JPH10298413A - Thermoplastic resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin molding which can give a processed product being excellent in surface gloss, transparency, color tone, etc., having the appearance of a quality article and having such excellent heat processability that when the molding is subjected to e.g. bending under heating, the molding has a low degree of distortion upon cooling and is excellent in impact resistance and can be used effectively as a material for interior materials and implements for living and to provide a rein composition for giving the same. SOLUTION: This molding has a degree of glossiness of 80% or above on at least one surface, a common logarithm of a storage modulus of 7-8 MPa in a temperature range higher than the glass transition temperature by 20-100 deg.C, a degree of deformation upon cooling from 130 deg.C to 50 deg.C of 1.0 kg/cm<2> . deg.C or below and an Izod impact strength of 2.0 kJ/m<2> or above. To produce this molding, it is desirable to use a thermoplastic resin composition comprising a polybutylene terephthalate resin, a polyethylene terephthalate resin, a (meth) acrylic resin, multilaryer structure polymer particles and an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin molded article, a method for producing the same, a processed article obtained by heating the above-mentioned thermoplastic resin molded article, and a method for producing the above-mentioned thermoplastic resin molded article. The present invention relates to a thermoplastic resin composition used. More specifically, the present invention is excellent in surface gloss, transparency, color tone, etc., has a high-class feeling, and is excellent in heat processing property, and when subjected to bending processing under heating, the cooling distortion rate Is small, because the internal strain in the processed product is small, excellent in impact resistance, a thermoplastic resin molded product that can obtain a processed product without cracks and breakage, the thermoplastic resin composition preferably used in the above, The present invention relates to a processed product obtained by heating a thermoplastic resin molded product and a method for producing the thermoplastic resin molded product. The thermoplastic resin molded product of the present invention makes use of the above-described excellent properties to make use of the housing such as a top plate of a system kitchen, a door, a wall, a top plate of a vanity stand, a waist wall of a unit bath, an apron, and a counter of a bay window. It can be effectively used for a wide range of applications, including interior materials and interior equipment.

[0002]

2. Description of the Related Art A melamine resin decorative board, an artificial marble using a (meth) acrylic resin or an unsaturated polyester resin, and the like are combined with other materials such as a plywood or a calcium silicate board to form a system kitchen ceiling. Boards, vanity tops, waist walls and aprons of unit baths, doors and walls of houses,
2. Description of the Related Art It has been widely used as interior materials and interior equipment for houses such as bay window counters.

[0003] However, those using a melamine resin decorative board have a disadvantage that they are poor in quality, have a large internal strain in a heated bending portion, and have an extremely low impact strength in a bent portion. It is not satisfactory. In addition, artificial marble using (meth) acrylic resin or unsaturated polyester resin has a higher quality than melamine resin decorative board, but (meth) acrylic resin and unsaturated polyester resin used there are Since it is a thermosetting resin, it cannot be manufactured smoothly by the extrusion molding method with high productivity, and the casting method and the pressing method, which are less productive than the extrusion molding method, are usually used, and the production cost is low. I have to be high. In addition, since these artificial marbles are difficult to bend under heating, the formation of a curved portion (R portion) must be performed by time-consuming and time-consuming cutting, and there is a disadvantage that the processing cost is increased. An artificial marble based on a (meth) acrylic resin that can be bent under heating is known, but it cannot be said that the heating processability is sufficient because the resin is crosslinked. There are restrictions on the shape formed by heat processing.

Further, for the purpose of obtaining a molded article having improved heat processability and impact resistance, a thermoplastic molding resin composition containing polybutylene terephthalate, polyethylene terephthalate, polycarbonate and an inorganic filler has been proposed. (JP-A-6-279665). However, barium sulfate, which is used as an inorganic filler in this resin composition, has a large difference in refractive index from the resin, and as a result, the resulting molded article has poor transparency and glossiness, and does not have a high-grade feel. Easy to be.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-grade thermoplastic resin molded article having excellent surface gloss, transparency and color tone. Further, an object of the present invention is to provide a work piece having a predetermined shape easily and smoothly by heating work such as bending work under heating without using cutting work or polishing work, which is excellent in heat workability. It is an object of the present invention to provide a thermoplastic resin molded product which can be manufactured at a time. An object of the present invention is to provide a thermoplastic resin molding that can obtain a processed product having a small cooling strain at the time of heat processing, a small residual distortion in the processed product, and therefore having excellent impact resistance and free from cracks and breakage. To provide goods.
Further, an object of the present invention is to provide a thermoplastic resin composition which can be effectively used for producing a thermoplastic resin molded article having the above-mentioned excellent properties. Another object of the present invention is to provide a method for producing the above-mentioned thermoplastic resin molded product, and a processed product obtained by subjecting the thermoplastic resin molded product to heat processing.

[0006]

The present inventors have made various studies to achieve the above object. As a result, the surface glossiness was 80% or more, and the glass transition temperature was 20 ° C to 100 ° C.
Has a specific storage modulus in the high temperature range of
A thermoplastic resin molded article having a cooling strain rate of not more than a specific value when cooled from 0 ° C. to 50 ° C. and having an Izod impact strength of not less than a specific value has excellent heat processability, and When the bending process is performed, the cooling strain rate is small and the residual strain in the processed product is extremely small, so the processed product obtained by heating is excellent in impact resistance, cracks and breakage etc. It does not occur and is suitable for use as interior materials and interior equipment for homes such as the top plate of a system kitchen, the top plate of a vanity table, the waist wall and apron of a unit bath, the doors and walls of a house, the counters of bay windows, etc. I found that I got it. In addition, the present inventors have found that the above-mentioned thermoplastic resin molded article is excellent in surface gloss, transparency, and color tone, has a high-grade appearance, and thus is not only heat-processed and used, but also heat-processed. It has been found that a molded article can be effectively used for a wide range of applications without any modification. further,
The present inventors have found that a thermoplastic resin molded product having the above-mentioned excellent properties contains a polybutylene terephthalate resin, a polyethylene terephthalate resin, a (meth) acrylic resin, a multilayer structure polymer particle, and an inorganic filler. By using a thermoplastic resin composition, it has been found that a molding method such as extrusion molding widely used in molding of a thermoplastic resin can be produced smoothly and with good productivity, and based on those findings, The present invention has been completed.

That is, according to the present invention, at least one surface has a glossiness of 80% or more, and has a glass transition temperature of at least 20%.
The common logarithm of the storage modulus in a temperature range higher than 100 ° C. to 100 ° C. is 7 to 8 MPa, the cooling strain rate when cooled from 130 ° C. to 50 ° C. is 1.0 kg / cm ² · ° C. or less, and Izod A thermoplastic resin molded product having an impact strength of 2.0 kj / m ² or more.

The present invention includes a thermoplastic resin molded product obtained by combining the above-mentioned thermoplastic resin molded product with another material, and a processed product obtained by subjecting the thermoplastic resin molded product to heat processing. I do.

Further, the present invention relates to (A) a polybutylene terephthalate resin, (B) a polyethylene terephthalate resin, (C) a (meth) acrylic resin, (D) multilayer polymer particles, and (E) an inorganic filler. It is a thermoplastic resin composition characterized by containing an agent. The present invention also includes a method for producing a thermoplastic resin molded article by extrusion molding using the above-described thermoplastic resin composition.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The thermoplastic resin molded article of the present invention has a glossiness of at least one surface of 80% or more, and a common logarithm of the storage elastic modulus in a temperature range of 20 ° C to 100 ° C higher than the glass transition temperature is 7 to 8 MPa. When the molded product is cooled from a temperature of 130 ° C. to a temperature of 50 ° C., the cooling distortion rate is 1.0.
kg / cm ² · ° C. or less and the Izod impact strength is 2.0 kj / m ² or more.

