentioned BMC does not harden when stored at 40 ° C for 2 months. That is, the BMC has excellent storage stability. [Example 3 0] In addition to using methyl propionate 1 1 8 parts and methyl propionate 丨 2 parts to Except for 30 parts of methyl methacrylate in Example 29, the rest was operated in the same manner as in Example 29 to start the polymerization reaction. 4.5 hours after the start of the polymerization reaction, the viscosity of the reaction solution became 30 to 35 pise ( 25 C), so at this point, the reaction is terminated, and the reaction solution is further __- 81 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- ΦII • ~ -m (Please read the notes on the back before filling this page) Order 438819 Printed by A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. After adding 35 parts of methyl methylpropionate to the description of the invention (79), It was cooled (quenched) to 40.0. Then, the same treatment as in Example 29 was performed in the above reaction mixture to obtain a (meth) propionic acid slurry C. The solid concentration of the (meth) acrylic acid slurry c was 28%, viscosity is 9.50, 86, and weight average molecular weight is 17,000. Second, 100 parts of (meth) propanoic acid slurry C is mixed with a third butylperoxy-2-ethyl 1 part of hexanoic acid ester, 4 parts of zinc stearate, and aluminum hydroxide (manufactured by Showa Denko Corporation) (/, 4 4 HS-320) 400 parts to obtain ingredients. Then, to this ingredient, add glass fiber (shreds of 1/4 inch length), and knead with a double wrist kneader. With this, get Bmc as a molding material. The ratio of the above-mentioned glass fibers in the BMC was adjusted to 50 /. After that, the obtained BMC was placed in a metal container and aged at 40 ° C for 1 day. After the ageing The ingredients, that is, BMC will not harden, and the surface of bmc will not dry. Secondly, the above-mentioned BMC is heated and pressurized. That is, using a mold of a predetermined size, set the upper mold temperature to Uol and the lower mold temperature to ii ° C. Then, the BMC cut into a predetermined size was filled in the above mold, and the mold was clamped at a pressure of 6 MPa, followed by heating and press molding for 7 minutes to form a molded product, that is, a plate having a thickness of 3 mm. At 120. (: The gelation time is 60 seconds. The obtained molded article has a gloss (60. Magic 88) of 85, which is good, and a yellowness (YI) of 2.10, which is low in colorability. Further, the molded article is Mesh-like floating caused by glass fibers is not seen on the surface, and the surface is excellent in smoothness. In addition, after 1,000 hours of accelerated weathering test, as a result, no discoloration or powdering on the shell was observed. The molded product was placed in a hearth furnace set at 150 C for 1 hour to evaluate the heat resistance. As a result, the molded product did not show any appearance degradation such as yellow owing, and did not lose the surface gloss. The above BMC was in I ΦII- Two (Please read the notes on the back before filling this page),?! 1--I---1 ---

4388 19 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. It will not harden if stored for 2 months under the invention description (so). That is, BMC has excellent storage stability. 0 [Example 3 1] To 100 parts of the (meth) acrylic acid slurry c obtained in Example 30, 8.4 parts of glycidyl methacrylate and triphenylphosphine were added. After 2 parts and 005 parts of hydrogen, it was stirred at 100 ° C. for 10 hours to perform an esterification reaction. The obtained (meth) acrylic acid slurry C had a solid concentration of 33%, a viscosity of 20 poise, and a weight-average molecular weight of 130,000. The number of double bonds per molecule of the (meth) acrylic acid polymer c, (meth) acrylic acid polymer solution c was measured in the same manner as in Example 13. As a result, the number of double bonds per molecule was 13. Then, except that the (meth) acrylic acid slurry C was used instead of the (meth) acrylic acid slurry C in Example 30, the same procedure as in Example 30 was performed, and the kneading and aging operations were performed to obtain BMC. In addition, the same molding operation as in Example 30 was performed to produce a molded product, that is, a plate having a thickness of 3 mm. The gelation time at 120 ° C was 55 seconds. The obtained molded article had a gloss (60. § 1088) of 85, which was good, and a yellowness (YI) of 2.43, which was low in colorability. Furthermore, the molded product does not have mesh-like floating caused by glass fibers on the surface, and has excellent surface smoothness. Further, a 1,000-hour accelerated weathering test was performed, and as a result, the molded article was not recognized to be substantially discolored or powdered. Furthermore, when the molded article was placed in a furnace set at 15 ° C. for 1 hour to evaluate the heat resistance, as a result, the molded article did not show any change in appearance such as yellowing and did not lose surface gloss. The BMC is 40. It will not harden under 2 months under C. That is, BMC has excellent storage stability. [Example 3 2] -83- ------------ v} · (Please read the precautions on the back before filling this page) Order r-438819 A7 ___B7 V. Description of the invention (81 ) In a reactor equipped with a thermometer, a cooler, a nitrogen pipe, and a stirrer, 200 parts of methyl methacrylate was fed, and then the reactor was replaced with nitrogen. Next, while stirring the contents, the temperature was raised to 85 ×: After that, 0.006 parts of aibn and 0.3 parts of n-dodecyl mercaptan were added to start a polymerization reaction. 5.5 hours after the start of the polymerization reaction, the viscosity of the reaction solution was 30 to 35 poise (25 ° C), so the reaction was terminated at this point. After further adding methyl methacrylate to the reaction solution, it was cooled ( (Cooling) to 40 ° C. Then, the same treatment as in Example 29 was carried out in the reaction mixture to obtain (meth) acrylic acid slurry C. The (meth) propionic acid slurry c had a solid concentration of 29%, a viscosity of 7.5 poise, a weight-average molecular weight of 105,000, and then, in the above (meth) acrylic acid slurry C 100 parts, Add 2 parts of dibenzoylperoxide to dissolve. Thereby, a molding material as a molding material was obtained. The obtained cast material was defoamed by reduced pressure. This injection molding material, that is, the ingredients, has excellent storage stability. Next, this injection-molded material was poured into the same mold chamber as in Example 1, and then heated to 60 ° C to harden it. The gelation time was measured in the same manner as in Example 1. As a result, the gelation time at 60 ° C was 45 minutes. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) and ‘after mold release’ is cured at 100 C to obtain a resin plate, which is a molded product. The obtained resin plate is insoluble in TJJF and acetone, that is, the above resin plate has excellent solvent resistance. [Example 3 3] Nitrogen substitution was performed in the reactor after feeding 93 parts of methyl methacrylate and 7 parts of methyl propionate in a reaction equipped with a thermometer, a cooling pipe, a nitrogen introduction pipe and a stirrer. . Secondly, while stirring the above mixture, the mixture is raised while the scale is suitable for CNS) A4 specifications 438819 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (82 temperature to 80X: After that, add 1 copy of AIBN and move as a chain 4 parts of n-dodecyl mercaptan was copolymerized for 4 hours to obtain a reaction mixture (untreated acrylic slurry). Then, glycidyl methacrylate as an unsaturated epoxy compound was added to the above reaction mixture. After 10 parts, 0.03 parts of zinc octoate and 0.01 parts of hydroquinone as the esterification catalyst, the temperature was raised to 100. (: The esterification reaction was carried out in an air atmosphere for 5 hours. A (meth) acrylic acid slurry E was obtained. The (meth) acrylic acid slurry E was colorless and transparent, with a solid concentration of 52%, a viscosity of 36 poise, and a weight average molecular weight of 17,000. Then, in the above (meth) acrylic acid In 100 parts of the slurry E, 2 parts of dibenzofluorene peroxide was added to dissolve it. Thereby, a molding material as a molding material was obtained. The obtained molding material was degassed by reduced pressure. In It has not been gelled for more than 3 hours at a temperature. That is, this cast material has excellent storage stability. Also, when the storage stability does not gel at room temperature even after 3 hours, it is judged as "good" and at room temperature When gelled within 3 hours, it was judged as "defective." Then, a mold chamber that was closed with a so-called elastic gasket (the two glass plates were arranged at a distance of 7 mm from each other) was used to perform injection molding. That is, after the injection molding material is injected into the mold cavity, it is heated to 60.2 to harden it. Further, after the cured injection molding material is released from the mold, it is performed for 2 hours at 1200c. After curing (the so-called after cure), a molded plate was obtained. The obtained molded plate was measured for a load deformation temperature (HDT; thermal deformation temperature) in accordance with JIS 6911 and was 120 ° C. The above main reaction conditions are shown in Table 13. Ϋ I I----i ^ i — -1 — —i-— ϋ I β r: c Please read the notes on the back first #fill in this purchase) tr -85 4 3 88 1 9 A7- ------- B7 V. Description of the invention (83) The results are shown in Table 15. [Example 3 4] Except that zinc octoate in 33 was changed to tin octoate, the rest was reacted in the same manner as in Example 33 to obtain (meth) acrylic acid slurry E. The (meth) acrylic acid polymer liquid E was colorless and transparent, and had a solid concentration of 52% and a viscosity of 35 Poise, weight-average molecular weight is 16,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained O-type material had excellent storage stability. Then, the same procedure as in Example 33 was performed. The operation 'obtained a shaped plate. The load deformation temperature of the obtained shaped plate was 118C. The above main reaction conditions are shown in Table 13. The obtained results are shown in Table 15. [Example 3 5] The same reaction as in Example 33 was carried out except that zinc octoate in Example 33 was changed to octanoate octoate to obtain (meth) propanoic acid slurry E. This (meth) acrylic acid slurry E was colorless and transparent, had a solid concentration of 52%, a viscosity of 35 poise, and a weight average molecular weight of 16,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained king-type material has excellent storage stability. Then, the same operation as in Example 33 was carried out to obtain a formed plate. The load deformation temperature of the obtained formed plate was ii8 ° c. The above main reaction conditions are shown in Table 13. The obtained results are shown in Table 15. [Example 36] The same reaction as in Example 33 was carried out except that zinc octoate in Example 33 was changed to zinc stearate to obtain (meth) acrylic acid slurry e. The (meth) acrylic acid -------______- 86-The paper size is suitable for financial ® National Standard (CNS) A4 size (2KΓ × 297mm) ......- —---I —φII: I r (Please read the notes on the back before filling out this page} 'Order printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 438819 A7 B7 E is colorless and transparent, with a solid concentration of 52%, a viscosity of 36 poise, and a weight average molecular weight of 17,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained cast material It has excellent storage stability. Then, the same operation as in Example 33 was performed to obtain a shaped plate. The load deformation temperature of the obtained shaped plate was 120 ° C. The above main reaction conditions are shown in Table 13. The obtained results are shown in Table 15. [Example 3 7] Except that zinc octoate in Example 33 was changed to zinc benzoate, the rest of the reaction was the same as that in Example 33 to obtain (meth) acrylic acid slurry E. The (meth) acrylic acid Slurry E is colorless and transparent, and the solid concentration is 5 2%, viscosity was 37 poise, weight average molecular weight was 17,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained cast material had excellent storage stability. Then, the same was performed as The operation of Example 33 resulted in a formed plate. The load deformation temperature of the obtained formed plate was 120 C. The above main reaction conditions are shown in Table 13. The obtained results are shown in Table 15. [Example 3 8] Except that zinc octoate was changed to zinc chloride (ZnCl2) in Example 33, the rest was the same as that in Example 33 to obtain (meth) acrylic acid slurry E. The (meth) acrylic acid slurry E was colorless and transparent, and the solid concentration was 51%, viscosity is 37 poise, weight-average molecular weight is 18,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained cast material had excellent storage stability. Then, it was performed in the same manner as in Example_ —_ -87- _______ This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) * _ ·· '^ m I (Please read the precautions on the back before filling this page)

