JPH11106411A - Thermoplastic molding resin composition and method for producing thermoplastic resin molded article - Google Patents

Abstract

(57) Abstract: A resin composition for thermoplastic molding, which has a good surface property and can easily obtain a molded article having a desired shape by a simple extrusion molding process, and a thermosetting resin composition. Provided is a method for producing a plastic resin molded article. SOLUTION: This is a thermoplastic molding resin composition containing a thermoplastic resin, a filler, an α, β unsaturated carboxylic acid monomer and a polymerization initiator, preferably 100 parts by weight of an acrylic resin powder as the thermoplastic resin. A thermoplastic molding resin composition containing 50 to 800 parts by weight of an inorganic filler as the filler, 5 to 40 parts by weight of a monomer having a boiling point of 102 ° C. or more as the monomer, and a polymerization initiator; and the resin for thermoplastic molding. When the composition is extruded, the composition is extruded so that the residual amount of the α, β unsaturated carboxylic acid monomer in the extruded product is 20% by weight or less of the added amount of the α, β unsaturated carboxylic acid monomer. Manufacturing method of thermoplastic resin molded body 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for thermoplastic molding used for obtaining a thermoplastic resin molded article by extrusion molding and a method for producing the resin molded article. In addition, the present invention relates to a thermoplastic molding resin composition and a method for producing a thermoplastic resin molded article that can obtain a molded article suitable as artificial marble, which is suitable for use in a vanity table, a sink top, a bathtub, and the like.

[0002]

2. Description of the Related Art Conventionally, an acrylic resin powder excellent in various properties such as transparency, hardness, weather resistance and heat resistance is used as a matrix, and aluminum hydroxide, magnesium hydroxide, carbonate calcium,
A material obtained by uniformly dispersing one or more kinds of silica or the like is called artificial marble, and is used for various purposes.

[0003] As a method for producing the above-mentioned artificial marble, a method of cast molding using an acrylic polymerizable syrup is generally used. However, in the casting method, there is a problem that the production has to be performed in a batch system, the productivity is not sufficient, and the cost of the molded body is high.

Therefore, Japanese Patent Application Laid-Open No. 59-91109 discloses a polymerizable syrup containing methacrylate as a main component,
An inorganic filler, a thermosetting catalyst as a catalyst for polymerizing the syrup, and a method comprising extruding and shaping a composition containing a lubricant, and polymerizing and curing the polymerizable syrup by heating are disclosed. I have. According to this method, since a molded body is obtained by extrusion molding, it is said that productivity can be increased as compared with the casting method.

However, in this method, since the composition containing the acrylic polymerizable syrup is shaped by an extruder and then polymerized and cured by heating, it is shaped by an extruder.
At the time of curing, there is a problem that it is difficult to cure while maintaining the formed shape. In addition, there is also a problem that the surface properties of the molded article are reduced due to curing shrinkage.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic molding which has a good surface property and can easily obtain a molded article having a desired shape by a simple extrusion molding process. It is an object of the present invention to provide a resin composition for use and a method for producing a thermoplastic resin molded article.

[0007]

Means for Solving the Problems The invention according to claim 1 (hereinafter referred to as the present invention 1) comprises a thermoplastic resin, a filler and α, β.
A thermoplastic molding resin composition comprising an unsaturated carboxylic acid monomer and a polymerization initiator. Also,
The invention described in claim 2 (hereinafter referred to as “invention 2”) is based on claim 1
A thermoplastic molding resin composition characterized by further adding a lubricant to the thermoplastic molding resin composition described in 1).

The invention according to claim 3 (hereinafter referred to as invention 3) is characterized in that the thermoplastic resin is 100 parts by weight of an acrylic resin powder, and the filler is an inorganic filler 50 to 8.
2. The composition according to claim 1, further comprising: 00 parts by weight, 5 to 40 parts by weight of the α, β unsaturated carboxylic acid monomer having a boiling point of 102 ° C. or more as the α, β unsaturated carboxylic acid monomer and a polymerization initiator. It is a resin composition for thermoplastic molding of the description. The invention according to claim 4 (hereinafter, the present invention 4)
Is a thermoplastic molding resin composition characterized by further adding 1 to 40 parts by weight of a lubricant to the thermoplastic molding resin composition according to claim 3. The invention according to claim 5 (hereinafter, the present invention 5) is a method for producing a thermoplastic resin molded article using the thermoplastic molding resin composition according to claim 1, wherein When extruding the resin composition for molding, the residual amount of the α, β unsaturated carboxylic acid monomer in the extruded product is adjusted to be 20% by weight or less of the added amount of the α, β unsaturated carboxylic acid monomer. This is a method for producing a thermoplastic resin molded article, which is characterized by extrusion molding.