In the thermoplastic resin molded product of the present invention, the glossiness of only one surface of the molded product is 80% or more, the glossiness of two or more surfaces is 80% or more, or The glossiness of all surfaces may be 80% or more, and it is preferable that at least the surface exposed to human eyes has a glossiness of 80% or more. When there is no surface with a glossiness of 80% or more in the thermoplastic resin molded product, the product has no high-grade appearance. Here, “the glossiness of at least one surface” in the molded article referred to in the present specification refers to a 60 ° specular glossiness when at least one surface of the molded article is measured according to JIS K 7105, The specific measuring method is as described in the following section of Examples.

Further, in the case of a thermoplastic resin molded product, the common logarithm of the storage elastic modulus in a temperature range of 20 ° C. to 100 ° C. higher than its glass transition temperature is 7 to 8 MPa,
A thermoplastic resin molded product and a processed product obtained by heating the thermoplastic resin molded product can be easily obtained. If the common logarithm of the storage modulus in the temperature range of 20 ° C. to 100 ° C. higher than the glass transition temperature of the thermoplastic resin molded product is less than 7 MPa, the surface of the molded product after heat molding will have a mark of the mold and the surface property May be harmful. On the other hand, the common logarithm is 8M
If it exceeds Pa, cracking may occur during heat molding, or suck-back (returning of molding) may occur immediately after molding, which may not be able to form a composite, which is not preferable. Here, the “common logarithm of the storage elastic modulus in a temperature range of 20 ° C. to 100 ° C. higher than the glass transition temperature” of the molded article referred to in the present specification means, using a dynamic viscoelasticity measuring device, The storage elastic modulus of the molded article in the temperature range of 20 ° C. higher temperature and 100 ° C. higher temperature was measured and its logarithm was used, and the details are as described in the following Examples.

[0013] The thermoplastic resin molded article of the present invention comprises:
When the cooling distortion rate at the time of cooling from 130 ° C. to 50 ° C. is 1.0 kg / cm ² · ° C. or less, the generation of distortion at the time of cooling when the thermoplastic resin molded article is heated is suppressed, and the residual A processed product with small distortion and excellent impact resistance can be obtained. If the above-mentioned cooling distortion rate of the thermoplastic resin molded product exceeds 1.0 kg / cm ² · ° C., when the thermoplastic resin molded product is heated and cooled to produce a processed product, the internal strain in the processed product is reduced. Are generated or remain, and deformation such as reduction in impact resistance, generation of cracks and breakage, and warpage is likely to occur. Here, the “cooling distortion rate when the molded article is cooled from 130 ° C. to 50 ° C.” in the present specification means that the molded article is 13% in accordance with ASTM D 638.
It is a value obtained by converting the stress generated when heated to a temperature of 0 ° C. and cooled to a temperature of 50 ° C. per 1 ° C., and details thereof are as described in the following Examples. .

Further, in the thermoplastic resin molded product of the present invention,
When the Izod impact strength is 2.0 kj / m ² or more, it is extremely excellent in impact resistance. Izod impact strength of thermoplastic resin molded product is 2.0
If it is less than kj / m ² , the impact resistance of the molded product is insufficient, and the molded product is likely to be damaged when used as it is or subjected to secondary processing, and the durability is lost. The “Izod impact strength” of a molded article referred to in this specification is based on JIS K
Izod impact strength measured according to 7110,
The details are as described in the following section of Examples.

The thermoplastic resin molded article of the present invention is a thermoplastic resin molded article made of a thermoplastic resin or a thermoplastic resin composition, and has at least one surface having a glossiness,
Commonly used logarithm of storage elastic modulus, cooling strain rate and Izod impact strength may be any thermoplastic resin molded product satisfying the above requirements, and any type of thermoplastic resin constituting the thermoplastic resin molded product may be used. The type and composition of the thermoplastic resin composition, the method of producing the molded article (molding method), and the like are not particularly limited, and may be determined according to the use of the molded article, the type of the thermoplastic resin or the thermoplastic resin composition constituting the molded article, and the like. You can choose. Among them, the thermoplastic resin molded article of the present invention having the above-mentioned various requirements includes (A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, (C) (meth) acrylic resin, and (D) multilayer. It can be produced smoothly by using a thermoplastic resin composition containing structural polymer particles and (E) an inorganic filler. Therefore, the present invention contains the above-mentioned components (A) to (E). As a preferred embodiment, a thermoplastic resin composition and a thermoplastic resin molded product comprising the same are included.

In particular, in the present invention, the thermoplastic resin composition has a weight ratio of (i) polybutylene terephthalate resin: polyethylene terephthalate resin of 4:
(Ii) polybutylene terephthalate resin and polyethylene terephthalate resin in total of 10
20 to 20 parts by weight of (meth) acrylic resin
0 parts by weight, and (iii) 10 to 100 parts by weight of the multilayer structure polymer particles based on 100 parts by weight of the total of the polybutylene terephthalate resin, the polyethylene terephthalate resin and the (meth) acrylic resin. And (iv) a thermoplastic resin composition containing 10 to 40 parts by weight of an inorganic filler with respect to 100 parts by weight of the thermoplastic resin composition. And
When using such a thermoplastic resin composition containing the respective components in the above-described specific ratio, the internal strain does not occur when performing a bending process or the like under heating with excellent heat processability. High quality, high quality thermoplastic resin molded products and processed products with excellent impact resistance, no cracks and breakage, and excellent surface gloss, transparency, color tone, etc. can be obtained very smoothly. .

In the above-mentioned thermoplastic resin composition, the polybutylene terephthalate-based resin and the polyethylene terephthalate-based resin impart good surface gloss, transparency, and texture to the thermoplastic resin molded product, thereby forming the thermoplastic resin molded product. It contributes to the luxury. In that case,
The ratio of the polybutylene terephthalate-based resin to the polyethylene terephthalate-based resin in the thermoplastic resin composition is preferably the above-described weight ratio of 4: 1 to 1: 1 and more preferably 3: 1 to 5: 2. Is more preferable. If the proportion of the polybutylene terephthalate resin exceeds 80% by weight (based on the total weight of the polybutylene terephthalate resin and the polyethylene terephthalate resin) (the proportion of the polyethylene terephthalate resin is less than 20% by weight), the thermoplastic The surface gloss of the resin molded article tends to be reduced, while when the proportion of the polybutylene terephthalate resin is less than 50% by weight (when the proportion of the polyethylene terephthalate resin exceeds 50% by weight), the thermoplastic Non-uniform portions (fluctuations), which are considered to be caused by phase separation, occur on the surface of the resin molded product, so that the smoothness of the surface is lost and the surface gloss tends to be reduced.

At this time, as the polybutylene terephthalate resin, a polybutylene terephthalate resin composed of a dicarboxylic acid unit mainly composed of terephthalic acid units and a diol unit mainly composed of 1,4-butanediol units is used. . As a typical example of the polybutylene terephthalate-based resin, polybutylene terephthalate consisting of only a terephthalic acid unit and 1,4-butanediol unit can be given. However, the present invention is not limited to polybutylene terephthalate. 20 mol% or less, if necessary, other dicarboxylic acid units and / or
Alternatively, a polybutylene terephthalate resin having a diol unit may be used.