A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The operation of invention description (85) 33, to obtain the forming plate. Table 14 shows the main reaction conditions of the obtained formed sheet at a load deformation temperature of 120 C Ji. The obtained results are shown in Table 15. [Example 3 9] A reaction was performed in the same manner as in Example 33 except that the center zinc octoate in Example 33 was changed to zinc hydrogen phosphate (ZnHpo4) to obtain (meth) propanoic acid slurry E. The (meth) propanoic acid ME was colorless and transparent, had a solid concentration of 51%, a buff of 36 poise, and a weight average molecular weight of 17,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained injection molding material has excellent stability and stability. Then, the same operation as in Example 33 was performed to obtain a formed plate. The load deformation temperature of the obtained formed plate was 120 ° C. The above reaction conditions are shown in Table 14. The obtained results are shown in Table 15. [Example 40] The same reaction as in Example 33 was carried out except that zinc octoate in Example 33 was changed to zinc acetamate [Zn (acac) j] to obtain (meth) acrylic acid slurry E. This (meth) acrylic acid slurry E was colorless and transparent, had a solid concentration of 52%, a viscosity of 45 poise, and a weight average molecular weight of 21,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained cast material has excellent storage stability. Then, the same operation as in Example 331 was performed to obtain a formed plate. The load deformation temperature of the obtained formed plate was 121 ° C. The above main reaction conditions are shown in Table 13. The obtained results are shown in Table 15. [Example 4 1] -88-This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210x ^ 97 mm) ------------ Λ «-m (Please read the note on the back first (Fill in this page again)

1T 5 438819 A7----- ______B7 、 Explanation of the invention (86) Except that the n-dodecyl mercaptan in Example 3 3 is changed to 3 • Hydrogenthiopropionic acid (thiol compound), the rest is the same as The reaction of Example 33 gave (meth) acrylic acid slurry E. This (meth) acrylic acid slurry E was colorless and transparent, had a solid concentration of 51%, a viscosity of 37 poise, and a weight average molecular weight of 18,000. Then, the same operation as in Example 33 was performed to obtain a cast material. The obtained / main material has excellent stability and stability. Then, the same operation as in Example 33 was performed to obtain a formed plate. The load deformation temperature of the obtained formed plate was 12 5 C. The above main reaction conditions are shown in Table 1 *. The obtained results are shown in Table 15. ----------— Μ ^ I r (Please read the notes on the back before filling this page) Table 13 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Example 33 34 35 36 37 Methacrylic acid Esters (parts) 93 93 93 93 93 Methacrylic acid (parts) 7 7 7 7 7 n-dodecyl mercaptan (parts) 4 4 4 4 4 ΑΙΒΝ (parts) 1 1 1 1 1 Reaction temperature (° C) 80 80 80 80 80 Reaction time (hr) 4 4 4 4 4 Glycidyl methylpropionate (parts) 10 10 10 10 10 Zinc octoate (parts) 0.03 One one — — Osmium octoate (parts) — 0.03 one — one Zirconium octoate (parts) — — 0.03 — — Zinc stearate (parts) one — one 0.03 one benzoic acid (parts) — one one — 0.03 reaction temperature (° c) 100 100 100 100 100 reaction time (hr) 5 5 5 5 5

、 1T -89-This paper size applies to China National Standard (CNS) Α4 size (210 × 297 mm) 4388 1 9 A7

7 B V. Description of the invention (87) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy 14 Example 3 8 3 9 40 41 Methyl methacrylate (parts) 93 93 93 93 Methacrylic acid (parts) 7 7 7 7 n-dodecyl mercaptan (parts) 4 4 4 — 3 -nitrothiopropionic acid (parts) — one to four AIBN (parts) 1 1 1 1 Reaction temperature (° c) 80 80 80 80 Reaction time (hr ) 4 4 4 4 Glycidyl methacrylate (parts) 10 10 10 10 Zinc octoate (parts) — 1 — 0.03 Zinc chloride (parts) 0.03 — 1 — Zinc hydrogen phosphate (parts) — 0.03 One — B锌 Zinc acetone (parts) — 0.03 one reaction temperature (° C) 100 100 100 100 reaction time (hr) 5 5 5 5 (Please read the precautions on the back before filling this page) -90- This paper size is applicable to China Standard (CNS) A4 specification (210X 297 mm) 438819 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs; printed paper A7 B7 invention description (88 Table 15 Example 33 34 3 5 3 6 37 weight average molecular weight ( X 10 4) 1.7 1.6 1.6 1.7 1.7 Poise 36 3 5 3 5 36 37 Solid concentration (%) 52 52 52 52 52 (meth) acrylic acid slurry colorless colorless colorless colorless colorless colorless load deformation temperature (° C) 120 118 118 120 120 Good storage stability Good Good Good Good Example 38 39 4 1 4 1 Weight average Molecular weight (X 104) 1.8 1.7 2.1 1.8 'Poise 37 36 45 3 7 Solid concentration (%) 5 1 51 52 5 1 (meth) acrylic acid slurry colorless colorless colorless colorless colorless load deformation temperature (° C 120 120 121 125 Good storage stability Good Good Good Except that zinc octoate in Example 33 was changed to cobalt octoate, the rest was reacted with Example 33 to obtain a (meth) acrylic acid slurry. The (meth) The acrylic slurry was a strong blue color, with a solid concentration of 54%, a viscosity of 40%, and a weight average molecular weight of 19,000. Then, the same operation as in Example 33 was performed to obtain a molding material for comparison. The obtained comparison The injection molding material had poor storage stability. Then, the same operation as in Example 33 was performed to obtain a molded plate. The obtained ^ type plate (degrees apply to the Zhongguanjia Standard (CNS) A4 specification cents (Please read the precautions on the back before filling in this page}

438819 A7 ------- B7 5. The load deformation temperature of the description of the invention (89) is 115 ° C. The above main reaction conditions are shown in Table 16. The results obtained are shown in Table 18. [Comparative Example 20] A reaction was carried out in the same manner as in Example 33 except that zinc octoate in Example 33 was changed to iron octoate to obtain a (meth) acrylic acid slurry. The (meth) acrylic acid slurry was dark brown, had a solid concentration of 51%, a viscosity of 3 5 poise, and a weight average molecular weight of 15,000. Then, the same operation as in Example 33 was performed to obtain a comparative injection molding material. The obtained comparative injection-molded material had poor storage stability. Then, the same operation as in Example 33 was performed to obtain a molded plate. The load deformation temperature of the obtained molded plate was 105X :. The above main reaction conditions are shown in Table 16. The results obtained are shown in the table; [8 中. [Comparative Example 21] The same procedure as in Example 33 was carried out except that zinc octoate in Example 33 was changed to triethylamine, to obtain a (meth) propionic acid slurry. The (meth) propionic acid slurry was dark brown, had a solid concentration of 52%, a viscosity of 36 Poise, and a weight average molecular weight of 17,000. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs --------- Φ—— (Please read the notes on the back before filling this page} Injection molding material. The obtained comparative injection molding material had poor storage stability. Then, the same operation as in Example 33 was performed to obtain a molded plate. The load deformation temperature of the obtained molded plate was 12 ° C. The reaction conditions are shown in Table 16. The results obtained are shown in Table 18. [Comparative Example 2 2] Except that the zinc octoate in Example 33 was changed to triethylbenzyl ammonium gas salt by -92-

