WO2019167292A1

WO2019167292A1 - Molding of polybutylene terephthalate resin composition

Info

Publication number: WO2019167292A1
Application number: PCT/JP2018/016019
Authority: WO
Inventors: 創貴吉田; 山中　康史
Original assignee: 三菱エンジニアリングプラスチックス株式会社
Priority date: 2018-03-01
Filing date: 2018-04-18
Publication date: 2019-09-06
Also published as: CN111788257A; CN111788257B

Abstract

This molding has a minimum thickness of more than 1 mm, has a sea-island structure, and is formed of a polybutylene terephthalate resin composition containing, as a styrene copolymer (B), a total amount of 45-100 parts by mass of an acrylonitrile-styrene copolymer (B1) and/or an epoxy-modified acrylonitrile-styrene copolymer (B2) with respect to 100 parts by mass of a polybutylene terephthalate resin (A). The molding is characterized in that: the polybutylene terephthalate resin (A) forms a continuous phase; the molding has a morphology in which domains including the styrene copolymer (B) are dispersed as island-like parts within the continuous phase of the polybutylene terephthalate resin (A), at least a portion of the island-like parts include the phase of the polybutylene terephthalate resin (A) in a lake-like manner, and the maximum value of the width of the island-like parts is at most 6 μm; and a total volatile organic compound (TVOC) amount of at most 30 μgC/g is detected when a gas generated by heat-treating the molding at 120°C for 5 hours is analyzed by gas chromatography.

Description

Polybutylene terephthalate resin composition molded article

The present invention relates to a molded article of a polybutylene terephthalate resin composition, and more particularly, to a molded article of a polybutylene terephthalate resin composition having low warpage and low specific gravity, a small amount of gas generation, and excellent mechanical properties at high temperatures.

Polybutylene terephthalate resin has excellent mechanical and electrical properties, as well as excellent chemical resistance and heat resistance. Injection molded products are used for various electrical and electronic equipment parts and automobiles. It is widely used as an interior part for vehicles and other general industrial products.

However, since polybutylene terephthalate resin is a crystalline resin, in its injection molding, shrinkage occurs due to crystallization of the resin in the process of cooling and solidifying in the mold, and thus molding shrinkage tends to occur. Since the degree of the molding shrinkage differs for each part of the molded product, the molded product is warped.

In order to suppress molding shrinkage, it is known to incorporate an amorphous resin in order to suppress molecular orientation due to crystallization of polybutylene terephthalate resin. As the amorphous resin, acrylonitrile-styrene copolymer is used. It has been proposed to use (see Patent Documents 1 to 3).

Japanese Patent Laid-Open No. 09-12849 JP 2006-16558 A International Publication No. 2016/190311

However, even with these inventions, it is not easy to achieve a sufficiently low warpage.
In addition, when polybutylene terephthalate resin material is used in the interior of an automobile, there is a regulation on TVOC (total volatile organic compounds), which is a strict guideline for the organic matter to be released. There is a strong demand for this.
An object (issue) of the present invention is to provide a polybutylene terephthalate resin composition molded article having low warpage and low specific gravity, a small amount of gas generation, and excellent mechanical properties at high temperatures.

As a result of diligent studies to solve the above-mentioned problems, the inventors of the present invention contain a specific amount of acrylonitrile-styrene copolymer relative to the polybutylene terephthalate resin, and the domain of the acrylonitrile-styrene copolymer Has found that a polybutylene terephthalate resin composition molded article having a sea-island structure dispersed in islands in a specific shape and having a specific TVOC amount can solve the problems described above.
The present invention relates to the following polybutylene terephthalate resin composition molded article.