Examples of other dicarboxylic acid units which may be contained in the polybutylene terephthalate resin include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid,
5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid and sodium 5-sulfoisophthalate; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecanedioic acid; 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexane Examples include alicyclic dicarboxylic acids such as dicarboxylic acids; and dicarboxylic acid units derived from ester-forming derivatives thereof (lower alkyl esters such as methyl esters and ethyl esters). The polybutylene terephthalate-based resin may have only one kind of the above-described dicarboxylic acid units, or may have two or more kinds of the above-mentioned dicarboxylic acid units.

Examples of other diol units which may be contained in the polybutylene terephthalate resin include ethylene glycol, propylene glycol, neopentyl glycol, 2-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, cyclohexane C2-10 aliphatic diols such as diols; diethylene glycol, polyethylene glycol, poly-
Examples thereof include diol units derived from polyalkylene glycol having a molecular weight of 6000 or less, such as 1,3-propylene glycol and polytetramethylene glycol. The polybutylene terephthalate-based resin may have only one kind of the above-mentioned diol units, or may have two or more kinds.

Further, if the polybutylene terephthalate resin is 1 mol% or less based on the total structural units, for example, it may be obtained from tri- or more functional monomers such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid. One or two of the derived structural units
It may have more than one species.

Although not limited, the polybutylene terephthalate resin has an intrinsic viscosity of 0.1 when measured as a solution dissolved in a phenol / tetrachloroethane (weight ratio = 1/1) mixed solvent. 5-1.5
The range of dl / g is preferable from the viewpoint of obtaining a thermoplastic resin molded product having excellent mechanical properties such as mechanical strength, elastic modulus, and impact resistance.

As the polyethylene terephthalate resin used together with the polybutylene terephthalate resin, a polyethylene terephthalate resin composed of a dicarboxylic acid unit mainly composed of terephthalic acid units and a diol unit mainly composed of ethylene glycol units is used. As typical examples of polyethylene terephthalate resin,
Polyethylene terephthalate comprising only a terephthalic acid unit and an ethylene glycol unit can be mentioned, but it is not limited to polyethylene terephthalate, and if necessary, other dicarboxylic acid units may be used if they are 20 mol% or less in all structural units. And / or a polyethylene terephthalate resin having a diol unit.

Examples of other dicarboxylic acid units that can be contained in the polyethylene terephthalate resin include the other dicarboxylic acid units described above for the polybutylene terephthalate resin (A), and the polyethylene terephthalate resin (B) , One of the other dicarboxylic acid units
It can have one or more species.

Examples of other diol units which can be contained in the polyethylene terephthalate resin include 1,4-butanediol and other diol units described above with respect to the polybutylene terephthalate resin. The resin (B) may have one or more of the other diol units.

Further, if the polyethylene terephthalate resin is 1 mol% or less based on the total structural units, if necessary, it may be derived from the same trifunctional or higher-functional monomer as described above for the polybutylene terephthalate resin. May have one or more structural units.

Although not limited, polyethylene terephthalate resin has an intrinsic viscosity of 0.5 when measured as a solution dissolved in a phenol / tetrachloroethane (weight ratio = 1/1) mixed solvent. ~ 1.5
The range of dl / g is preferable from the viewpoint of obtaining a thermoplastic resin molded product having excellent mechanical properties such as mechanical strength, elastic modulus, and impact resistance.

The (meth) acrylic resin used together with the polybutylene terephthalate resin and the polyethylene terephthalate resin contributes to improving the heat processability of the thermoplastic resin molded article. The content of the (meth) acrylic resin in the thermoplastic resin composition,
20 ° C to 10 ° C from the glass transition temperature of the thermoplastic resin molded product
The common logarithm of the storage modulus in a temperature range higher by 0 ° C. is 7 to 8M.
As described above, the amount is preferably 20 to 200 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the total of the polybutylene terephthalate-based resin and the polyethylene terephthalate-based resin. More preferred. When the content of the (meth) acrylic resin is less than the above 20 parts by weight, the common logarithm of the storage elastic modulus in the temperature range of 20 ° C. to 100 ° C. higher than the glass transition temperature of the thermoplastic resin molded product is 7 as described above. -8 MPa, the thermoplastic resin molded article tends to have reduced heat processability. On the other hand, when the content of the (meth) acrylic resin exceeds 200 parts by weight, it becomes difficult to mix a large amount of an inorganic filler added to reduce the linear expansion coefficient of the thermoplastic resin molded article, Therefore, the coefficient of linear expansion of the thermoplastic resin molded article tends to increase, and the surface smoothness and mechanical properties of the thermoplastic resin molded article tend to decrease.

The (meth) acrylic resin mainly comprises a structural unit derived from a methacrylic acid ester,
If necessary, a (meth) acrylic resin having a structural unit derived from an acrylate ester and / or another unsaturated monomer is preferably used. As the methacrylate at that time, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
Alkyl esters of methacrylic acid such as pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, trimethylcyclohexyl methacrylate, trifluoroethyl methacrylate; phenyl methacrylate, fluorophenyl methacrylate, chlorophenyl methacrylate, bromophenyl methacrylate, bromophenyl methacrylate, Examples thereof include aromatic hydrocarbon esters of methacrylic acid such as benzyl acrylate, and the (meth) acrylic resin has a structural unit derived from one or more of the above-mentioned methacrylic esters. be able to. Among them, the fact that 80 mol% or more of the structural units constituting the (meth) acrylic resin is mainly composed of structural units derived from methyl methacrylate is the common logarithm of the storage modulus of the thermoplastic resin molded article. It is preferable because it can be smoothly adjusted to the above range of 7 to 8 MPa.

The (meth) acrylic resin may have a small amount (generally 10 mol% or less of the total structural units) of structural units derived from an acrylate ester, if necessary. Examples of the acrylate in that case include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, trimethylcyclohexyl acrylate, trifluoroethyl acrylate, and the like. Acrylic acid alkyl esters; aromatic hydrocarbon esters of acrylic acid such as phenyl acrylate, fluorophenyl acrylate, chlorophenyl acrylate, bromophenyl acrylate, and benzyl acrylate; and (meth) Acrylic resin is
It may have a structural unit derived from one or more of the above-mentioned acrylates.

Further, if necessary, a small amount of (meth) acrylic resin (generally, not more than 10 mol% of all structural units)
May have a structural unit derived from another unsaturated monomer, and in this case, as the other unsaturated monomer, for example,
(Meth) acrylic acid; metal salts of (meth) acrylic acid; vinyl chloride; vinyl acetate; acrylonitonyl; acrylamide; styrene-based monomers such as styrene and α-methylstyrene; vinyltoluene; it can. The (meth) acrylic resin can have structural units derived from one or more of these unsaturated monomers.

The (meth) acrylic resin preferably has a viscosity average degree of polymerization of from 500 to 1800.
More preferably, it is 0-1600. When a (meth) acrylic resin having the above-mentioned viscosity average polymerization degree is used, the glass transition temperature of the thermoplastic resin composition becomes appropriate, and the moldability of the thermoplastic resin composition is improved.
Irregularities do not occur on the surface of the molded product, and when the molded product is heated, no trace of the mold remains on the surface of the molded product, so that a processed product having good appearance can be obtained. If the degree of polymerization of the (meth) acrylic resin is too high, irregularities are likely to occur on the surface of the molded article during the production of the molded article of the thermoplastic resin, and the molded article tends to have a poor appearance. If the ratio is too low, the glass transition temperature of the thermoplastic resin composition and the molded article formed therefrom becomes low, so that when subjected to heat processing, traces of the mold easily remain on the surface of the processed article.