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 438819 A7 ______B7 5. Except for the description of the invention (90), the rest was reacted in the same manner as in Example 33 to obtain a (meth) acrylic acid slurry. The (meth) acrylic acid slurry was light brown, had a solid concentration of 53%, a viscosity of 36 poise, and a weight average molecular weight of 16,000. Then, the same operation as in Example 33 was performed to obtain a comparative injection molding material. The obtained comparative injection-molded material had poor storage stability. Then, the same operation as in Example 33 was performed to obtain a molded plate. The resulting molded plate had a load deformation temperature of 110. (: The above main reaction conditions are shown in Table 16. In addition, the obtained results are shown in Table 18. [Comparative Example 2 3] Except that glycidyl methylpropionate was not added in Example 3, The rest was reacted in the same manner as in Example 33 to obtain a (meth) acrylic acid slurry. The (meth) propionic acid slurry was colorless and transparent, with a solid concentration of 5000/0, a viscosity of 30 poise, and a weight average molecular weight of 14 〇〇〇。 Then, the same operation as in Example 33 was performed to obtain a comparative injection molding material. The obtained comparative injection molding material had poor storage stability. Then, the same operation as in Example 33 was performed to obtain a molding. The load deformation temperature of the obtained molded plate is as low as 90. (:, the thermal strength is poor. The above main reaction conditions are shown in Table 16. In addition, the obtained results are shown in Table 18. [Comparative Example 2 4 ] Except that zinc octoate was not added in Example 33, the rest was reacted with Example 33 to obtain a (meth) acrylic acid slurry. The (meth) propionic acid slurry was colorless and transparent, and the solid concentration was 46%. Viscosity of 27 p〇ise, weight Average molecular weight of 14, 〇〇〇 In turn, the operation performed with the embodiment of Example 33, to give a comparative profile of the note

This paper rule Chinese national standard TFns) M specifications (21〇x29H I -----------: 2 (Please read the precautions on the back before filling this page), π 4 3 381 9 A7 B7 5 (91) of the invention. The obtained comparative injection-molded material has poor storage stability. Then, the same operation as in Example 33 was performed to obtain a molded plate. The load deformation temperature of the obtained molded plate was as low as 90X: The thermal strength is poor. The above main reaction conditions are shown in Table 17. In addition, the obtained results are shown in Table 18. [Comparative Example 25] Except using 100 parts of methyl methacrylate instead of Example 33 93 parts of methyl propionate methyl acid and 7 parts of methacrylic acid, and the addition amount of n-dodecyl mercaptan was changed from 4 parts to 3 parts, and the rest were reacted in the same manner as in Example 33 to obtain ( (Meth) acrylic acid slurry. The (meth) acrylic acid slurry was colorless and translucent, with a solid concentration of 46%, a dryness of 27 poise, and a weight average molecular weight of 14,000. Then, the same operation as in Example 33 was performed to obtain a comparison. The injection molding material used. The obtained comparison injection molding material has a storage safety Poor performance. Then, the same operation as in Example 33 was performed to obtain a molded plate. The load deformation temperature of the obtained molded plate was as low as 90. (:, the thermal strength is poor. The above main reaction conditions are shown in Table 17. Also, The results obtained are shown in Table 18. (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -94 丁 r-8 8 3 4 9

7 B V. Description of the invention (92) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 16 Comparative Example 19 20 2 1 22 23 Methyl methacrylate (parts) 93 93 93 93 93 Methacrylic acid (parts) 7 7 7 7 7 n-dodecyl mercaptan (parts) 4 4 4 4 4 AIBN (parts) 1 1 1 1 1 Reaction temperature (° c) 80 80 80 80 80 Reaction time (hf) 4 4 4 4 4 Methyl Glycidyl acrylate (parts) 10 10 10 10 — Caprylic acid (parts) 0.03 — Mono-monocaprylate (parts) — 0.03 Mono-triethylamine (parts). — 0.03 — — Triethyl Benzyl ammonium chloride salt (parts) — — 0.03 zinc octoate (parts) — — — 0.0 3 Reaction temperature (° c) 100 100 100 100 100 Reaction time (hr) 5 5 5 5 5 Table 17 Comparative Examples 24 25 methyl methylpropionate (parts) 93 100 methacrylic acid (parts) 7 n-dodecyl mercaptan (parts) 4 3 AIBN (parts) 1 1 reaction temperature (° c) 80 80 reaction time ( hr) 4 4 Glycidyl methacrylate (parts) 10 10 Zinc octoate (parts)-0.03 Dust temperature (° c) 100 100 Reaction time hr) 5 5 (Please read the notes on the back before filling out this page) -95- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) Table 1 8 4388 1 9 A7 _______ 5. Description of the invention ( 93) Example 1 9 20 ---- 1 21 22 — 23 Weight average molecular weight (X 104) 1.9 1. 1.5 1.7 1.6 1.4 Poise 40 3 5 3 6 36 --- Q Λ solid concentration (%) 54 5 1 52 53 5 〇 (Meth) acrylic acid slurry color strong tea brown tea brown light brown ^ U ----- load deformation temperature (° c) 115 105 120 110 ——. Ο poor storage stability Poor fu --- Poor Comparative Example 24 25 Weight-average molecular weight (X104) 1.4 1.4 Poise 27 27 Solid concentration (%) 46 46 (Meth) acrylic acid slurry Colorless and colorless Deformation temperature (° C) 90 90 Poor storage stability. It is clear from Tables I3 to 1S that Examples 33 to 41 have very little coloring and excellent storage stability ... The molded product (hardened product) obtained by forming the above material: material is hot. When the strength is excellent. [Example 4 2] In a reactor equipped with a thermometer, a cooler, a nitrogen introduction tube, and a stirrer, 8 parts of methyl methacrylate II, 2 parts of methacrylic acid, 2 parts, and N-cyclohexyl maleate were fed. After 40 parts of imine and 30 parts of styrene, nitrogen was replaced in the reactor. Secondly, while stirring the above mixture, the temperature was raised ________-96-This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297 mm) ----------- ^ 9. — '·: (Please read the notes on the back before filling this page)-Order printed by the Central Consumers Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives of the Ministry of Economic Affairs Printed by the Central Consumers Bureau of the Ministry of Economics, printed by 4388 1 9 at B7 ) After reaching 85 ° C, 0.006 parts of AIBN and 0.3 parts of n-dodecyl mercaptan were added to start the polymerization reaction. 4.5 hours after the start of the polymerization reaction, the viscosity of the reaction became 30 to 35 poise (25 ° C), so the reaction was terminated at this point. After adding 35 parts of methyl methacrylate to the reaction solution, it was cooled to 40 ° C (Chill). Next, 8.4 parts of glycidyl methylpropionate, 0.2 parts of zinc octoate, and 0.05 parts of hydroquinone were added to 100 parts of the reaction mixture, and then stirred at 100 ° C for 10 hours to perform an esterification reaction. The obtained (meth) acrylic acid slurry E had a solid concentration of 32%, a viscosity of 15 poise, and a weight-average molecular weight of 140,000. In the same manner as in Example 13, Group) The number of double bonds per molecule of acrylic polymers. As a result, the number of double bonds per molecule was 14. Next, 1 part of the (meth) propionic acid slurry E 100 was mixed with 1 part of tert-butylperoxy-2-ethylhexanoate, 4 parts of zinc stearate, and Ming hydroxide (Showa 400 parts manufactured by Denko Co., Ltd. (^, 彳 夕 今 彳 HS-320), thereby obtaining BMC as a molding material. The ratio of the glass fiber in the BMC was adjusted to 5%. Thereafter, the obtained BMC was placed in a metal container and aged at 40 ° C. for 1 day. After ripening, the ingredients, namely BMC, will not harden, and the surface of BMC will not wither. Next, the B MC is formed by heating and pressing. That is, using a mold of a predetermined size, the upper mold temperature was set at 120 ° C, and the lower mold temperature was set at 110 ° C. In addition, the BMC cut into a predetermined size is filled in the above mold, and the mold is clamped at a pressure of 6MP a, and heated and press-molded for 7 minutes to form a molded product. _____- 97- This paper size applies Chinese National Standard (CNS) A4 Specifications (21〇χ297mm) --------- Φ—, i II (Please read the notes on the back before filling out this page) Order printed by the Central Consumers Bureau of the Ministry of Economic Affairs Consumer Cooperatives 4 388 1 9 A7 ________B7 V. Description of the Invention (95) ^ ~~ ^ One by one ^ &quot; It is a plate with a thickness of 3 mm. The gelation time at 12 (rc is "seconds." The obtained I molded product, gloss (60. gl0ss # 87, is good, and the yellowness (YI) is 2.00 'is low colorability. Further, the molded product On the surface, no mesh-like floating caused by broken glass fibers was observed, and the surface was excellent in smoothness. Furthermore, after a 1,000-hour accelerated weathering test, as a result, no substantial discoloration or powdering was observed in the molded product. Further, The molded product was placed in a furnace set at 150 ° C for 1 hour to evaluate the heat resistance. As a result, the molded product did not show appearance changes such as yellowing, and did not lose the surface gloss. The above BMCs4 (reserved under rc 2) It will not harden for a month. That is, BMC has excellent storage stability. [Example 4 3] In a reactor equipped with a thermometer, a cooler, a gas-nitrogen introduction pipe, and a blender, an aqueous solution is fed. (It is obtained by dissolving 0.2 parts of polyvinyl alcohol (PVA-205, manufactured by Yuki K. Co., Ltd.) as a dispersion stabilizer in a dispersion medium (solvent), that is, 180 parts of deionized water.) In another container, 19 parts of methyl methacrylate, methacrylate, and n-dodecyl mercaptan were mixed. 0.05 parts and 0.2 parts of AIBN to obtain a mixture. The above mixture was added to the reactor and stirred at 500 rpm to form a homogeneous suspension. Then, the temperature was raised to 75 ° C while blowing nitrogen gas, and the temperature was continued at this temperature. A suspension polymerization reaction was performed for 5 hours. Then, water was removed from the polymerization suspension (reaction mixture) to remove the polymer. Furthermore, 30 parts of the polymer was dissolved in 70 parts of methyl methacrylate. „ Then, to 100 parts of the polymer solution, add methacrylic acid to shrink ___ -98- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page )-Order_ 438819 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (96) 2.5 parts of glyceride, 0.1 part of zinc octoate, and 0 part of hydroquinone, under ι〇〇χ: Tantalum is used for esterification reaction. The obtained (meth) acrylic acid slurry E is colorless and transparent, with a solid concentration of 31%, a dryness of 5.5 poise, and a weight average molecular weight of 60,000. In the above (methyl To 100 parts of the propionic acid slurry E, 2 parts of dibenzoylperoxide was added to dissolve it. Thereby, a cast material was obtained as a molding material. The obtained cast material was defoamed under reduced pressure. This The injection molding material has excellent storage stability. In addition, the storage stability is judged as "good" when it has not gelled even after 3 hours at room temperature, and it is judged as "bad" when it gels within 3 hours at room temperature. Then, the mold material is cast by using a mold chamber composed of an elastic pad (a pair of glass plates arranged in a circle opposite to each other at a space (7 mm gap)). That is, the injection mold is injected into the mold chamber. After molding the material, it is heated to 60 ×: to harden it. Furthermore, after the cast material after hardening was released from the mold, it was post-cured (so-called after cure) at 120 ° C for 2 hours to obtain a molded plate. The load deformation temperature (HDT; heat deformation temperature) of the obtained molded plate was measured according to the method of jis 6911, and was 118 ° C. [Example 4 4] In a reactor equipped with a thermometer, a cooler, a nitrogen gas introduction pipe, and a stirrer, 55 parts of methyl methacrylate, 3 parts of methacrylic acid, and 20 parts of styrene were fed, and After 22 parts of N_cyclohexylmaleimide, nitrogen was exchanged in the reactor. Next, while stirring the escape mixture and warming to 90 ° C, 0.1 parts of AIBN and i.o parts of n-dodecyl mercaptan were added to start the polymerization reaction. -99- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21〇χ297mm) Φ — (Please read the notes on the back before filling out this page} Order 438819 A7 B7 V. Description of invention (97 start polymerization reaction After 420 minutes, 'the viscosity of the reaction solution became 3 to 35 poise (25 C)', so the reaction was terminated at this point, and 35 parts of methyl methacrylate was further added to the reaction solution, followed by cooling (quenching). The reaction mixture had a viscosity of 7 poise (25 ° C), a solid concentration of 23.5%, and a weight average molecular weight of 91,000 °. Then, to 100 parts of the obtained reaction mixture, 0.35 parts of maleic anhydride and triethyl ether were added. After 0.02 parts of amine was stirred for 15 minutes, the n-dodecyl mercaptan added to the reaction mixture was treated. The maleic anhydride was added to the n-dodecyl mercaptan system by 1.4 times mole. The triethylamine is added to the added n-dodecyl mercaptan based on the amount of 0.88 moles. Thus, a (meth) propionic acid slurry A is obtained. Next, it is added to the (meth) acrylic acid slurry A 1 〇〇part, 1 part of mixed magnesium oxide, 1 part of pentaenyl succinic acid , Third butyl peroxy · 2 · ethylhexanoate, 4 parts of zinc stearate, and 150 parts of aluminum hydroxide (manufactured by Showa Denko Co., Ltd., 4th and 9th Yusho 彳 HS-320) 'Get the ingredients. Then, apply the ingredients to a certain thickness on the surface of the polyethylene film, and evenly spread the glass fiber on this coating (cut by 1 inch long). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Furthermore, on this, a superimposed coating (which is formed by coating ingredients with a certain thickness on the surface of polyethylene #) is formed. That is, the glass fiber is held by the ingredients. Thereby, SMC is obtained as a molding material. The proportion of the above-mentioned glass fibers in the SMC is 25%. After that, the s μ C obtained by packaging with a glass film is matured at 40 ° C. for one day. Next, the above-mentioned SMC is formed by heating and pressing. Use a mold of a predetermined size to set the upper mold temperature to 120. (:, lower mold temperature setting -100 ---------- Φ II * ► · &quot;-(Please read the (Please fill in this page again)