Further, the invention according to claim 6 (hereinafter referred to as the present invention 6) is a method for producing a thermoplastic resin molded article using the thermoplastic molding resin composition according to claim 2,
Upon extrusion molding the thermoplastic molding resin composition,
A thermoplastic resin, which is extruded so that the residual amount of the α, β unsaturated carboxylic acid monomer in the extruded product is 20% by weight or less of the added amount of the α, β unsaturated carboxylic acid monomer. This is a method for producing a molded article.

[0010] An invention according to claim 7 (hereinafter referred to as the present invention 7) is a method for producing a thermoplastic resin molded article using the thermoplastic molding resin composition according to claim 3,
Upon extrusion molding the thermoplastic molding resin composition,
A thermoplastic resin, which is extruded so that the residual amount of the α, β unsaturated carboxylic acid monomer in the extruded product is 20% by weight or less of the added amount of the α, β unsaturated carboxylic acid monomer. This is a method for producing a molded article.

The invention according to claim 8 (hereinafter referred to as invention 8) uses polymethyl methacrylate powder as the acrylic resin powder according to claim 3 and at least aluminum hydroxide as the inorganic filler. The extrusion temperature of the extruder is set to 140 to 199 ° C.
The method for producing a thermoplastic resin molded article according to the above.

In the following description, when the present inventions 1 to 8 are generally described, the present invention is simply described as the present invention. For example, when matters relating to the present invention 2 are described, the present invention 2 is described in principle.

(Thermoplastic Resin) As the thermoplastic resin usable in the present invention, for example, an acrylic resin,
Widely marketed such as polyethylene, polypropylene, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, fluororesin, polyphenylene sulfide, polystyrene, ABS resin, polycarbonate, polyvinyl chloride, polyurethane, polyphenylene oxide, ethylene-vinyl acetate copolymer, etc. Resin.

In the present invention, since an α, β unsaturated carboxylic acid monomer which acts as a plasticizer at the time of extrusion molding is used as an essential component, a resin having a high affinity for such a monomer is preferable. Acrylic resin, polypropylene, polystyrene, ethylene-vinyl acetate copolymer and the like are preferably used. Among them, an acrylic resin is preferable in that an artificial marble-like molded product can be manufactured,
This will be described later. The shape of the thermoplastic resin may be a powder or a pellet, but the average particle size is 160 μm.
m or more is preferred. If the thickness is less than 160 μm, the cohesive force between the resin powders increases, and the filling amount of the filler may decrease.

(Acrylic resin powder) The present inventions 3, 4,
In 7 and 8, an acrylic resin powder is used as the resin of the resin composition for thermoplastic molding. As the acrylic resin powder, a single thermoplastic acrylic resin or a thermoplastic methacrylic resin can be used, but a plurality of types of thermoplastic (meth) acrylic resins may be used in combination. Is used, a homopolymer of methyl methacrylate is used.

In the present specification, (meth) acryl is a generic term for acryl and / or methacryl. Average particle size (median diameter) D of acrylic resin powder
50 is preferably 160 to 2000 μm. When the average particle size is smaller than 160 μm, the cohesive force between the acrylic resin powders becomes too large, and the filling amount of the inorganic filler during extrusion molding may decrease. If it exceeds 2000 μm, it becomes difficult to sufficiently knead the inorganic filler and the acrylic resin powder, and a mottled pattern may be formed.

(Inorganic Filler) In the present inventions 3, 4, 7, and 8, it is possible to use an inorganic filler which is not particularly limited as the above-mentioned filler, and specific examples thereof include aluminum hydroxide, ettringite, silica sand, and the like. Borax, alumina, talc, kaolin, calcium carbonate, silica, magnesium hydroxide, mica, fly ash, calcium silicate,
Mica, molybdenum dioxide, talc, glass fiber, glass beads, titanium oxide, asbestos, magnesium oxide, barium sulfate, clay, dolomite, calcium silicate,
Calcium aluminate hydrate and the like, and commercial products of these inorganic fillers can be used.

The above-mentioned inorganic filler may be used alone.
More than one species may be used in combination. Among the above-mentioned inorganic fillers, it is preferable to use aluminum hydroxide because the cost is low and the refractive index is close to that of the acrylic resin, so that a marble-like deep molded body can be obtained, An acrylic-based composite material molded article optimal for marble can be obtained.

The average particle size of the inorganic filler is 1 to 100 μm
Is preferably within the range. If it is smaller than 1 μm, the material viscosity in the extruder increases, and uniform kneading may not be achieved. If it exceeds 100 μm, the surface properties of the molded product may decrease.