The multilayer polymer particles used in the thermoplastic resin composition of the present invention can be used to improve the impact resistance of a thermoplastic resin molded product and to provide a processed product obtained by subjecting a thermoplastic resin molded product to heat processing. It contributes to the reduction of residual strain and the improvement of impact resistance. As described above, the content of the multilayer polymer particles in the thermoplastic resin composition is 100 total of polybutylene terephthalate resin, polyethylene terephthalate resin and (meth) acrylic resin.
It is preferably from 10 to 100 parts by weight, more preferably from 20 to 50 parts by weight, based on parts by weight. When the content of the multilayer structure polymer particles is less than the above 10 parts by weight, the cooling distortion rate of the thermoplastic resin molded article increases, and the impact resistance tends to decrease. On the other hand, when the content exceeds the above 100 parts by weight. Although the cooling distortion rate of the thermoplastic resin molded product is low, traces of the mold easily remain on the surface of the thermoplastic resin molded product at the time of heat processing, and the appearance of the processed product is easily impaired.

As the polymer particles having a multilayer structure, polymer particles having a multilayer structure of two or three or more layers in which at least the outermost layer is composed of a hard polymer layer and at least a rubbery polymer layer is present inside are described. It is preferably used. By using such multi-layered polymer particles, the multi-layered polymer particles are uniformly dispersed in the thermoplastic resin composition and a molded article comprising the same while maintaining high compatibility, and a good impact resistance improving effect is obtained. Can be fully exhibited.

Although not limited, the multilayer polymer particles preferably used in the present invention include, for example,
Two-layer structured particles consisting of a hard polymer layer (outermost layer) / rubber polymer layer (inner layer), hard polymer layer (outermost layer) / rubber polymer layer (intermediate layer) / hard polymer layer (center layer) 3)
Layered particles, three-layer particles composed of hard polymer layer (outermost layer) / rubber polymer layer (intermediate layer) / rubber polymer layer (center layer), hard polymer layer (outermost layer) / hard polymer Layer (middle layer)
/ Rubber polymer layer (center layer), three-layer particles, hard polymer layer (outermost layer) / rubber polymer layer (intermediate layer) / hard polymer layer (intermediate layer) / rubber polymer layer ( (A central layer).

In the multilayer polymer particles, the hard polymer layer constituting the outermost layer is preferably made of a polymer having a glass transition temperature of 25 ° C. or higher and an elastic modulus of 10 ⁸ MPa. The rubbery polymer layer present inside the multilayer polymer particles preferably comprises a polymer having a glass transition temperature of 25 ° C. or lower.

The hard polymer constituting the hard polymer layer in the multilayer polymer particles is, for example, a chain alkyl or cyclic alkyl ester of methacrylic acid such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and isobutyl methacrylate. Aromatic hydrocarbon esters of methacrylic acid such as phenyl methacrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; obtained by polymerizing one or more unsaturated monomers such as acrylonitrile Is preferred, and more preferably a polymer mainly composed of methyl methacrylate and / or styrene.

The rubbery polymer constituting the rubbery polymer layer in the multilayer polymer particles may be any polymer having a glass transition temperature of 25 ° C. or less and is not particularly limited. Conjugated diene-based polymers such as, for example, polybutadiene, polyisoprene, butadiene-isoprene copolymer, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and acrylate-butadiene copolymer; Hydrogenated polymer; olefin rubber such as ethylene-propylene copolymer, ester-propylene-diene copolymer, ethylene-vinyl acetate copolymer rubber, polyisobutylene rubber; acrylic rubber; silicone rubber; ; Polyurethane elastomer, polyester elastomer Chromatography, and thermoplastic elastomers such as polyamide elastomer can be cited, rubbery polymer layer in the multilayer structure polymer particles can consist of one or more of these rubber polymer. Among them, it is preferable that the rubbery polymer layer is made of an acrylic rubber, a conjugated diene-based polymer and / or a hydrogenated product of the conjugated diene-based polymer.

In the multilayer polymer particles, it is preferable that the rubbery polymer layer has a crosslinked molecular structure in that rubber elasticity can be exhibited in a wide temperature range. Further, it is preferable that one rubbery polymer layer and a hard polymer layer or another rubbery polymer layer adjacent thereto are chemically bonded. The particle size of the multilayer polymer particles is not particularly limited,
In general, having an average particle size of about 0.05 to 1 μm is effective for improving dispersibility in a thermoplastic resin composition, impact resistance of a thermoplastic resin molded product, and surface uniformity. It is preferable from the point of view. In the multilayer polymer particles, the proportion of the hard polymer layer is 5 to 50% by weight and the proportion of the rubbery polymer layer is about 50 to 95% by weight. It is preferable from the viewpoints of the dispersibility in a thermoplastic resin molded article, the effect of exhibiting impact resistance, the extrusion stability, and the like.

Further, the inorganic filler used in the thermoplastic resin composition of the present invention has a function of reducing the linear expansion coefficient of the thermoplastic resin molded product, and therefore has a function of cooling when the thermoplastic resin molded product is heated. It contributes to reducing the distortion rate and improving the impact resistance of the processed product. In addition, inorganic fillers
This also contributes to a reduction in warpage that is likely to occur when a thermoplastic resin molded article is bonded to another material such as plywood simultaneously with heat processing.

The content of the inorganic filler in the thermoplastic resin composition is, as described above, 100% of the thermoplastic resin composition.
Parts by weight (1 part of the thermoplastic resin composition including the inorganic filler)
(00 parts by weight), preferably 10 to 40 parts by weight, more preferably 20 to 30 parts by weight. When the content of the inorganic filler is less than the above 10 parts by weight, the processed product obtained by heating the thermoplastic resin molded product may be warped, and it may be difficult to form a composite with another material, It tends to have low impact resistance. On the other hand, when the content of the inorganic filler exceeds 40 parts by weight, the rigidity of the thermoplastic resin molded article is increased, and the impact resistance is liable to be lowered.

As the inorganic filler, a polybutylene terephthalate-based resin is used in order to obtain a thermoplastic resin molded article having excellent gloss, transparency, and high quality.
Refractive index of a mixture of polyethylene terephthalate resin and (meth) acrylic resin (generally 1.51 to 1.5
An inorganic filler having a refractive index close to about 6) is preferably used.

The inorganic filler has a Mohs hardness of 4
It is preferred that: When an inorganic filler having a Mohs hardness of 4 or less is used, when the inorganic filler and the multilayer polymer particles are mixed and melt-kneaded with an extruder or the like in a resin material, equipment such as an inner wall or a screw of a melt-kneading apparatus is used. Is prevented from being scratched and worn by the inorganic filler,
The service life of the equipment can be increased, and furthermore, the mixing of metal powder generated by the abrasion and abrasion of the equipment in the thermoplastic resin molded article is eliminated, so that the color tone of the thermoplastic resin molded article is improved, and for example, dyes and pigments are improved. When manufacturing a colored thermoplastic resin article by adding and mixing, coloring can be performed freely and sharply, and furthermore, deterioration of the thermoplastic resin article due to the metal powder can be prevented.