-In In HI sheet paper size is applicable to Chinese National Standard (CNS) A4 specification (21GX297 公 董 438819 ^ —

5. Description of the invention (98) in 1UTC. Then, the SMC cut into a predetermined size was filled in the above mold, and the mold was clamped at a pressure of 6 MPa, followed by heating and press molding for 7 minutes to form a molded product, that is, a plate having a thickness of 3 mm. At 120. (: The gelation time is 90 seconds. The molded article obtained has a gloss (60. gioss) of 80 in accordance with jis κ 7105, which is good, and is measured in accordance with JIS K71〇3. The yellowness (γι) is 4.08, which is a low coloring property. Furthermore, the molded product does not see the mesh-like floating of 51 fibers on the surface, and the surface has excellent smoothness. In addition, according to JIS A 1415, a weather meter is used. As a result of conducting a weather resistance test for 1,000 hours, no substantial discoloration or pulverization was observed in the molded product. Further, the molded product was placed in a furnace set at 150 ° C for 1 hour to evaluate heat resistance. As a result, the molded product does not show appearance changes such as yellowing, nor does it lose the surface gloss. The above-mentioned SMC is stored at 40. (: It will not harden even after being stored for 2 months. That is, SMC has excellent storage stability. The above main results are summarized in Table 19. [Example 4 5] First, the same reaction and treatment as in Example 4 4 were performed to obtain (meth) acrylic acid slurry A. Next, this (methyl) ) Acrylic acid slurry a, except for using 100 parts of aluminum hydroxide and glass powder (Nitto Textile Co., Ltd. Co., Ltd., FMB 3 0W-00 1) 50 parts of the mixture was used instead of 150 parts of aluminum hydroxide in Example 44, and the rest was the same as that in Example 44 to obtain SMC. The same procedure as in Example 44 was performed. The maturation and molding operations make a molded product, that is, a plate having a thickness of 3 mm. The gelation time in 120: (90). The obtained molded product has a gloss (60. gloss) of 83, which is good. The yellowness (YI) is 3.92, which is low in colorability. Furthermore, the molded product cannot be seen on the surface -101-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ------ ------ Final Γ (Please read the notes on the back before filling out this page), 1T Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4388 1 9 A7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economics B7 5. [Explanation of the Invention] Mesh-like floating caused by glass fibers is excellent in surface smoothness. Furthermore, a 1,000-hour accelerated weathering test was performed, and as a result, no substantial discoloration or powdering was observed in the molded product. Further, , Evaluate the heat resistance by placing the molded product in an oven set at 150 ° C for 1 hour As a result, the molded product did not show appearance changes such as yellowing, and did not lose the surface gloss. The above 8 訄 (:: will not harden even after being stored at 40.0% for 2 months. That is, the SMC is superior Storage stability. The above main results are summarized in Table 19. [Example 4 6] First, the same reaction and treatment as in Example 44 were performed to obtain (meth) acrylic polymer solution A. Secondly, 'here In 100 parts of (meth) propanoic acid slurry a, 1 part of magnesium oxide, 2 parts of pentaenylsuccinic acid, 1 part of tert-butylperoxy · 2-ethylhexanoate, and stearic acid were mixed. 4 parts of zinc and 350 parts of aluminum hydroxide (manufactured by Showa Denko Co., Ltd., / 44, HS_320) were obtained. Then, add glass fiber (1 / 4-inch long shreds) to the ingredients and knead with a double-wrist kneader. Thereby, bMC was obtained as a molding material. The proportion of the glass fiber in the BMC is adjusted to 5%. Thereafter, the obtained BMC was placed in a metal container at 40 ° C. (: Maturation! Day. After maturation, the ingredients, namely BMC, will not harden, and the surface of bmc will not dry. Then, the same molding operation as in Example 44 was performed to form a molded product, that is, a plate with a thickness of 3 mm. The gelation time at 120 ° C is 60 seconds. It is known that the molded product 'gloss (60. gloss) is 85, which is good, and the yellowness (YI) is 2.02', which is low coloring property. , The molded product can not see the mesh-like floating caused by glass fiber on the surface, and the surface is excellent in smoothness. It was also tested for 1,000 hours to promote the weather resistance. Standard (CNS) A4 specification (210X297 mm) ------------ »Production ·· * (Please read the precautions on the back before filling this page)