The amount of the inorganic filler to be added is preferably 50 to 800 parts by weight based on 100 parts by weight of the acrylic resin powder. If the amount is less than 50 parts by weight, the mixing ratio of the acrylic resin powder becomes relatively high, so that the cost is high and the mechanical properties are sometimes lowered. If the amount is more than 800 parts by weight, kneading with the acrylic resin becomes insufficient, and the extrudability may decrease. Further, the above-mentioned inorganic filler may be subjected to a surface treatment with a silane coupling agent or a titanium coupling agent as necessary.

(Α, β Unsaturated Carboxylic Acid Monomer) The α, β unsaturated carboxylic acid monomer plasticizes a thermoplastic resin, particularly an acrylic resin, to increase the filling ratio of an inorganic filler, and It is polymerized by heating and acts to maintain the shape formed during extrusion molding.

The α, β unsaturated carboxylic acid monomer preferably has a boiling point of at least 102 ° C. When the boiling point is lower than 102 ° C., the composition is volatilized at the time of extrusion molding and may leave air bubbles on the surface of a molded product.

Specifically, examples of the α, β unsaturated carboxylic acid include (meth) acrylic acid.
α, β unsaturated carboxylic acid ester monomers include:
Ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) ) Alkyl acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylate Hydroxypropyl, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl methyl chloride (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tetrohydrofurfuryl (meth) acrylate, ( Allyl (meth) acrylate, di (meth) acryl Ethylene glycol, di (meth) polyethylene glycol acrylate, di (meth) tetraethylene glycol acrylate, di (meth) acrylate 1,3-butylene glycol dimethacrylate, 1,
Examples thereof include 6-hexanediol, trimethylolpropane trimethacrylate, 2-ethoxyethyl methacrylate, β-hydroxyethyl acrylate, and hydroxypropyl acrylate.

The boiling point of the α, β unsaturated carboxylic acid monomer must be lower than the extrusion temperature of the extruder. For example, when extruding at 150 ° C., the boiling point is 15
It is preferable to use n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, or the like having a temperature of 0 ° C. or lower.

The α, β unsaturated carboxylic acid monomer is used in an amount of 100 parts by weight of the above-mentioned acrylic resin powder.
It is used in the range of 5 to 40 parts by weight. If the amount is less than 5 parts by weight, the acrylic resin powder cannot be sufficiently plasticized, the inorganic filler cannot be filled at a high level, and the extrudability decreases. If the amount is more than 40 parts by weight, the material viscosity decreases. Too much, bubbles and the like are intermingled, and the surface properties and physical properties of the molded article are reduced.

(Polymerization Initiator) In the present invention, the above-mentioned polymerization initiator is used to polymerize the above-mentioned α, β unsaturated carboxylic acid monomer by heating, and induces the polymerization of the unsaturated carboxylic acid monomer. Any polymerization initiator can be used as long as it can.

Specifically, examples of the polymerization initiator include organic peroxides such as ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxydiponates, and peroxyesters. An oxide-based polymerization initiator can be used. More preferably, a polymerization initiator having a 10-hour half-life temperature of 60 ° C. or higher is preferable. If the polymerization initiator is lower than 60 ° C., the α, β unsaturated carboxylic acid-based monomer is rapidly polymerized and cured during extrusion molding, Extrusion moldability may decrease.

More specifically, the organic peroxide-based polymerization initiator includes, for example, methyl acetoacetate peroxide, 1,1-bis (t-hexylperoxy)
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2- Bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, -T-butyl peroxide, lauroyl peroxide, stearoyl peroxide, 2,4-dichlorobenzoyl peroxide, octanoyl peroxide, benzoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) Sun, 1-cyclohexyl -
1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t -Hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,
5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dithimer-2,5-bis (m
-Toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,
5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, 2,4,4-trimethylpentyl-2-hydroper Oxide and the like.

Assuming that the 10-hour half-life temperature of the polymerization initiator that can be used is T (° C.), the relation of T 0 −70 (° C.) <T <T 0 −10 (° C.) is satisfied with respect to the extruder extrusion temperature T 0. Is preferable, whereby the curing speed is set to an appropriate size, and a decrease in extrudability can be prevented.

The combination and the mixing ratio of the polymerization initiator and the α, β unsaturated carboxylic acid monomer vary depending on the kind of the polymerization initiator, but a gel time tester (No. 153 formula YASUUD) under the same temperature conditions as the extrusion temperature.
Preferably, the gelation time is adjusted to be 30 to 600 seconds in the measurement by ASEIKI SEISAKUSHO. By setting the content in this range, good extrusion moldability and improvement in the surface properties of the molded product can be achieved.