Further, the inorganic filler preferably has an average particle size of 1 to 10 μm from the viewpoint of dispersibility in the resin, surface smoothness and mechanical properties of the obtained thermoplastic resin molded article. . When the average particle size of the inorganic filler is less than 1 μm, the dispersibility in the resin is reduced, and the mechanical properties such as the smoothness and the bending strength of the surface of the thermoplastic resin molded article are easily reduced. If it exceeds, the glossiness of the thermoplastic resin molded article is reduced, and it is likely to have no luxury.

In the present invention, any inorganic filler that satisfies the above conditions is preferably used. Representative examples of the inorganic filler preferably used include calcium carbonate, magnesium hydroxide, non-binding silica, and talc. And clay. These inorganic fillers may be used alone or in combination of two or more.

In the present invention, in addition to the above components,
Organic and / or inorganic dyes and pigments having a particle size of from 10 to 10 as required within a range not to impair the objects and effects of the invention.
One or more kinds of mica, natural stone powder, glass flake, crosslinkable synthetic resin powder of about 500 μm, and the like may be used. Further, in the present invention, in addition to the above-mentioned components, as long as the effects of the present invention and the effects thereof are not impaired, if necessary, an antibacterial agent, a fungicide, an antioxidant, a thermal decomposition inhibitor, a light stabilizer, an ultraviolet ray Absorbent, flame retardant, flame retardant aid, reinforcing agent, crystallization accelerator, terminal sealant, release agent, antistatic agent,
One or two of hydrolysis inhibitors, adhesion aids, adhesives, etc.
More than one species may be used.

The thermoplastic resin composition of the present invention described above using a polybutylene terephthalate resin, a polyethylene terephthalate resin, a (meth) acrylic resin, a polymer having a multilayer structure, an inorganic filler and other components as required. In producing the product, the production method is not particularly limited, and any method can be employed as long as the components can be uniformly mixed. Although not limited, for example, a polybutylene terephthalate-based resin, a polyethylene terephthalate-based resin, a (meth) After pre-mixing acrylic resin, multilayer polymer particles, inorganic filler and other components as required at a predetermined ratio, a single-screw extruder or a twin-screw extruder,
Using a mixing roll, Banbury mixer, etc.
The thermoplastic resin composition of the present invention can be obtained by melt mixing under heating in a batch system or a continuous system. In this case, it is generally preferable to perform the melt mixing at a temperature of about 240 to 285 ° C. The thermoplastic resin composition obtained thereby can be further formed into pellets or other forms as necessary.

In producing a thermoplastic resin molded article using the above-described thermoplastic resin composition, a molding method generally used for a thermoplastic resin or a composition thereof is used.
Molding can be performed using a molding device, for example, extrusion molding, injection molding, blow molding, calendar molding, casting,
Various molded products can be manufactured by press molding or the like. The shape, structure, dimensions, and the like of the thermoplastic resin molded article of the present invention are not particularly limited, and can be determined according to the purpose of use or application. The thermoplastic resin molded product obtained thereby may be used as it is, or may be subjected to secondary molding or processing by bending, compression molding, vacuum molding or the like.

Among them, the glossiness of at least one surface is 80% or more, and the glass transition temperature is 20 ° C. to 1 ° C.
The common logarithm of the storage modulus in the temperature range higher by 00 ° C. is 7 to 8
MPa, the cooling strain rate when cooled from 130 ° C. to a temperature of 50 ° C. is 1.0 kg / cm ² · ° C. or less, and the Izod impact strength is 2.0 kj / m ² or more. The thermoplastic resin molded article of the present invention, particularly a plate-shaped thermoplastic resin molded article, is excellent in heat workability, particularly excellent in bending workability under heating, and when subjected to heat processing, by cooling, Extremely low residual strain,
For this reason, it is possible to obtain processed products with excellent mechanical properties such as impact resistance, and by utilizing such properties, top plates for system kitchens, doors, walls, top plates for vanities, and waist walls for unit baths. , Apron, bay window counter, etc. can be effectively used for interior materials and equipment for housing.

In particular, the present invention described above contains a polybutylene terephthalate resin, a polyethylene terephthalate resin, a (meth) acrylic resin, a multilayer polymer particle, an inorganic filler and, if necessary, other components. When a thermoplastic resin composition is used, a molded article such as a plate-like body can be smoothly obtained with high productivity by extrusion molding. The extrusion molding method and the extrusion molding device at that time are not particularly limited, and the extrusion molding method and the extrusion molding device conventionally used for the thermoplastic resin and its composition can be used. Although not limited, for example, using a single-screw extruder having an I-die, a T-die, a coat hanger die and the like arranged in a head portion, the thermoplastic resin composition is melt-kneaded at a cylinder temperature of 240 to 280 ° C. Guiding the molten resin composition to a die set at a temperature of about 255 to 265 ° C., flowing it out of the die, and cooling the discharged molten resin composition between a plurality of vertically or horizontally arranged nip rolls. Thereby, a plate-shaped thermoplastic resin molded product can be obtained with high productivity.

When the thermoplastic resin molded article of the present invention is a plate-like body, if the plate thickness is set to 3 mm or less, the heat conductivity becomes good and the heating is performed uniformly during bending. In addition, the internal residual strain in the bent product is further reduced, the impact resistance is improved, and the occurrence of cracks and breakage in and around the bent portion is more effectively prevented. Further, in performing the heat processing such as bending using the thermoplastic resin molded article of the present invention, it is possible to perform the heat processing using the thermoplastic resin molded article alone, or plywood, calcium silicate plate, slate plate A composite product may be manufactured by performing a heating process in combination with a steel plate having a thickness of 2 mm or less and other materials. And when performing the heating process using the thermoplastic resin molded product of the present invention, the heating process of the thermoplastic resin molded product, and the bonding between the thermoplastic resin molded product and the plywood and other materials described above are performed simultaneously. Can be.

[0052]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto. In the following examples, the surface gloss of the thermoplastic resin molded product (plate-like thermoplastic resin molded product) is 20 ° C. from the glass transition temperature.
Common logarithm of storage elastic modulus in the temperature range of 〜100 ° C. higher, 1
The cooling strain rate when cooled from 30 ° C. to 50 ° C. and the Izod impact strength were determined as follows.

[Glossiness of Surface of Thermoplastic Resin Molded Product] A plate-shaped thermoplastic resin molded product produced in the following Examples or Comparative Examples was cut with a running saw to obtain a test piece (length × width × thickness = 50 mm x 50 mm x 1.2 mm) was manufactured and a digital gonio-gloss meter ("UGV-
D)), the 60 ° specular gloss (%) of one surface of the test piece was measured in accordance with JIS K 7105.

[Common Logarithm of Storage Elastic Modulus of Thermoplastic Resin Molded Product] (1) A plate-shaped thermoplastic resin molded product produced in the following Examples or Comparative Examples was cut with a running saw to obtain a test piece (width × width). (Length x thickness = 8 mm x 50 mm x 1.2 mm), and using a dynamic viscoelasticity measurement device ("PL-DMTA" manufactured by Polymer Laboratories), the following was placed at the center in the longitudinal direction of the test piece. A sinusoidal stress of bending is applied while raising the temperature under the conditions, and the sinusoidal loss is measured as a function of the temperature from the ratio of the out-of-phase stress component to the strain amplitude, and the α-dispersion peak temperature of the loss modulus is defined as the glass transition temperature. The storage elastic modulus in the temperature range of 20 ° C. to 100 ° C. higher than the glass transition temperature was read, and the common logarithm was obtained to obtain the common logarithm of the storage elastic modulus of the thermoplastic resin molded article.