[1] Acrylonitrile-styrene copolymer (B1) and / or epoxy-modified acrylonitrile-styrene copolymer as styrene copolymer (B) with respect to 100 parts by mass of polybutylene terephthalate resin (A) A molded body comprising a polybutylene terephthalate resin composition containing 45 to 100 parts by mass of (B2), having a sea-island structure, and having a minimum thickness of more than 1 mm,
The polybutylene terephthalate resin (A) forms a continuous phase,
The domain containing the styrene copolymer (B) is dispersed in an island shape in the continuous phase of the polybutylene terephthalate resin (A), and at least a part of the domain is in the island-shaped portion. The phase of A) exists as a lake, and has a morphology in which the maximum width of the island-shaped part measured by the following method is 6 μm or less,
The amount of volatile organic compounds (TVOC) detected when a gas generated by heat-treating the molded body at 120 ° C. for 5 hours is analyzed by gas chromatography is 30 μg C / g or less.
A molded article of polybutylene terephthalate resin composition characterized by the above.
How to measure the maximum width of islands:
The maximum value of the width of the island portion is measured from the SEM image (magnification is 3000 times) in the cross section including the center point in the thickness direction of the portion where the thickness of the molded body is maximum.
[2] The polybutylene terephthalate resin composition molded article according to the above [1], wherein at least a part of the island-shaped portion of the polybutylene terephthalate resin (A) is an island-shaped portion having a branched portion.
[3] The polybutylene terephthalate resin composition molded article according to the above [1] or [2], wherein the TVOC amount from the molded article is 20 μg C / g or less.
[4] The amount of the styrene monomer detected when a gas generated by heat-treating the polybutylene terephthalate resin composition at 270 ° C. for 10 minutes is analyzed by gas chromatography is 45 ppm by mass or less. ] A molded article of the polybutylene terephthalate resin composition according to any one of [3] to [3].
[5] The polybutylene terephthalate resin composition molded article according to any one of the above [1] to [4], wherein the polybutylene terephthalate resin composition further contains an epoxy-modified acrylic polymer (C).
[6] The polybutylene terephthalate resin composition comprises 45 to 100 parts by mass of an acrylonitrile-styrene copolymer (B1) with respect to 100 parts by mass of the polybutylene terephthalate resin (A), and an epoxy-modified acrylic polymer (C). The polybutylene terephthalate resin composition molded article according to any one of the above [1] to [5], comprising 0.2 to 3 parts by mass and glass fiber (D) 10 to 100 parts by mass.
[7] The polybutylene terephthalate resin composition is a total of acrylonitrile-styrene copolymer (B1) and epoxy-modified acrylonitrile-styrene copolymer (B2) with respect to 100 parts by mass of the polybutylene terephthalate resin (A). The content ratio of (B1) and (B2) is 6 or less, and the glass fiber (D) is contained in an amount of 10 to 100 parts by mass. [1] A molded article of the polybutylene terephthalate resin composition according to any one of [4].
[8] The molded body according to any one of [1] to [7], which is a vehicle interior part.

[9] With respect to 100 parts by mass of the polybutylene terephthalate resin (A), 45 to 100 parts by mass of the acrylonitrile-styrene copolymer (B1), 0.2 to 3 parts by mass of the epoxy-modified acrylic polymer (C), And a polybutylene terephthalate resin composition comprising 10 to 100 parts by mass of glass fiber (D).
[10] In the above [9], the amount of the styrene monomer detected when the gas generated by heat-treating the polybutylene terephthalate resin composition at 270 ° C. for 10 minutes is analyzed by gas chromatography is 45 ppm or less. The polybutylene terephthalate resin composition described.
[11] The polybutylene terephthalate resin composition according to the above [9] or [10], wherein the acrylonitrile-styrene copolymer (B1) is a bulk polymer.
[12] Containing 45 to 100 parts by mass of acrylonitrile-styrene copolymer (B1) and epoxy-modified acrylonitrile-styrene copolymer (B2) with respect to 100 parts by mass of polybutylene terephthalate resin (A). , (B1) and (B2) content mass ratio (B1) / (B2) is 6 or less, and further contains 10 to 100 parts by mass of glass fiber (D), polybutylene terephthalate resin Composition.
[13] The polybutylene terephthalate resin composition according to the above [12], wherein the mass ratio (B1) / (B2) of the contents of (B1) and (B2) is 0.5 to 6.
[14] The above [12], wherein the amount of styrene monomer detected when a gas generated by heat treatment of the polybutylene terephthalate resin composition at 270 ° C. for 10 minutes is analyzed by gas chromatography is 45 ppm or less The polybutylene terephthalate resin composition according to [13].
[15] The polybutylene terephthalate resin composition according to any one of [12] to [14] above, wherein the acrylonitrile-styrene copolymer (B1) is a bulk polymer.