(Lubricant) The lubricant used in the present inventions 2, 4, and 6 is not particularly limited. Examples thereof include hydrocarbons (liquid paraffin, natural paraffin, microwax, polyethylene wax, etc.) and higher fatty acids (stearic acid). Fatty acid amides (stearic acid amide, palmitic acid amide, methylene bisstearamide, ethylene bisstearamide, etc.), esters (butyl stearate, hydrogenated castor oil, ethylene glycol monostearate, etc.), alcohols (Cetyl alcohol, stearyl alcohol, etc.) and metal soaps (zinc stearate, calcium stearate, lead stearate, etc.) are possible.

Although it depends on the type of resin used, it is preferable that the resin exhibit strong external lubricity. In this respect, hydrocarbons, higher fatty acids and metal soaps are preferably used. This is because, in extrusion molding of a thermoplastic molding resin composition highly filled with a filler, the smaller the resistance to the mold during cooling shaping, the more significantly the moldability is improved. The amount of the lubricant added is 1 to 40 parts by weight. If the amount is less than 1 part by weight, the effect of addition is difficult to be exhibited, and if it exceeds 40 parts by weight, the extrusion kneading property and the physical properties of the molded article are reduced.

(Production method of thermoplastic resin molded article) In the production method of the present invention, the thermoplastic molding resin composition obtained by blending the above-mentioned components is lightly stirred so as to be uniform.
Put into extruder. The charging of the resin composition into the extruder may be performed by lightly mixing the materials in advance, and may be charged as a powder.
A method may be adopted in which a powdery substance excluding the α, β unsaturated carboxylic acid-based monomer is charged from a hopper, and the α, β unsaturated carboxylic acid-based monomer is dropped directly on a kneading shaft of an extruder by a pump. As the extruder, either a single-screw extruder or a twin-screw extruder can be used, but a twin-screw extruder is preferably used in order to improve kneading properties.

Further, if necessary, a reinforcing material such as carbon fiber, other fillers such as wood powder, marble powder, metal powder and the like may be blended and extruded. The molding temperature of the extruder varies depending on the type of the inorganic filler, but for example, when aluminum hydroxide is used, it is preferably 140 to 199 ° C. When the temperature is lower than 140 ° C., the aluminum hydroxide cannot be sufficiently kneaded, and the extrudability decreases. When the temperature is higher than 199 ° C., water of crystallization in aluminum hydroxide is desorbed, and the physical properties and surface properties of the obtained molded product may be deteriorated.

In the case of inorganic fillers other than aluminum hydroxide, the extrusion temperature is usually in the range of about 100 to 250 ° C. Further, the residual amount of the unsaturated carboxylic acid monomer in the molded product obtained by extrusion molding is desirably 20% by weight or less of the unsaturated carboxylic acid monomer added. When the residual monomer ratio exceeds 20% by weight,
The physical properties of the resulting molded article may be reduced.

(Applications) In the present invention, a molded product is obtained by extrusion molding by the above-mentioned production method. This molded product is, for example, particularly when an acrylic resin is used as a thermoplastic resin, a washstand, It is used for various applications where it is desirable to use artificial marble, such as a top plate for a sink and a bathtub.

(Function) In the resin composition for thermoplastic molding according to the first aspect of the present invention, the composition containing a thermoplastic resin resin and a filler contains the α, β unsaturated carboxylic acid monomer and the polymerization initiator. When it is subjected to extrusion molding, the α, β unsaturated carboxylic acid monomer acts as a plasticizer upstream of the extruder to increase the filling of the filler and to extrude the thermoplastic resin at a low temperature. In the downstream portion of the extruder, the α, β unsaturated carboxylic acid-based monomer is polymerized and cured to become a polymer, which acts to maintain the shape of the extruded molded product, Since the .beta.-unsaturated carboxylic acid monomer becomes a polymer in the downstream portion of the extruder as described above, it does not adversely affect the physical properties of the final molded product.

In the thermoplastic molding resin composition according to the second aspect of the present invention, a resin composition obtained by further adding a lubricant to the thermoplastic molding resin composition according to the first aspect is used. The resistance to the mold during cooling shaping is reduced, and the extrudability such as profile extrusion is significantly improved.

In the thermoplastic resin composition according to the third aspect of the present invention, the composition containing the acrylic resin powder and the inorganic filler is added to the unsaturated carboxylic acid-based composition having a boiling point of at least 102 ° C. Since the monomer and the polymerization initiator are blended, when subjected to extrusion molding, the α, β unsaturated carboxylic acid-based monomer acts as a plasticizer upstream of the extruder, thereby increasing the amount of the inorganic filler and increasing the acryl content. Low-temperature extrusion of the base resin, α, β
The unsaturated carboxylic acid monomer is polymerized and cured to become a polymer, which acts to maintain the shape of the extruded acrylic molded product. Moreover, since the α, β unsaturated carboxylic acid monomer becomes a polymer downstream of the extruder as described above, it does not adversely affect the physical properties of the final acrylic molded article.