Measurement conditions Measurement frequency: 1 Hz Dynamic strain amount: 32 μm Measurement mode: Dual Cantilever beam Drive clamp: Knife Edge 5 mm Width Frame length: 16 mm Measurement temperature: 30 to 250 ° C. Heating condition: 3 ° C./min

[Cooling Strain Rate of Thermoplastic Resin Molded Product] A dumbbell-shaped test piece conforming to TYPE-1 of ASTM-D638 is prepared from a plate-shaped thermoplastic resin molded product produced in the following Examples or Comparative Examples. Then, the cooling strain of the test piece was measured using a tensile tester for measuring the cooling strain. That is, as a tensile tester, a device in which a thermostat, a 100 kgf load cell and a tensile jig were attached to “Autograph AGS100G-2000B” manufactured by Shimadzu Corporation was used, and a test piece was attached to a sample fixing portion above the tensile jig. After preheating the test piece to a temperature of 130 ° C., the lower end of the test piece is fixed to the sample fixing portion below the pulling jig, the door of the thermostat is closed and heated for 5 minutes,
When the temperature of the entire test piece reaches 130 ° C., 100 m
The test pieces fixed by the upper sample fixing part and the lower sample fixing part at an interval of m are stretched by 10% at a crosshead speed of 100 mm / min.
After holding for 1 minute, the temperature of the thermostat is raised at a rate of 1 ° C./5 minutes for 5 minutes.
The temperature was lowered to 0 ° C., and the stress generated at that time was read from the load value of the load cell attached to the upper part of the sample fixing portion, and the temperature was changed from 130 ° C. to 130 ° C. in the test piece (thermoplastic resin molded product) by the following equation 1. The cooling strain rate when cooled to 50 ° C. was determined.

[0057]

## EQU1 ## Cooling strain rate (kg / cm ² · ° C.) = (W ₁₃₀ −W
₅₀ ) / (130 ° C.-50 ° C.) where W ₁₃₀ = load value at load cell at temperature of 130 ° C. (kg / cm ² ) W ₅₀ = load value at load cell at temperature of 50 ° C. (kg
/ Cm ² )

[Izod Impact Strength of Thermoplastic Resin Molded Product] Using a plate-shaped thermoplastic resin molded product manufactured in the following Examples or Comparative Examples, an Izod impact strength tester (stock) according to JIS K 7110 was used. Notched Izod impact strength was measured at 23 ° C. using a Toyo Seiki Seisakusho Co., Ltd.).

Further, a composite of a plate-shaped thermoplastic resin molded product (resin plate) and a plywood (backing material) is prepared by the following method, and its falling ball impact strength, warpage, and coefficient of linear expansion of the resin plate are prepared. Was measured as follows.

[Preparation of Composite of Resin Plate and Plywood] A method of preparing a composite will be described with reference to FIGS. (1) Production of backing material: width 1800 mm, thickness 18 mm
Fully water-resistant plywood (Type 1 plywood manufactured by Yuasa Corporation)
From, using a circular saw, length 450mm × width 1800mm
And a plate having a length of 50 mm and a width of 1800 mm are cut out, and one of the cut ends of each plate is processed into a curved surface having a radius of curvature (R) of 18 mm using a planar, As shown in FIG. 1A, a processed plate 1 and a processed plate 2 were manufactured in which one edge of the plate was processed into a curved surface having a circumference of 1/4. Next, an adhesive (vinyl acetate emulsion adhesive; manufactured by Konishi Co., Ltd.) is applied to the opposite surfaces of the curved edge portions of the processed plate 1 and the processed plate 2 in order to obtain a cut edge having a half circumference. CH-18 "), and then pressure-bonded with both applied surfaces in contact with each other to form a curved surface having a radius of curvature (R) of 18 mm with a １ ／ circumference on one side in the longitudinal direction. The backing material 3 shown in FIG. 1B was manufactured.

(2) Adhesion between resin plate and backing material: A resin plate 4 having a length of 540 mm and a width of 1800 mm is cut out from a plate-shaped thermoplastic resin molded product manufactured in the following Examples or Comparative Examples. And backing material 3 produced in (1) above
A solvent type rubber-based adhesive (“Hybon 1887” manufactured by Hitachi Chemical Co., Ltd.) is spray-coated on the adhesive surface of
After the solvent contained in the adhesive was blown off by air drying for a minute, as shown in FIG. 2A, the resin plate 4 slightly protruded from the edge of the backing material 3 where the curved surface was not processed. The resin plate 4 and the backing material 3 are superimposed and 5 kg / cm ²
Under the pressure of the above, the flat portions were bonded.

(3) Bending under heating: Using an iron bender type post-form molding machine (“PE10 / 42” manufactured by Brandt) with the resin plate 4 on the table of the molding machine. The laminate manufactured in the above (2) was installed and fixed. The temperature of the resin plate is 125-145
° C, the temperature of the heater bar of the molding machine and the contact time of the heater bar with the resin plate 4 are selected, and under the above conditions, an air cylinder attached to the heater bar is used to drive through synthetic paper (not shown). By pressing the heater bar against the surface of the resin plate 3 to move the heater bar along the curved surface of the backing material 3 to the lower surface (wraparound portion) as shown in FIGS. 2B to 2D. The bending process of the end portion of the resin plate 4 and the bonding process of the resin plate 4 and the backing material 3 are simultaneously performed, and the resin plate 4 and the backing material (plywood) 3 shown in FIG.
To produce composite 5.

[Falling Ball Impact Strength of Composite] Using the composite 5 obtained above, JIS K 7211 and JI
A falling ball impact test was performed according to SA4401. That is, the mass was 28.1 g, 500 g, and 1000 using a column / drop weight detaching device (manufactured by Toyo Seiki Seisaku-sho, Ltd.)
The falling ball impact test was performed using a spherical falling weight of g and changing the height at which the falling weight was dropped. At this time, the test of the top plate portion (resin plate) of the composite was carried out by placing the resin plate side of the composite 5 on the wood (specific gravity 0.7 or more, thickness 3 cm) placed on a smooth concrete floor. The falling weight was dropped in a state where it was placed so as to be a falling ball collision surface). In the test of the curved surface processed portion (R portion) of the composite 5, the composite 5 was disposed vertically with its long side 6 in contact with the concrete floor surface, and the curved surface processed portion (R portion) of the composite 5 was placed. ), The falling weight was dropped vertically. The maximum value of the product (cm) of the mass (kg) of the falling weight and the falling height when the composite 5 was not damaged was defined as the falling ball impact strength (kg · cm).

[Composite warpage] The composite 5 is vertically supported without any extra external force so that the long side 6 of the composite 5 is in contact with the floor surface, and the composite 5 is raised 25 m from the center P of the bent portion.
m, a stainless steel wire (diameter: 0.2 mm) 9 is stretched horizontally from one short side 7 to the other short side 8 of the composite 5, and the plane of the wire 9, the composite 5 and the wire 9 Was measured with a gap gauge. A wire 9 is stretched in the same manner for the backing material 3 before bonding to the resin plate 4, and the maximum gap dimension (C) (mm) generated between the wire 9 and the plane of the backing material 3 is measured with a gap gauge. The measurement was made in advance, and the warpage of the composite 5 was determined by the following equation (2).