、 1T 438819 -------V. Description of the invention (100) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Furthermore, the molded article was placed in an oven set at 150 ° C for 1 hour to evaluate the heat resistance. As a result, the molded article showed no change in appearance such as yellow wheat and did not lose the surface gloss. The above-mentioned BMCS will not harden if stored for 2 months at 40t. That is, BMC has superior storage stability. The main results described above are shown in Table 19. [Example 4 7] First, the same reaction, treatment and the like as in Example 4 were performed to obtain (meth) acrylic acid slurry A. Next, 90 parts of this (meth) acrylic acid slurry A was mixed with 0 parts of trimethylolpropane trimethacrylate, 2 parts of magnesium oxide, and 5 parts of pentaenylsuccinic acid. 1 part of _2_ ethylhexanoate, 4 parts of zinc stearate, and 350 parts of aluminum hydroxide (manufactured by Showa Denko Co., Ltd., Yuki Imagine HS-320) were obtained. Using the obtained ingredients, the same operation as in Example IX was performed to obtain BMC. Further, the same molding operation as in the example was performed to form a molded product, that is, a plate having a thickness of 3 mm. The gelation time in 120 ×: was 50 seconds. ^ The obtained molded article had a gloss (60.0%) of 85, which was good, and a yellowness (YI) of 2.12, which was low in colorability. Furthermore, the molded product does not have mesh-like floating caused by glass fibers on the surface, and has excellent surface smoothness. In addition, a 1,000-hour accelerated weathering test was performed, and as a result, no substantial discoloration or powdering was observed during molding. Furthermore, the molded article was placed in a furnace set at 150 t for 1 hour to evaluate the heat resistance. As a result, the molded article showed no change in appearance such as yellowing and did not lose the surface gloss. The above bmc will not harden even if stored for 2 months under 4th generation. That is, BMC has superior storage stability. The main results described above are shown in Table 19. Color glass quality --------- Φ II t W ί (Please read the precautions on the back before filling this page), 11

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 1 438819 A7 _ _B7 V. Description of the Invention (101) [Example 4 8] Except for Example 4, methacrylic acid was not used, and The amount (feed amount) of the methyl ester was changed from 55 parts to 58 parts, and the same reaction and treatment as in Example 44 were performed to obtain a (meth) acrylic acid slurry. The resulting (meth) propionic acid slurry had a dryness of 7 poise (25 ° C), a solid concentration of 22.7%, and a weight average molecular weight of 90,000. Next, 100 parts of this (meth) acrylic acid slurry were mixed with 1 part of tert-butylperoxy-2-ethylhexanoic acid vinegar, 4 parts of stearic acid, and chlorine oxidation hall (manufactured by Showa Denko Corporation) , Yatsuki Kanbu HS-320) 400 parts, to obtain ingredients. Using the obtained ingredients, the same operation as in Example 46 was performed to obtain BMC. The forming operation of Example 44 was performed to form a molded product, that is, a plate having a thickness of 3 mm. The gelation time at 120 ° C was 70 seconds. The obtained molded article 'gloss (60. gloss) was 85, which was good, and yellowness (YI) was 2.12, which was low in colorability. Furthermore, the molded product does not have mesh-like floating caused by glass fibers on the surface, and has excellent surface smoothness. Further, an accelerated weathering test was performed for 10,000 hours. As a result, no substantial discoloration or powdering was observed in the molded article. Furthermore, the molded article was placed in a furnace set at 150 ° C for 1 hour to evaluate the heat resistance. As a result, the molded article showed no change in appearance such as yellowing and did not lose the surface gloss. The above 61 ^ € will not harden if stored for 2 months at 401. That is, BMC has superior storage stability. The above results are shown in Table 19. [Example 4 9] The same reaction as in Example 44 was carried out except for IIN-phenyl melamine-imine (N-cyclohexylmaleimide in y). --- • Ψ Two (Please read the notes on the back before filling this page)

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438819 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 -------- B7_ V. Description of Invention (1〇2)

It is known that (meth) acrylic acid slurry A. The viscosity of the obtained (meth) acrylic acid slurry A was 6 Poise (25 ° C), the solid concentration was 22.8%, and the weight-average molecular weight was 96,000. Next, the same operation as in Example 44 was performed using this (meth) acrylic acid slurry A to obtain SMC. The same maturation and forming operations as in Example 44 were performed to form a molded product, that is, a plate having a thickness of 3 mm. The gelation time at 12 ° C was 98. The molded product obtained had a yellowness (¥ 1) of 21 3 and a yellow color. Although the taste is strong, the gloss (60 ° gloss) is 79, which is good. Furthermore, the mesh-like floating caused by broken glass fibers is not seen on the surface of the molded product, and the surface is excellent in smoothness. Also, it is performed for 1,000 hours As a result of the accelerated weathering test, no substantial discoloration or powdering was observed in the molded product. Furthermore, the molded product was placed in a furnace set at 150 C for 1 hour to evaluate the heat resistance. As a result, the molded product did not show yellow. Changes in appearance, without losing the surface gloss. The above main results are summarized in Table 19. [Example 50] Except using N-isopropylmaleimide (vinyl compound) instead of implementation Except for N-cyclohexylmaleimide in Example 4, the rest was reacted with Example 4 to obtain (meth) acrylic acid slurry A. The viscosity of the obtained (meth) propionic acid slurry eight was 7 卩 〇 丨 86 (25 ° (^), solid concentration is 23.8%, weight average molecular weight is 110 Next, using the (meth) propionic acid slurry A, the same operation as in Example 4 4 was performed to obtain SMC. The aging and forming operations were performed in the same manner as in Example 44 to form a molded product, that is, a thickness of 3 mm. Plate. At 120. (: The gelation time of the medium is 100__ _-105- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) I ------- φ-I 7 Second (Please read the notes on the back before filling this page)

, 1T economy, which is printed by the Consumer Standards Cooperative of the Central Bureau of Standards 438819 A7 1 ^^ — __ B7_______ 5. Description of the invention (103) seconds. The obtained molded product had a gloss (60. gloss) of 80, which was good, and a yellowness (YI) of 5.31, which was low in colorability. Furthermore, the molded product does not have mesh-like floating caused by slope glass fibers on the surface, and has excellent surface smoothness. Further, a 1,000-hour accelerated weathering test was performed, and as a result, no substantial discoloration or powdering was observed in the molded product. Furthermore, when the molded article was placed in a furnace set at 50 c for 1 hour to evaluate the heat resistance, as a result, the molded article showed no change in appearance such as yellowing and did not lose the surface gloss. The main results mentioned above are summarized in Table 19. [Comparative Example 2 6] Except that sf-cyclohexylmaleimide was not used in Example 44, and the amount of methyl methacrylate (feed amount) was changed from 55 to 77 parts, The rest was the same as the reaction and treatment of Example 44 to obtain a (meth) acrylic acid slurry. The viscosity of the obtained (meth) acrylic acid slurry was 7 poise (25X :), the solids concentration was 23.9%, and the weight average molecular weight was 98,000. Next, using this (meth) acrylic acid slurry, the same operation as in Example 44 was performed to obtain a comparative SMC. In addition, the same maturation and molding operation as in Example 44 was performed to prepare a comparative molded product, that is, a plate having a thickness of 3 mm. Gelation time at 120 ° C is 130 seconds. The obtained comparative molded article had a gloss (60. gloss) of 18, which was not good. Furthermore, when comparing molded articles, it was found that the mesh-like floating caused by the glass fibers had poor surface smoothness. Also, the comparative molded product was placed in a furnace set at 150 ° C for 1 hour, and the heat resistance was evaluated. As a result, the molded product was observed to have appearance changes such as yellowing. __ _-106 -__ This paper Standards are applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) --------- 4— 丨: (Please read the precautions on the back before filling this page) Order 438819 V. Description of the invention (1 〇4) Also, the surface also loses its luster, which produces a good anti-king mark. The above persons are shown in Table 19. Wang f ... Fruits printed by the Central Standards Bureau of the Ministry of Economic Affairs

It is clear from Table 19 that the molding materials of Examples 44 to 50 are suitable for press molding and can be hardened in a relatively short time. In addition, various physical properties such as agricultural properties, storage stability, and the like are obtained by pressing to form the material. -107 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ------------ t 2 (Please read the precautions on the back before filling this page)-Order

• I-I--I Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4388 1 9 A7 B7 V. Description of the invention (105) [Example 5 1] It is equipped with a thermometer, a cooler, a nitrogen introduction pipe, and a mixer Into the reactor, 98 parts of methyl methacrylate and 2 parts of methacrylic acid were fed, and then the reactor was replaced with nitrogen. Next, while the above mixture was stirred and heated to 80 ° C, 0.01 parts of AIBN and 0.3 parts of n-dodecyl mercaptan were added to start the polymerization reaction. Five hours after the start of the polymerization reaction, the viscosity of the reaction solution became 100 to 110 poise (25 ° C). Therefore, the reaction was stopped at this point. After adding hydroquinone to the reaction solution, it was cooled. The hydrogen S Kun system was added at 50 ppm based on the weight of the reaction solution. Next, to 100 parts of the obtained reaction mixture, 0.1 part of maleic acid liver and 0.005 part of triethylamine were added, and then stirred for 15 minutes to treat the n-dodecyl mercaptan remaining in the reaction mixture. Thereby, the (meth) propionic acid slurry A of this invention is obtained. This (meth) acrylic acid slurry A had a solid concentration of 40.5% and a weight average molecular weight of 101,000. Next, in 90 parts of this (meth) acrylic acid slurry A, 10 parts of methyl tripropane trimethacrylate, 0.5 parts of magnesium oxide, 1 part of pentadecylsuccinic acid, and 3 parts of butyl peroxy 1 part of 2-ethylhexanoate, 4 parts of stearyl carboxyzinc, and 350 parts of aluminum hydroxide (manufactured by Showa Denko Co., Ltd. 4 Hs 310) were obtained to obtain ingredients. Then, glass fiber (shreds with a length of 6 mm) was added to the ingredients, and kneaded with a double-wrist kneader for 30 minutes. Thereby, a block-shaped molding material is obtained. The glass-breaking fiber ratio in the molding material was adjusted to 9%. Thereafter, the obtained molding material was placed in a closed volume, and matured at 40 ° C for 1 day. After maturation, the surface of the forming sealant is not dry, and the handleability is good. -108- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297mm) --------- ΦII *. ‘Second (Please read the precautions on the back before filling this page)