In the thermoplastic molding resin composition according to the fourth aspect of the present invention, a resin composition obtained by further adding a lubricant to the acrylic molding resin composition according to the third aspect is used. The resistance to the mold during cooling and shaping during molding is reduced, and the extrudability of the acrylic molded article, such as profile extrusion, is significantly improved.

In the method for producing a thermoplastic resin article according to the fifth aspect of the present invention, when the resin composition for thermoplastic molding according to the first aspect of the present invention is extrusion-molded, the resulting molded article may have Since the extrusion molding is performed so that the amount of the residual monomer is 20% by weight or less of the amount of the unsaturated carboxylic acid-based monomer added, α,
Since the content of the β-unsaturated carboxylic acid monomer is reduced, it is possible to obtain a molded article excellent in physical properties and the like.

In the method for producing a thermoplastic resin molded article according to the present invention, a resin composition obtained by further adding a lubricant to the thermoplastic molding resin composition according to the present invention is extruded. At this time, the amount of the residual monomer in the obtained molded article is 20% of the amount of the unsaturated carboxylic acid-based monomer added.
Since the extrusion molding is carried out so as to be not more than 5% by weight, it is possible to obtain a molded body having excellent physical properties and the like as in the case of claim 5, and the resistance to the die during cooling and shaping of the extrusion molding is small. Thus, the extrudability of the thermoplastic resin molded article, such as profile extrusion, is significantly improved.

In the method for producing a thermoplastic resin molded article according to the invention of claim 7, when the resin composition for thermoplastic molding according to the invention of claim 3 is subjected to extrusion molding, the molded product obtained by extrusion molding may be used. Since the extrusion molding is performed so that the amount of the residual monomer is 20% by weight or less of the amount of the unsaturated carboxylic acid-based monomer added, α,
Since the content of the β unsaturated carboxylic acid monomer is reduced, it is possible to obtain an acrylic molded article excellent in physical properties and the like.

In the production method according to the present invention, methyl acrylic acid powder is used as the acrylic resin powder and at least aluminum hydroxide is used as the inorganic filler.
The extrusion temperature of the extruder is 140 to 199 ° C. Therefore, since the extrusion molding is performed at a lower temperature than the extrusion molding temperature of a normal acrylic resin, it is possible to use aluminum hydroxide which releases crystallization water at a high temperature.

[0045]

The present invention will be clarified by the following non-limiting examples and comparative examples. Hereinafter, “parts” means “parts by weight”.

Example 1 Methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: SUMIPEC BLG6A, average particle diameter D50 = 300 μm) as an acrylic resin powder 100 parts Calcium carbonate (Nitto Powder Co., Ltd.) as an inorganic filler 800 parts, α-, β-unsaturated carboxylic acid monomer, 2-ethylhexyl methacrylate 20 parts, cumene hydroperoxide as a polymerization initiator (10-hour half-life temperature: 159 ° C) 0.05 The above components were stirred so as to be uniform, and charged into an extruder from a hopper. The extrusion temperature is 210 ° C.
It was extruded into a sheet having a size of 3 mm.

Example 2 100 parts of methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: SUMIPEC BLG6A, average particle size D50 = 300 μm) as an acrylic resin powder, aluminum hydroxide (Sumitomo Chemical Co., Ltd.) as an inorganic filler (Product name: CW308) 400 parts n-butyl methacrylate as an α, β unsaturated carboxylic acid monomer 20 parts t-butyl peroxybenzoate as a polymerization initiator (10-hour half-life temperature 105 ° C.) 0 The above components were stirred so as to be uniform, and charged into the extruder from a hopper. When the extrusion temperature is 150 ° C.,
It was extruded into a sheet having a size of 3 mm.

Example 3 As acrylic resin powder, 100 parts of methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumipec BLG6A, average particle diameter D50 = 300 μm) As an inorganic filler, aluminum hydroxide (Sumitomo Chemical Co., Ltd.) 500 parts of α, β unsaturated carboxylic acid-based monomer, 20 parts of cyclohexyl methacrylate as polymerization initiator Cumene hydroperoxide as polymerization initiator (10-hour half-life temperature: 159 ° C.) 0.05 part or more Was stirred so as to be uniform, and charged into the extruder from a hopper. Extrusion temperature is 180 ° C, 150
It was extruded into a sheet having a size of 3 mm.