[0065]

## EQU2 ## Warpage of the composite (mm) = D (mm) -C (mm)

[Coefficient of linear expansion of resin body] A resin plate (about 5 mm
× 15 mm × predetermined thickness) and a thermal analyzer (TMA4000 of System 001) manufactured by Mac Science Co., Ltd. in accordance with ASTM D 696 under the following conditions at a reference temperature of the second run of 30 to 80 ° C. The linear expansion coefficient of the resin plate was determined from the data. Condition ○ constant load: 10 g ○ heating rate: 30 ° C. / min ○ Cycle: room temperature to 200 DEG ° C. in heated, was gradually cooled to room temperature, warmed to room temperature to 200 DEG ° C. [second run (2nd Ru
n)]

<< Synthesis Example 1 >> [Production of polybutylene terephthalate] 88 parts by weight of dimethyl terephthalate, 49 parts by weight of 1,4-butanediol and 0.0035 parts by weight of tetraisopropyl titanate were charged into a reaction vessel, and 170 parts by weight under normal pressure.
The ester exchange reaction was performed while gradually raising the temperature from 230 ° C. to 230 ° C. When 28 parts by weight of methanol flowed out,
0.2m while raising the temperature from 230 ° C to 250 ° C
The pressure was reduced to mHg, and the state was maintained for about 2 hours to perform a polycondensation reaction. Next, nitrogen gas was supplied to the reaction tank to return to normal pressure, and the reaction was stopped. As a result, polybutylene terephthalate (hereinafter, referred to as “PBT-1”) having an intrinsic viscosity of 1.15 dl / g measured in a phenol / tetrachloroethane mixed solvent (1/1 weight ratio) was obtained.

<< Synthesis Example 2 >> [Production of polybutylene terephthalate] 100 parts by weight of dimethyl terephthalate, 60 parts by weight of 1,4-butanediol and 0.004 parts by weight of tetraisopropyl titanate were charged into a reaction vessel, and 145 were placed under normal pressure. ° C
The ester exchange reaction was carried out while gradually raising the temperature to 230 ° C., and when 26 parts by weight of methanol flowed out, the temperature was raised to 240 ° C., and the pressure was reduced to 0.2 mmHg. The polycondensation reaction was performed while keeping the temperature. Next, nitrogen gas was supplied to the reaction tank to return to normal pressure, and the reaction was stopped. As a result, polybutylene terephthalate (hereinafter, referred to as “PBT-2”) having an intrinsic viscosity of 0.90 dl / g measured in a phenol / tetrachloroethane mixed solvent (1/1 weight ratio) was obtained.

<< Synthesis Example 3 >> [Production of polyethylene terephthalate] 97 parts by weight of dimethyl terephthalate, 64 parts by weight of ethylene glycol and 0.03 parts by weight of manganese acetate were charged into a reaction vessel and gradually heated from 140 ° C. to 230 ° C. under normal pressure. The ester exchange reaction is carried out while the temperature is raised to
When 8 parts by weight flowed out, 0.04 parts by weight of antimony trioxide was added. When a total of 32 parts by weight of methanol flowed out, 0.02 parts by weight of trimethyl phosphate was added to stop the transesterification reaction. Next, while increasing the temperature to 280 ° C., the pressure of the reaction vessel was increased to 0.2 mmH.
g, and the polycondensation reaction was carried out while maintaining the state for about 3 hours. Next, nitrogen gas was supplied to the reaction tank to return to normal pressure, and the reaction was stopped. Thereby, phenol /
Polyethylene terephthalate (hereinafter, referred to as “PET”) having an intrinsic viscosity of 0.60 dl / g measured in a mixed solvent of tetrachloroethane (1/1 weight ratio) was obtained.

<< Production Example 1 >> [Production of Multilayered Polymer Particles] (1) In a polymerization vessel equipped with a stirrer, a cooling pipe and a dropping funnel, under a nitrogen atmosphere, 600 parts by weight of distilled water, lauryl sarcosine acid 0.168 parts by weight of sodium and 2.1 parts by weight of sodium stearate were added, and dissolved by heating to 70 ° C. Then, butyl acrylate 150
Parts by weight and 0.15 parts by weight of allyl methacrylate were added and stirred for 30 minutes.
The polymerization was started by adding 15 parts by weight. Four hours later, it was confirmed by gas chromatography that all of the monomers had been consumed, and a copolymer of butyl acrylate and allyl methacrylate had been formed in the polymerization vessel. (2) Then, after adding 0.15 parts by weight of potassium peroxydisulfide to a reactor containing the copolymer, a mixture of 48 parts by weight of methyl methacrylate and 2.0 parts by weight of ethyl acrylate was added from a dropping funnel. The mixture was added dropwise over 2 hours, and then a polymerization reaction was performed for 30 minutes to obtain a latex containing multilayer polymer particles having an average particle diameter of 0.3 μm. (3) After coagulating the latex obtained in the above (2) at −20 ° C. for 24 hours, the coagulated product is taken out,
Was washed three times with hot water, and then dried under reduced pressure at 80 ° C. for 2 days to obtain multilayer-structured polymer particles. The glass transition temperature of the outermost layer of the obtained multilayer polymer particles was 105 ° C.

The contents of the acrylic resin and the inorganic filler used in the following Examples and Comparative Examples are as follows. ○ Acrylic resin : 94% by weight of methyl methacrylate unit
And a copolymer of 6% by weight of methyl acrylate units [degree of polymerization 1300, melt flow index 15.1 / 10
(ASTM D1238 1 condition)] Acrylic resin : 88% by weight of methyl methacrylate unit
And a copolymer of methyl acrylate units 12% by weight [degree of polymerization 1600, melt flow index 3.3 / 10
(ASTM D1238 1 condition)] Inorganic filler : (1) Calcium carbonate (“Whiten P-30” manufactured by Shiraishi Industry Co., Ltd.) (2) Talc (“Micron White # manufactured by Hayashi Kasei Co., Ltd.)
2000S ")

Example 1 (1) Polybutylene terephthalate produced in Synthesis Example 1 or 2, polyethylene terephthalate produced in Synthesis Example 3, the above-mentioned acrylic resin, or multilayer polymer particles produced in Production Example 1, The above-mentioned inorganic filler is mixed in advance in a ratio shown in Table 1 or 2 using a high-speed rotary mixer ("Super Mixer" manufactured by Kawada Seisakusho Co., Ltd.), and the resulting mixture is mixed in the same direction. Rotary twin screw extruder (“BT-40” manufactured by Nippon Kogyo Co., Ltd.)
And melt-kneaded under the conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 150 rpm.
Extruded into a water bath at a water temperature of 35 ° C. from a die at a temperature of 35 ° C., and when the temperature of the strand reached 60 ° C., it was pulled and cut by a rotary blade type cutter, and pellets of a thermoplastic resin composition (diameter 3 mm, length 3.5 mm). (2) The pellets of the thermoplastic resin composition obtained in the above (1) are subjected to a vented single-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a coat hanger die (1000 mm in width), a polishing roll (three vertical type). It is supplied to a plate-like body manufacturing device consisting of a belt drive type using a cooling roll) and a take-off machine (also used for applying a masking material), and the cylinder temperature of the feed section of the extruder is 288 ° C, the other cylinder temperature is 265 ° C, and the screw rotates. Several hundred rpm, die temperature 260 ° C., die lip opening 2.5 mm, distance between die and first roll 100 mm, polishing roll temperature 80 ° C. upper roll, 90 ° C. intermediate roll, 70 lower rolls
The molding was carried out under the conditions of a temperature of ° C. and a line speed of 1.84 m / min to produce a plate-shaped thermoplastic resin molded product having a thickness of 1.2 mm and a width of 985 mm.