1T 438819 A7 B7 V. Description of the Invention (106) The employee of the Central Government Bureau of the Ministry of Economic Affairs, the Consumer Cooperative, printed it / person, and compression-molded the above-mentioned forming materials. That is, a box-shaped forming mold having an outer size of 38 cm X 28 cm x 9 cm height is used, and the upper mold temperature is set to 125 ° C, and the lower mold temperature is set to 丨 ⑺ ^. Then, 2,200 g of the above-mentioned molding material was filled in the mold, and the mold was clamped at a pressure of 6 MPa, and compression-molded for 7 minutes to form a box-shaped molded product having a thickness of 7 mm. The obtained molded article had a linear shrinkage of 0.25%, and was able to be smoothly demolded, and cracks, cracks, warpage, and deformation were not observed, and the moldability was good. In addition, the gloss (60. gloss) of the bottom surface of the molded article was 80, and the gloss (60. gloss) of the side surface of the box was 75, which was good. Furthermore, no unevenness is seen on the surface of the molded product, and the surface is excellent in smoothness. The strength of the molded product was measured in accordance with jIS K 6911. As a result, the flexural strength was 88 MPa and the flexural modulus was 12.5 GPa. [Example 5 2] Except using 0.02 parts of AIBN and 02 parts of n-dodecyl mercaptan to replace 0.01 parts of AIBN in Example 51 and 03 parts of n-dodecyl mercaptan, the rest were the same as the above implementation By the method of Example 51, the (meth) propionic acid slurry A of the present invention was obtained. This (meth) acrylic acid slurry A had a solid concentration of 41 5% and a weight average molecular weight of 108,000. Hereinafter, the same procedure as in Example 51 was performed to obtain a block-shaped molding material. Thereafter, the obtained molding material was placed in a closed container and matured at 40 ×: for 1 day. After ripening, the molding material has no surface grains and is easy to handle. Next, the above-mentioned molding material was compressed and shaped in the same manner as in Example 51 to obtain a box-shaped molded product. The obtained box-shaped molded article had a linear shrinkage of 0,171 and good moldability. The gloss of the obtained box-shaped molded product is the same as -109- China National Standard (CNS) A4 specification (2τ ^^ Ι 1ιϋ ^ 11 In i— m ——- I nn emmmMMt I · — n 1 **-(Please read the notes on the back before filling this page)