Example 4 100 parts of methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumipec BLG6A, average particle size D50 = 300 μm) as an acrylic resin powder, aluminum hydroxide (Sumitomo Chemical Co., Ltd.) as an inorganic filler Co., Ltd., trade name: CW308) 700 parts As an α, β unsaturated carboxylic acid-based monomer, butyl methacrylate 40 parts As a polymerization initiator cumene hydroperoxide (10-hour half-life temperature 159 ° C.) 0.1 part or more Was stirred so as to be uniform, and charged into the extruder from a hopper. Extrusion temperature is 180 ° C, 150
It was extruded into a sheet having a size of 3 mm.

(Example 5) 100 parts of methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumipec BLG6A, average particle diameter D50 = 300 μm) as an acrylic resin powder 700 parts of fly ash α, 20 parts of 2-ethylhexyl methacrylate as a β-unsaturated carboxylic acid monomer 20 parts of cumene hydroperoxide as a polymerization initiator (10 hour half-life temperature 159 ° C.) 0.05 parts It was put into the machine from the hopper. The extrusion temperature is 210 ° C.
It was extruded into a sheet having a size of 3 mm.

Example 6 Methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: SUMIPEC BLG6A, average particle diameter D50 = 300 μm) as an acrylic resin powder 100 parts Calcium carbonate (Nitto Powder Co., Ltd.) as an inorganic filler 800 parts, α-, β-unsaturated carboxylic acid monomer, 2-ethylhexyl acrylate 20 parts, Cumene hydroperoxide as a polymerization initiator (10-hour half-life temperature: 159 ° C) 0.05 The above components were stirred so as to be uniform, and charged into an extruder from a hopper. The extrusion temperature is 210 ° C.
It was extruded into a sheet having a size of 3 mm.

(Example 7) 100 parts of polypropylene (manufactured by Nippon Polychem Co., Ltd., trade name: Novatec PP) as a thermoplastic resin Aluminum hydroxide (manufactured by Sumitomo Chemical Co., trade name: CW308 500 parts) as an inorganic filler α 20 parts of cyclohexyl methacrylate as a β-unsaturated carboxylic acid-based monomer and 0.05 part of cumene hydroperoxide as a polymerization initiator The above components were uniformly stirred and charged into an extruder from a hopper. To 180 ° C and 150
It was extruded into a sheet having a size of 3 mm.

(Example 8) In Example 7, zinc stearate (SZ2000, manufactured by Sakai Chemical Co., Ltd.) was used as a lubricant.
Prototypes were obtained in the same manner except that parts were formed and the deformed shaped body 2 was formed by joining two square pipes by cooling and shaping with the deformed mold 1 shown in FIG.

(Example 9) In Example 7, the thermoplastic resin was changed from polypropylene to polymethyl methacrylate, and zinc stearate (SZ2 manufactured by Sakai Chemical Co., Ltd.) was used as a lubricant.
000) and cooled and shaped by the deformed mold 1 shown in FIG.
A prototype was obtained in the same manner except that was manufactured.

Comparative Example 1 100 parts of methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumipec BLG6A, average particle size D50 = 300 μm) as an acrylic resin powder, calcium carbonate (Nitto Powder Co., Ltd.) as an inorganic filler (Manufactured by the company, trade name: NS-100) 200 parts The above components were stirred so as to be uniform, and charged into the extruder from a hopper. The extrusion temperature is 210 ° C.
It was extruded into a sheet having a size of 3 mm.

(Comparative Example 2) 100 parts of methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumipec BLG6A, average particle diameter D50 = 300 μm) as an acrylic resin powder, calcium carbonate (Nitto Powder Co., Ltd.) as an inorganic filler Company name, NS-100) 900 parts 2-ethylhexyl methacrylate as an α, β unsaturated carboxylic acid monomer 20 parts Cumene hydroperoxide as a polymerization initiator (10-hour half-life temperature 159 ° C.) 0.05 The above components were stirred so as to be uniform, and charged into an extruder from a hopper. The extrusion temperature is 210 ° C.
It was extruded into a sheet having a size of 3 mm.

Comparative Example 3 Methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumipec BLG6A, average particle diameter D50 = 300 μm) as an acrylic resin powder 100 parts Aluminum hydroxide (Sumitomo Chemical Co., Ltd.) as an inorganic filler 200 parts, methyl methacrylate (boiling point: 101 ° C.) as an α, β unsaturated carboxylic acid monomer 20 parts t-amyl peroxy-2-ethylhexanoate (10 hours half as a polymerization initiator) (Initial temperature: 70 ° C.) 0.1 parts The above components were stirred so as to be uniform, and charged into the extruder from a hopper. Extrusion temperature is 130 ° C, 150
It was extruded into a sheet having a size of 3 mm.