(3) From the glossiness and the glass transition temperature of the surface of the plate-shaped thermoplastic resin molded product obtained in (2) above,
The common logarithm of the storage elastic modulus in the temperature range higher by 0 ° C. to 100 ° C., the cooling strain rate when cooled from 130 ° C. to 50 ° C., and the Izod impact strength were measured by the methods described above. Or, as shown in Table 2. Further, with respect to the composite 5 produced by the above-described method using the plate-like thermoplastic resin molded product (resin plate) obtained in the above (2), its falling ball impact strength, linear expansion coefficient and warpage are obtained. Was measured by the method described above, and the result was as shown in Table 1 or Table 2 below. (4) For reference, commercially available melamine decorative boards, crosslinked type methacrylic resin-based artificial marbles and unsaturated polyester resin-based artificial marbles were similarly measured for glossiness and storage modulus. The logarithm of the common use, the cooling strain rate, the Izod impact strength, the impact strength of a falling ball, the coefficient of linear expansion, and the warpage were examined.

Comparative Example 1 The polybutylene terephthalate produced in Synthesis Example 1 or 2, the polyethylene terephthalate produced in Synthesis Example 3, the acrylic resin described above, or the multilayer polymer particles produced in Production Example 1 and the inorganic particles described above A resin molded article and a composite were produced in the same manner as in Example 1 except that the use ratio of the filler was changed at the ratio shown in Table 3 below, and the various physical properties were the same as in Example 1. The results were as shown in Table 3 below.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

From the results of Tables 1, 2 and 3 above,
When the glossiness of at least one surface is 80% or more, the common logarithm of the storage elastic modulus in the temperature range of 20 ° C to 100 ° C higher than the glass transition temperature is 7 to 8 MPa, and when cooled from 130 ° C to 50 ° C. Has a cooling distortion rate of 1.0 kg / c
m ² · ° C or less and Izod impact strength of 2.0
The thermoplastic resin molded products of Experiment Nos. 1 to 6 having a kj / m ² or more have high glossiness on the surface, excellent appearance, and excellent impact resistance, and heat the thermoplastic resin molded products. It can be seen that when the bending process is performed downward, a processed product with little internal distortion, extremely small warpage, excellent impact resistance, and no cracking or breakage can be obtained. further,
From the results in Tables 1, 2 and 3, the thermoplastic resin molded products having the above-mentioned excellent properties are polybutylene terephthalate resin, polyethylene terephthalate resin, (meth) acrylic resin, and multilayer polymer. It can be seen that a thermoplastic resin composition containing particles and an inorganic filler, particularly a thermoplastic resin composition containing those components in the above-described specific ratio, can be obtained smoothly.

[0079]

The thermoplastic resin molded article of the present invention has excellent surface gloss, is transparent, has a clear color tone, has a high-grade feel, and has been subjected to heat processing or other processing as it is. It can be effectively used for various applications as a processed product. In particular, the thermoplastic resin molded article of the present invention is excellent in bending workability under heating, and therefore, easily and smoothly under heating without using various bending structures and curves without cutting or polishing. It can be a product with dimensions. In addition, when the thermoplastic resin molded product of the present invention is used, the internal strain in the processed product is reduced due to the small cooling strain during the heating process, whereby the impact resistance is excellent, and cracks and breakage do not occur. A processed product can be obtained. The thermoplastic resin molded product of the present invention makes use of the above-described characteristics to provide a home interior such as a system kitchen top plate, a door, a wall, a vanity top plate, a unit bath waist wall, an apron, and a bay window counter. It can be used effectively for a wide range of applications including materials and equipment.

The thermoplastic resin composition of the present invention, which contains a polybutylene terephthalate resin, a polyethylene terephthalate resin, a (meth) acrylic resin, multilayer polymer particles, and an inorganic filler, particularly, a polybutylene terephthalate resin The weight ratio of the resin to the polyethylene terephthalate resin is from 4: 1 to 1: 1. The total amount of the polybutylene terephthalate resin and the polyethylene terephthalate resin is 100 parts by weight, and the amount of the (meth) acrylic resin is 20 to 200 parts by weight. In a proportion of 10 to 100 parts by weight of the multi-layered polymer particles with respect to 100 parts by weight of the total of the polybutylene terephthalate resin, the polyethylene terephthalate resin and the (meth) acrylic resin. Inorganic filler to 100 parts by weight of the plastic resin composition When the thermoplastic resin composition of the present invention containing 0 to 40 parts by weight is used, a thermoplastic resin molded product having the above-mentioned excellent properties can be produced at a high production rate by extrusion molding or other hot melt molding. And can be easily and smoothly manufactured.

[Brief description of the drawings]

FIG. 1 is a diagram showing a backing material used in Examples in the present specification.

FIG. 2 is a diagram showing a process for producing a composite and a composite obtained thereby in the examples of the present specification.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Processing plate 2 Processing plate 3 Backing material 4 Resin plate 5 Composite 6 Long side 7 Short side 8 Short side 9 Wire

Claims (9)

[Claims] The glossiness of at least one surface is 80% or more, the common logarithm of the storage modulus in the temperature range of 20 ° C. to 100 ° C. higher than the glass transition temperature is 7 to 8 MPa, and 130 ° C. to 50 ° C. A thermoplastic resin molded article having a cooling strain rate of 1.0 kg / cm ² · ° C. or less when cooled to 0 ° C. and an Izod impact strength of 2.0 kj / m ² or more. 2. The thermoplastic resin molded article according to claim 1, which is a plate-like body. 3. (A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, (C)
The thermoplastic resin molded product according to claim 1 or 2, comprising a thermoplastic resin composition containing (meth) acrylic resin, (D) multilayer polymer particles, and (E) an inorganic filler. 4. The weight ratio of (i) polybutylene terephthalate resin: polyethylene terephthalate resin is 4:
(Ii) polybutylene terephthalate resin and polyethylene terephthalate resin in total of 10
20 to 20 parts by weight of (meth) acrylic resin
0 parts by weight, and (iii) 10 to 100 parts by weight of the multilayer structure polymer particles based on 100 parts by weight of the total of the polybutylene terephthalate resin, the polyethylene terephthalate resin and the (meth) acrylic resin. The thermoplastic resin molded product according to claim 3, which comprises a thermoplastic resin composition containing (iv) 10 to 40 parts by weight of an inorganic filler based on 100 parts by weight of the thermoplastic resin composition. 5. The composite material according to claim 1, which is compounded with another material.
5. The thermoplastic resin molded article according to any one of the above items 4. 6. A processed product obtained by subjecting the thermoplastic resin molded product according to claim 1 to heat processing. 7. (A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, (C)
A thermoplastic resin composition comprising a (meth) acrylic resin, (D) multilayer polymer particles, and (E) an inorganic filler. 8. (i) The weight ratio of polybutylene terephthalate resin to polyethylene terephthalate resin is 4:
(Ii) polybutylene terephthalate resin and polyethylene terephthalate resin in total of 10
20 to 20 parts by weight of (meth) acrylic resin
0 parts by weight, and (iii) 10 to 100 parts by weight of the multilayer structure polymer particles based on 100 parts by weight of the total of the polybutylene terephthalate resin, the polyethylene terephthalate resin and the (meth) acrylic resin. The thermoplastic resin composition according to claim 7, which further comprises (iv) 10 to 40 parts by weight of an inorganic filler based on 100 parts by weight of the thermoplastic resin composition. 9. A method for producing a thermoplastic resin molded article by extrusion molding using the thermoplastic resin composition according to claim 7.