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-K Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4388 19 A7 B7_____ V. Description of the invention (107) After the measurement as in Example 51, the gloss (60 ° gloss) of the flat surface of the box is 79, and the gloss of the side of the box (60 ° gloss) is 73, which is good. Furthermore, no unevenness is seen on the surface of the box-shaped molded product, and the surface of the box-shaped molded product is excellent in smoothness. The strength of the obtained box-shaped molded article was measured in accordance with JIS K 6911, and the flexural strength was 70 MPa and the flexural modulus was 11.9 GPa. [Comparative Example 27] Into a reactor equipped with a thermometer, a cooler, a nitrogen introduction pipe, and a stirrer, 98 parts of methyl methacrylate and 2 parts of methacrylic acid were fed, and then nitrogen substitution was performed in the reactor. Next, after raising the temperature of the mixture to 80 ° C, the polymerization reaction was started by adding 0.02 parts of AIBN and 0.2 parts of n-dodecyl mercaptan. Five hours after the start of the polymerization reaction, the viscosity of the reaction solution became 100 to 110 poise (25 ° C). Therefore, the reaction was stopped at this point. After adding hydroquinone to the reaction solution, it was cooled. Hydroquinone was added at 50 ppm based on the weight of the reaction solution. Then, using the obtained reaction mixture, the same operation as in Example 51 was performed to obtain ingredients. Then, glass fiber (6 mm long shreds) was added to the ingredient, and the mixture was kneaded with a double-wrist kneader for 30 minutes. Thereby, a comparative molding material in the form of a block was obtained. The ratio of the glass fiber in the comparative molding material was adjusted to 20%. Thereafter, the same maturation and compression molding as in Example 51 were performed to prepare a box-shaped molded article for comparison. The obtained comparative molded product had a gloss (60. gloss) on the bottom surface of the box of 65 and a gloss (60 ° gloss) on the side of the box of 63, which was not good. Furthermore, unevenness was observed on the entire surface of the molded product, and the surface was smooth and uneven. The strength of the molded product was measured to be 101 MPa, and the flexural modulus was 14.5 GPa. __ -110- This paper size applies to Chinese National Standard (CNS) A4 (210X297mm) ----------— 1 0 ^ (Please read the precautions on the back before filling this page) Order 438819 Printed by A7 _____B7 Wumingming (108) &quot; ^ [Example 5 3] Except in Example 51, the ratio of adding 3 mm long glass fiber to the molding material is: 9%, except that the glass fiber of Table 6 mm was replaced, and the rest were the same as the reaction and operation of Example 51 to obtain a molding material. Thereafter, a box-shaped molded article was prepared by aging and compression molding as in Example 51. The obtained molded product had a linear shrinkage of 0.27%, and could be smoothly demolded without cracking, cracking, warping, deformation, and good formability. And shaping. The gloss (60. gloss) at the bottom of the box was 83, and the gloss (60. gloss) at the side of the box was 78, which was good. Furthermore, no unevenness is seen on the surface of the molded product, and the surface is excellent in smoothness. When the strength of the molded article was measured, the flexural strength was 8 9 MPa and the flexural modulus was 12.9 GPa. [Example 5 4] First, the same reaction and treatment as in Example 51 were performed to obtain ingredients. Then, 5 parts of glass fiber (cutting wire with a length of 6 mm) and commercially available polymethylpropionate (weight average molecular weight 9,000) were added to the ingredients, and Knead with a double wrist kneader for 30 minutes. Thereby, a massive shaped material was obtained. The ratio of the glass fiber in the molding material was adjusted to 9%. Thereafter, it was used for maturation and compression molding in Example 51 to produce a box-shaped molded article. The obtained molded article had a linear shrinkage of 1.7%, and was able to be smoothly released from the mold, and cracks, cracks, warpage, and deformation were not observed, and the moldability was good. The gloss (60. gl0ss) of the bottom surface of the molded product was 84, and the gloss (60. g10ss) m of the side surface of the box was good. 1 two, the m of the shame product does not show any indentation, and the surface is smooth. The strength of the molded product was measured. As a result, the bending strength was 8 3 _________ -111-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Φ II t It (Please read the precautions on the back before filling this page ) Order 438819 A7 _____B7 5. Description of the invention (109) MPa, flexural modulus is 12.5 GPa. [Example 5 5] Except using 15 parts of a commercially available polystyrene (weight average molecular weight 18,000) as a low shrinkage agent as the polymethyl methacrylate in Example 54 The rest is the same as the reaction, operation, etc. of Example 51 to obtain a molding material. Thereafter, the same maturation and compression molding as in Example 51 were performed to produce a box-shaped molded product. The obtained molded product had a linear shrinkage ratio of 8%, and could be smoothly demolded without cracking, cracking, warping, deformation, and good formability. The gloss (60. gloss) of the bottom surface of the molded product was 85, and the gloss (60. gloss) of the side surface of the box was 84, which was good. Furthermore, no unevenness is seen on the surface of the molded product, and the surface is excellent in smoothness. When the strength of the molded article was measured, the flexural strength was 86 MPa and the flexural modulus was 12.7 GPa. As is clear from Examples 5 to 5 5 and Comparative Example 27, the molding material of this example has a low linear shrinkage and good moldability. In addition, it was found that the molded article obtained by molding this molding material is excellent in gloss and surface smoothness. Furthermore, although the molding material of this example is slightly lower in strength than the molding material of the comparative example, it has practically sufficient strength. [Example 5 6] After feeding 188 parts of methyl methacrylate and 12 parts of methacrylic acid in a reactor equipped with a thermometer, a cooler, a nitrogen introduction pipe, and a stirrer, nitrogen substitution was performed in the reactor. . Next, while stirring the mixture, the mixture was raised, and then MBN 0- · MM was added to start the polymerization reaction. __ _-112- This paper size applies to China National Standard (CNS) Α4 size (210X tear mm) I-. —0-- I II (Please read the notes on the back before filling this page) Set the central standard of the Ministry of Economic Affairs Printed by the Bureau I Consumer Cooperative 438819 A7 B7 V. Description of the invention (110) 5.5 hours after the start of the polymerization reaction, the viscosity of the reaction solution became 30 ~ 35 poise (25 ° C), so the reaction was stopped at this point and further After 35 parts of methyl methacrylate was added, it was cooled to 40 ° C (quick cooling). Then, after adding isobutyl acetamyl ether to the above reaction mixture, the temperature was raised to 100 ° C and stirred for 30 minutes to treat the n-dodecyl mercaptan remaining in the reaction mixture. The isobutyl vinyl ether is added at 2.0 times mole relative to the n-dodecyl mercaptan added during polymerization. Subsequently, 8.4 parts of glycidyl methacrylate, 0.2 parts of triphenylphosphine, and 0.05 parts of hydroquinone were added to 1000 parts of the reaction mixture (methacrylic acid slurry C) after the treatment. Stir down for 10 hours at C to perform the vinegar reaction. The obtained (meth) acrylic acid slurry C1 had a solid concentration of 31%, a viscosity of U.0 poise, and a weight average molecular weight of 115,000,000. The number of double bonds per molecule of the (meth) acrylic polymer in the (meth) acrylic acid slurry c was measured in the same manner as in Example 13. As a result, the number of double bonds per molecule was twelve. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Secondly, in this (meth) acrylic acid slurry c, 80 parts, as a thermoplastic polymer (thermoplastic elasticity) 20 parts of acetophenone / ethylene / propylene copolymers (manufactured by Co., Ltd., July 7th &gt; 2005, styrene content 20%) 20 'using a South-speed mixer (manufactured by Special Machine Chemical Co., Ltd., homogeneous) Mixer) while stirring at 10,000 rpm for 10 minutes. The obtained dispersion (molding material) was opaque. The particle size distribution of the dispersed phase was measured using a particle size measuring device (Paeific Scientific, see Sona 370), and it was 50 to 100 m. In the above-mentioned dispersion liquid, as a hardener, Bu Shuang (third hexylperoxy) -3,3,5-dimethylcyclohexyl pit (manufactured by Nippon Oil & Fats Co., Ltd., Bayi ~ Fengchuang-113- Paper size applies Chinese National Standard (CNS) A4 specification (210x297 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Public Economics 4 3 8 8 19 A7 _ B7 V. Description of the invention (111) TMH, 10-hour half-life temperature 86.7 ° C) 1 part, 67 parts of magnesium oxide i, and 100 parts of oxynitride (manufactured by Showa Denko Corporation, v, 4 ^ today's HS-320), to obtain ingredients. Thereafter, the obtained ingredients were matured at 40X: 1. Put the thickened ingredients into a cylinder heated to 120 ° C in diameter 丨. 3 mm, and cover the front end of the cylinder to prevent the ingredients from leaking out. Then, make the front end of the cylinder a lower side to The cymbal was inserted, and a pressure of 20 kgf / cm2 was applied to the inside of the cylinder with the cymbal to harden the ingredients. The hardened product obtained had a volume shrinkage of 3.0%. Moreover, the hardened material was not visible on its surface. Pinhole or uneven gloss sentence 'Excellent surface smoothness. Cut the hardened material into two pieces and use a scanning electronic display After observing its cross-section through a microscope, many holes of about 30 micron can be seen in the center of the hardened material. Then, the above-mentioned ingredients before thickening were applied to a polyethylene film with a certain thickness, and then evenly spread on the coating. Glass fiber (reinforced cut bundle) as a reinforcing material. Furthermore, a coating material (which is formed by coating ingredients at a thickness of one layer on the surface of a polyethylene film) is superimposed thereon. The glass fiber is held. In this way, an SMC is obtained as a molding material. The proportion of the glass fiber in the SMC is adjusted to 25%. Thereafter, the obtained SMC is packaged in a cellophane film and matured at 40 ° C to 1 Next, the SMC is heated and press-molded. That is, using a mold having a size of 300 mm &lt; 300 mm, the mold temperature on the upper side is set to 11.0, and the mold temperature on the lower side is set to 100X: In addition, the SMC cut into a size of 150 mm x 150 mm was filled in the above mold, and the mold was clamped at a pressure of 6 MPa, heated and pressurized for ^^ 0 minutes to make a ▲ product, which is 3 thick! No pinholes or light can be seen on the front and back Uneven, with ------- 114- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) --------- Φ II te-(Please read the back Please fill in this page for the matters needing attention) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 438819 A7 B7 _ V. Description of the invention (112) Has a good surface. [Example 5 7] It is equipped with a thermometer, a cooler, and nitrogen introduction After feeding 188 parts of methyl methacrylate and 12 parts of methacrylic acid into the reactor of the tube and the stirrer, nitrogen replacement was performed in the reactor. Secondly, while the temperature of the above mixture was disturbed while raising the temperature to 85 ° C, 0.006 parts of AIBN and 0.3 part of n-dodecyl mercaptan were added to start the polymerization reaction. 5.5 hours after the start of the polymerization reaction, the viscosity of the reaction solution became 30 to 35 poise (25 ° C), so the reaction was stopped at this point. After adding 35 parts of methyl methacrylate to the reaction solution, it was cooled to 40 ° C. (Chilling). Then, 8.4 parts of glycidyl methacrylate, 0.2 parts of zinc octoate, and 0.05 parts of hydroquinone were added to 100 parts of the obtained reaction mixture, and then stirred at 100 ° C for 10 hours to perform an esterification reaction. The obtained (meth) acrylic acid slurry E had a solid concentration of 30%, a viscosity of 10.5 poise, and a weight average molecular weight of 110,000. The number of double bonds per molecule of the (meth) acrylic polymer in the (meth) acrylic acid slurry E was measured in the same manner as in Example 13. As a result, the number of double bonds per molecule was twelve. Next, using this (meth) acrylic acid slurry E, the same operation as in Example 56 was performed to obtain a dispersion. The obtained dispersion was opaque, and after measuring the particle size distribution of the dispersed phase, it was 50 nm to 100 &quot; m. Further, using the above dispersion liquid, the same operation as in Example 56 was carried out to obtain ingredients. After that, the obtained ingredients are matured at 4 ° C to 1 day. The dried ingredients are hardened in the same manner as in Example 56. The obtained __ -115- This paper size applies Chinese national standards A4 Specification (21〇χ297 公 董-— ~ 'I .----------, Μ (Please read the notes on the back before filling this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4388 19 A7 __— _ B7 —_ _ V. Description of the invention (113) The hardened product has a volume shrinkage of 3.0%. Moreover, the hardened product does not show pinholes or uneven gloss on the surface, and the surface The smoothness is excellent. After the hardened material is divided into two and the cross section is observed with a scanning electron microscope, many holes of about 30 micron can be seen in the center of the hardened material. Then, the ingredients before the thickening are presented After coating with a certain thickness on the polyethylene film, the glass fiber (a 1-inch length bundle) as a reinforcing material is evenly spread on this coating. Furthermore, a coating is superposed on it (the ingredients are formed to a certain thickness) It is constituted by coating on the surface of a polyethylene film). That is, the glass fiber is held by the ingredients. An iSMC was obtained as a molding material. The proportion of the above-mentioned glass fibers in the SMC was adjusted to 25%. Thereafter, the obtained SMC was packaged in a cellophane film and matured at 40 ° C. for one day. Next, the SMC was heated. Press molding. That is, using a 300 mm X 300 mm mold, set the upper mold temperature to U0 ° C and the lower mold temperature to 100 ° C. Also, cut into 150 mm X 150 The SMC with a size of mm is filled in the above mold, and the mold is clamped at a pressure of 6 MPa, and heated and pressed for 10 minutes to form a molded product, that is, a molded plate with a thickness of 3 mm. The obtained molded plate has no pinholes on the surface and the back. Or uneven gloss, and good surface properties. [Example 5 8] In the same reactor as described in Example 1, 200 parts of methyl methacrylate was fed, and then the reactor was replaced with nitrogen. Second, While stirring the above methyl methacrylate, the temperature was raised to 80 ° C, and then 0.1 parts of AIBN and 1.0 parts of n-dodecyl reverse rattan were added to start the polymerization reaction. After the polymerization reaction, the viscosity of the reaction solution became 30 to 35 poise (25t). Point in time, stop the reaction, the reaction _ -116 -This paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) ------------ c I (Please read the notes on the back before filling this page) Order 4 3 88 1 9 Member of the Central Standards Bureau of the Ministry of Economic Affairs; printed by the Consumer Cooperative A7 B7 5. Description of the invention (114) After adding 35 parts of methyl methacrylate, cool (quench) to 4 (^). Then, in the obtained reaction mixture After isobutyl vinyl ether was added, the temperature was raised to 1000 c and stirred for 30 minutes, and the n-dodecyl mercaptan added to the reaction mixture was treated. The isobutyl vinyl ether is added 20 times moles to the n-dodecyl mercaptan added during polymerization. Then, 5 parts of methacrylic acid was added to 95 parts of the reaction mixture after the above-mentioned treatment to obtain (meth) acrylic acid slurry D of the present invention. Next, 1 part of the (meth) acrylic acid slurry D 100 was mixed with 1 part of bis (4-tert-butylcyclohexyl) peroxydicarbonate and aluminum hydroxide (manufactured by Showa Denko Corporation, / (44, H-320 ST) After 200 parts, this mixture was kneaded and defoamed. In this way, a molding material is obtained as a molding material. This injection molding material, that is, the ingredients, has excellent storage stability. Secondly, the obtained injection molding material is injection-molded using a glass mold chamber. That is, after the injection molding material is injected into the mold cavity, it is at 60. Hardened at 〇 for 1 hour. In addition, after demolding, it is post-cured at 10 ° C for 2 hours to obtain a molded article, which is an artificial marble plate. The obtained marble plate has a surface with gloss, excellent smoothness, and has a so-called high-quality and texture. Also, The artificial marble board is insoluble in TJJF &amp; acetone, and has good solvent resistance. Furthermore, the artificial marble board has excellent heat resistance, weather resistance, and water resistance. The above-mentioned main reaction conditions and results are summarized in Table 20. [Example 59] After taking the heart load of Example 1 (True &quot; into the container, and then passing 200 parts of Ping ~ Mezinate), the reactor was replaced with nitrogen. Secondly, the above was stirred -117- This paper size is suitable for China National Standard (CNS) A4 Specification (210X297mm) J · ^ II I 1 (Please read the notes on the back before filling out this page) Order 4 3 88 1 9 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (115) After the temperature of methyl methacrylate is raised to 80 ° C, 0.1 part of AIBN and 1.0 part of n-dodecanethiol are added to start the polymerization reaction. After the polymerization reaction is started, the viscosity of the reaction solution becomes 30 to 35 poise (25 ° C) The reaction was terminated, and 25 parts of methyl methacrylate and 10 parts of methacrylic acid were further added to the reaction solution, and then cooled to 40 ° C. Then, isobutyl vinyl was added to the obtained reaction mixture. After the ether, the temperature was raised to 100 C and stirred; after 30 minutes, the n-dodecyl mercaptan added to the reaction mixture was treated. The above isobutyl vinyl ether was compared with the n-dodecyl added during polymerization. By adding 2.0 times moles of thiol, the (meth) acrylic acid slurry D of the present invention can be obtained. Then, using (meth) acrylic acid slurry D, the same operations, forming, and the like as in Example 10 are performed to make artificial Marble board. In addition, the injection molding material, that is, the ingredients, has excellent storage stability. The obtained marble board has a surface with gloss and smoothness, and has the so-called high-quality and texture. Also, the artificial marble board is insoluble in THf And acetone, the solvent resistance is good. Furthermore, the artificial marble board has excellent heat resistance, weather resistance and water resistance. The above main reaction conditions and results are summarized in Table 20. [Example 6 0] Same as in Example 1 After loading 200 parts of methyl methacrylate into the reactor, nitrogen was substituted in the reactor. Secondly, while stirring the above methacrylic acid methyl ester to 80 ° C, ABN 0.1 was added. Part and n-dodecyl alcohol to start the polymerization reaction. After the polymerization reaction started, when the viscosity of the reaction solution became 30 to 35 pise (25 ° C), the reaction was terminated. The scale is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) I ------- 41— (Please read the note on the back Ϋ-item before filling out this page) Order 438819 A7 _______B7_ V. Description of the invention (116 ) After adding 35 parts of methyl methacrylate to the reaction solution, it was cooled to 40 t. Then, in the obtained reaction mixture, after adding isobutyl vinyl ether, the temperature was raised to 1000 ° C and stirred for 30 minutes, and the n-dodecyl mercaptan added to the reaction mixture was processed. The isobutyl vinyl ether was added at 2.0 mol times to the n-dodecyl mercaptan added during the polymerization to obtain (meth) acrylic acid slurry C. Next, after adding 5 parts of methacrylic acid to 95 parts of this (meth) acrylic acid slurry C, the same operations as in Example 1 and forming were performed to prepare an artificial marble slab. In addition, the injection molding material using the above-mentioned (meth) acrylic acid slurry C, that is, the formulation system has excellent storage stability. The surface of the obtained marble slab has gloss and smoothness, and at the same time has a so-called high-quality and texture. In addition, artificial marble slabs are insoluble in THF and acetone and have good solvent resistance. Furthermore, the artificial marble slab has excellent heat resistance, weather resistance, and water resistance. The main reaction conditions and results are summarized in Table 20. (Please read the notes on the back before filling this page) Member of the Central Standards Bureau of the Ministry of Economic Affairs 1 Printed by Consumer Cooperatives 20 Example 58 5 9 60 Aluminium hydroxide (parts) 200 200 200 The formed material after curing is good good good solvent resistance THF insoluble, insoluble, insoluble, acetone, insoluble, insoluble, insoluble, heat resistant, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good in water resistance. 19 V. Description of the Invention (117)