Comparative Example 4 Methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: SUMIPEC BLG6A, average particle diameter D50 = 300 μm) as an acrylic resin powder 100 parts Aluminum hydroxide (Sumitomo Chemical Co., Ltd.) as an inorganic filler Company, trade name: CW308) 400 parts n-butyl methacrylate as an α, β unsaturated carboxylic acid monomer 50 parts t-butyl peroxybenzoate as a polymerization initiator (10-hour half-life temperature 105 ° C.) 0. 125 parts or more of the components were stirred so as to be uniform, and charged into the extruder from a hopper. When the extrusion temperature is 150 ° C.,
It was extruded into a sheet having a size of 3 mm.

(Evaluation of Examples and Comparative Examples) The extrusion moldability in Examples and Comparative Examples and the surface properties of the obtained molded articles were evaluated in the following three grades.

A: Extrusion molding was possible, and the surface properties of the obtained molded product were good. B: Although extrusion molding was possible, air bubbles were formed on the surface of the molded product, and kneading failure was observed. C: Extrusion molding could not be performed.

The residual ratio of the α, β unsaturated carboxylic acid monomer in the obtained molded article (remaining monomer amount / used monomer amount) × 100 (%) was measured. Further, the bending strength of the obtained molded article was measured according to JIS K7055. Table 1 below shows the mixing ratios and production conditions of the above Examples and Comparative Examples, and Table 2 shows the evaluation results.

[0062]

[Table 1]

[0063]

[Table 2]

As is clear from Table 2, in Comparative Example 1,
Since the α, β unsaturated carboxylic acid monomer and the polymerization initiator were not blended, extrusion molding could not be performed even at a temperature of 210 ° C. when calcium carbonate was blended at a ratio of 200 parts.

In Comparative Example 2, the compounding ratio of the inorganic filler was 9
Extrusion could not be performed, probably because it was too high of 00 parts. In Comparative Example 3, aluminum hydroxide was used as the inorganic filler, but the extrusion molding temperature was too low at 130 ° C.
Extrusion molding was not good, the surface properties of the obtained molded product were not sufficient, and the bending strength of the obtained molded product was as low as 12 MPa.

In Comparative Example 4, extrudability was not good, probably because the compounding ratio of n-butyl methacrylate as an α, β unsaturated carboxylic acid monomer was too high at 50 parts. The bending strength was as low as 13 MPa.

On the other hand, in Examples 1 to 6, the acrylic molding resin composition according to the third aspect of the present invention was used, and the residual amount of the α, β unsaturated carboxylic acid type monomer was reduced by the added α. , Β-unsaturated carboxylic acid-based monomer is molded so as to be 20% by weight or less, so that the moldability is good, the surface properties of the molded article are good, and the bending strength of the obtained molded article is good. Was also as high as 53 MPa or more. On the other hand, it is clear from Example 7 that a molded article having good physical properties was obtained with good moldability even when polypropylene was used as the thermoplastic molding resin. Further, in Examples 8 and 9, by adding a lubricant, a molded article having a good surface property and an irregular shape was easily obtained.

[0068]

According to the resin composition for thermoplastic molding according to the first aspect of the present invention, an α, β unsaturated carboxylic acid monomer and a polymerization initiator are added to a composition containing a thermoplastic resin and a filler. Therefore, when used in extrusion molding, the filler can be highly filled by the action of the α, β unsaturated carboxylic acid monomer, and in the later stage of the extrusion process, the monomer is polymerized and hardened, resulting in high filling. Since it is a molecule, it is possible to reliably obtain a molded article having a desired surface shape and a desired shape while maintaining the formed shape.

According to the second aspect of the present invention, in addition to the above, extrudability such as profile extrusion is remarkably improved.

In the thermoplastic resin composition according to the third aspect of the present invention, the composition containing the acrylic resin powder and the inorganic filler is added to the unsaturated carboxylic acid-based composition having a boiling point of at least 102 ° C. Since the monomer and the polymerization initiator are blended, when subjected to extrusion molding, it is possible to achieve high filling of the inorganic filler and low-temperature extrusion of the acrylic resin, and have good surface properties and shape. It is possible to reliably obtain an acrylic molded article having a desired shape while maintaining the formed shape. Further, in the invention according to claim 4, since a resin composition obtained by further adding a lubricant to the acrylic molding resin composition according to claim 3 is used, the resin composition is formed with a mold at the time of cooling and shaping in extrusion molding. Resistance is reduced, and in addition to the above, extrudability such as profile extrusion of an acrylic molded article is significantly improved.

In the method for producing a thermoplastic resin article according to the fifth aspect of the present invention, when the resin composition for thermoplastic molding according to the first aspect of the present invention is extrusion-molded, the molded article obtained by the extrusion method may be used. Since the extrusion molding is performed so that the amount of the residual monomer is 20% by weight or less of the amount of the unsaturated carboxylic acid-based monomer added, a molded article excellent in physical properties and the like can be obtained.

According to the production method of the invention described in claim 6, when the composition obtained by further adding a lubricant to the resin composition for thermoplastic molding according to claim 1 is extruded, a molded product obtained is obtained. Since the extrusion molding is performed so that the amount of the residual monomer in the mixture is 20% by weight or less of the amount of the unsaturated carboxylic acid-based monomer added, it is possible to obtain a molded product excellent in physical properties and the like as in claim 5. In addition, the extrudability of the thermoplastic resin molded article, such as profile extrusion, is significantly improved.

According to the production method of the invention described in claim 7, when the resin composition for thermoplastic molding according to the invention of claim 3 is extruded, the amount of residual monomer in the obtained molded product is as follows: Since the extrusion molding is performed so as to be 20% by weight or less based on the amount of the unsaturated carboxylic acid-based monomer added, the content of the α, β unsaturated carboxylic acid monomer in the obtained molded article is reduced. Thus, it is possible to obtain an excellent acrylic molded article.

According to the production method of the present invention, the extrusion molding is carried out at a temperature lower than the usual extrusion molding temperature of 140 to 199 ° C. of acrylic resin using methyl methacrylate and aluminum hydroxide. It is possible to use aluminum hydroxide, which is an excellent flame retardant that releases water of crystallization at high temperatures. Therefore, in particular, a safe resin molded body that does not generate toxic gas can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a prototype deformed mold used to obtain a thermoplastic resin molded article of the present invention.

FIG. 2 is a perspective view showing one example of a thermoplastic resin molded article of the present invention.

[Explanation of symbols]

 1: deformed mold 2: thermoplastic resin molding

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/00 C08K 3/00 3/22 3/22 5/098 5/098 C08L 33/00 C08L 33/00 51/00 51 / 00 // B29K 33:04

Claims (8)

[Claims] 1. A resin composition for thermoplastic molding comprising a thermoplastic resin, a filler, an α, β unsaturated carboxylic acid monomer and a polymerization initiator. 2. The thermoplastic molding resin composition according to claim 1, further comprising a lubricant added to the thermoplastic molding resin composition according to claim 1. 3. 100 parts by weight of an acrylic resin powder as the thermoplastic resin, and an inorganic filler 50 as the filler.
2 to 800 parts by weight, 5 to 40 parts by weight of an α, β unsaturated carboxylic acid monomer having a boiling point of 102 ° C. or more as the α, β unsaturated carboxylic acid monomer and a polymerization initiator. 5. The resin composition for thermoplastic molding according to item 1. 4. A thermoplastic molding resin composition, further comprising 1 to 40 parts by weight of a lubricant added to the thermoplastic molding resin composition according to claim 3. 5. A method for producing a thermoplastic resin molded article using the resin composition for thermoplastic molding according to claim 1, wherein the resin composition for thermoplastic molding is extrusion-molded.
A thermoplastic resin, which is extruded so that the residual amount of the α, β unsaturated carboxylic acid monomer in the extruded product is 20% by weight or less of the added amount of the α, β unsaturated carboxylic acid monomer. A method for producing a molded article. 6. A method for producing a thermoplastic resin molded article using the resin composition for thermoplastic molding according to claim 2, wherein the resin composition for thermoplastic molding is extrusion-molded.
A thermoplastic resin, which is extruded so that the residual amount of the α, β unsaturated carboxylic acid monomer in the extruded product is 20% by weight or less of the added amount of the α, β unsaturated carboxylic acid monomer. A method for producing a molded article. 7. A method for producing a thermoplastic resin molded article using the resin composition for thermoplastic molding according to claim 3, wherein the thermoplastic resin composition is extruded.
A thermoplastic resin, which is extruded so that the residual amount of the α, β unsaturated carboxylic acid monomer in the extruded product is 20% by weight or less of the added amount of the α, β unsaturated carboxylic acid monomer. A method for producing a molded article. 8. An extruder having an extrusion temperature of 140 to 199 ° C., wherein polyacrylic methacrylate powder is used as the acrylic resin powder according to claim 3, and at least aluminum hydroxide is used as the inorganic filler. Claim 7
The method for producing a thermoplastic resin molded article according to the above.