It is clear from Table 20 that the method of this embodiment can be used to produce stable and stable materials when used as a molding material. L Propylene bismuth slurry C and (meth) acrylic acid slurry D. In addition, the molding materials of this (8) to 60 are suitable for Lijiao's “Examples and excellent pressure molding”. The molding W obtained is excellent (heat resistance, solvent resistance, weather resistance, and other physical properties. 'In the implementation of the present invention, there is a lack of implementation, and the specific implementation ideas or embodiments are basically used to clearly disclose the technical content of the present invention, and should not be limited to this. Specific examples are explained in a narrow sense. In the spirit of the present invention and the following description, please make various changes and implement it within the scope of the patent. Industrial application possibilities The present invention (manufacturing method can be compared with the conventional one) (Meth) acrylic acid polymer solution with excellent storage stability when used as a molding material can be produced in a shorter time. In addition, a (meth) acrylic acid solution with excellent storage stability when used as a molding material can be provided. Furthermore, We can provide a molding material that can be hardened in a shorter time than conventionally known, and that it can obtain molded products with excellent physical properties such as heat resistance, solvent resistance, weather resistance, and water resistance. The molding material of the present invention is formed by molding Molded products, Examples include: so-called lighting covers, benches, tables, troughs, bulletin boards, waterproof boards, etc. used outside the house, constituting materials such as purification tanks, cars, trains, ships, etc. Suitable materials: artificial marble suitable for bathtubs, Weifang fluid counters (kitchen ceiling), various counter tops, vanity tops, etc .; electrical appliances, etc., but there are no special restrictions. The moldings are good-looking and suitable for all kinds of aesthetics. Use. In addition, the molding material containing fillers is molded ^^^ Marble is used to remove the ginger floor—the elephant ^ is used as artificial marble. -120 This paper is suitable for Guancai County (CNS) A4 size (21GX297).

Claims (1)

Patent application scope 438819 No. 85112105 patent_read case-a patent application scope amendment ~ 1 · A method of manufacturing (meth) acrylic acid slurry, which contains (meth) acrylic acid (please read the note on the back first) Please fill in this page again.) The monomer component of sour vinegar, and the vinyl monomer containing carboxyl group is 0.5 to 20% by weight based on the total amount of the monomer component and the vinyl monomer. After the polymerization is performed in the presence, the reaction mixture is treated with anhydrous maleic acid and a basic compound. 2. A method for producing a (meth) acrylic acid slurry, wherein 100% by weight of a monomer component containing (meth) acrylic acid vinegar and 100% by weight of the monomer component and the ethyl ethyl monomer-based monomer are 0.5 ~ 20% by weight of a carboxyl group-containing vinyl monomer 'is polymerized in the presence of a thiol compound, and then an ethynyl ether compound and / or a vinyl sulfide compound is added to the reaction mixture. 3 · —A method for producing (meth) acrylic acid syrup, using a monomer component containing (meth) acrylic acid ► vinegar and 100% by weight relative to the total amount of the monomer component and the vinyl monomer 0.5 to 20% by weight of a carboxyl group-containing vinyl monomer ′ is polymerized in the presence of a thiol compound, and then the carboxyl group in the reaction mixture is treated with glycidyl (meth) acrylate and / or (methyl ) Esterification of methyl glycidyl acrylate and treatment of the thiol compound remaining in the reaction mixture. 4 · A method for producing (meth) acrylic acid slurry, which contains monomer components printed with sour vinegar by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics (Meth) Propylene The total amount of monomers is 100% by weight, 0.5 to 20% by weight, a reaction mixture obtained by polymerizing a carboxyl-containing vinyl monomer in the presence of a thiol compound, and an unsaturated epoxy compound. The reaction is carried out in the presence of a box compound containing at least one element selected from the group consisting of zinc, tin and zirconium. 5 · If any one of (1) to (4) in the scope of the patent application, the size of the (meth) acrylic acid liquid is applicable to the Chinese National Standard (CNS) A4 specification (21ΌX 297 mm) 4388 1 9 A8 B8 C8 D8 The scope of the patent application is the manufacturing method printed by the staff consumer cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, and φ »acr _, 〃 T. The above-mentioned early body composition further contains N-substituted maleimide. 6. As described in Shen Qiao Patent | The manufacturing method of the (meth) propionic acid polymer solution of item 5, wherein the N-substituted maleimide is ν_cyclohexylmaleimide. The bis (meth) acrylic acid slurry 'is obtained by the production method described in any one of claims 1 to 4 of the scope of patent application. 8. An f-shaped material containing a (meth) acrylic liquid as described in item 7 of the scope of the patent application. 9. For the forming material under the scope of patent application No. 8, in which the step further contains a filler. 10. For example, the patent application scope No. 10 of Cheng Ganzhan β, II, Xinzhantong materials, where the filling agent is relative to (meth) propionic acid slurry 100 weight ^ Wangli 1 knife 410 ~ 600 weight price 々Ming Wai included. Dry 11. For example, the molding material in the scope of patent application No. 8 contains vinyl monomers containing carboxyl groups. 12. Forming materials such as tackifier and succinic acid derivative in the scope of patent application item 8. 11 Reinforcement materials such as the forming material in the scope of patent application No. 8. 14. If the content of the molding material in item 13 of the scope of patent application is 9% by weight or less. 15. If the length of the forming material in the scope of patent application item 13 is 6 mm or less. 16. If the Forming Material Section of the scope of patent application No. 8 further contains more of which further contains which further contains the above-mentioned reinforcing materials, among which the above-mentioned reinforcing materials further contains heavy (please read the precautions on the back before filling in (This page), 1T i · ----- I -2- This paper size applies Chinese National Standard (CNS) A4 specification (2l0X297 &gt; ^ y 1---II · -I 438819 A8 Βδ C8 D8 Patent application The amount of the thermoplastic polymer having a range-average molecular weight of less than 20,000, such as polymethyl methacrylate, phenyl ethyl sulfonate, and the like, does not include thermoplastic polymers containing several groups. ) 100 parts by weight of the propionic acid slurry is 5 to 50 parts by weight. 17. The molding material according to item 8 of the scope of patent application, which further contains a material selected from the group consisting of thermoplastic elastomers, thermoplastic resins, and rubbers. Soil thermoplastic polymer, which is dispersed in (meth) acrylic acid slurry. As for the molding material of the 17th patent scope, the thermoplastic polymer is phenethyl Based thermoplastic elastomer - (Please read the Notes on the back to fill out this page), 1T -JAW Ministry of Economic Affairs Bureau of Standards X workers consumer cooperatives printed 3-