The molded article of the polybutylene terephthalate resin composition of the present invention has less warpage, less gas generation, can meet VOC regulations, has low specific gravity, and has mechanical properties such as mechanical strength in an environment that assumes high temperature inside the vehicle. In particular, it can be suitably used as a vehicle interior part.

2 is a SEM image of the molded body of Example 1 using a scanning electron microscope. 3 is a SEM image of the molded product of Example 2 using a scanning electron microscope. 3 is a SEM image of the molded product of Example 3 using a scanning electron microscope. 6 is a SEM image of the molded product of Example 4 using a scanning electron microscope. 6 is a SEM image of the molded product of Example 7 using a scanning electron microscope. 10 is a SEM image of the molded product of Example 9 using a scanning electron microscope. 4 is a SEM image of the molded product of Example 11 using a scanning electron microscope. 2 is a SEM image of a molded article of Comparative Example 1 using a scanning electron microscope. 4 is a SEM image of a molded article of Comparative Example 2 using a scanning electron microscope. 6 is an SEM image of a molded article of Comparative Example 4 using a scanning electron microscope. It is a schematic diagram for showing the width | variety of the island-shaped part of the sea island structure of this invention.

Hereinafter, embodiments of the present invention will be described in detail. The following description may be made based on embodiments and specific examples, but the present invention is not construed as being limited to such embodiments and specific examples.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The molded article of the polybutylene terephthalate resin composition according to the first invention of the present application is an acrylonitrile-styrene copolymer (B1) and / or an epoxy-modified acrylonitrile-styrene copolymer as the styrene copolymer (B). A molded article comprising a polybutylene terephthalate resin composition containing 45 to 100 parts by mass of the polymer (B2), having a sea-island structure, and having a minimum thickness of more than 1 mm,
The polybutylene terephthalate resin (A) forms a continuous phase,
The domain containing the styrene copolymer (B) is dispersed in an island shape in the continuous phase of the polybutylene terephthalate resin (A), and at least a part of the domain is in the island-shaped portion. The phase of A) exists as a lake, and has a morphology in which the maximum width of the island-shaped part measured by the following method is 6 μm or less,
A volatile organic compound amount (TVOC) detected when a gas generated by heat-treating the molded body at 120 ° C. for 5 hours is analyzed by gas chromatography is 30 μg C / g or less.
How to measure the maximum width of islands:
The maximum value of the width of the island portion is measured from the SEM image (magnification is 3000 times) in the cross section including the center point in the thickness direction of the portion where the thickness of the molded body is maximum.

The molded product of the present invention has a minimum thickness of more than 1 mm, but the minimum thickness is preferably 1.2 mm or more, more preferably 1.5 mm or more, further preferably 1.8 mm or more, and particularly 2.0 mm or more. Preferably there is. The maximum thickness of the molded body is not limited, but is preferably 10.0 mm or less, more preferably 8.0 mm or less, and even more preferably 6.0 mm or less.

[Morphology]
The observation of the molded body morphology with a scanning electron microscope is performed using the SEM image obtained by the scanning electron microscope at the cross section including the center point in the thickness direction of the molded body, which is the thickest part (maximum thickness part). .
That is, first, in the maximum thickness part of a molded object, it cut | disconnects in the thickness direction. At this time, the injection gate portion at the time of molding is excluded as the maximum thickness portion of the molded body. In addition, when there are a plurality of maximum thickness portions in the molded body, from any one place, in the case of a molded body having a uniform thickness, the length of the injection gate portion and the flow end portion of the resin Cut near the center of the direction.
A sample for SEM observation having a cross section including the center point in the thickness direction of the cut surface is cut out from the cut surface with a diamond knife to obtain a block-shaped sample having an observation surface of 500 μm in length × 500 μm in width and about 1 cm in thickness. After observing the observation surface of the obtained sample with ruthenium tetroxide, an SEM image is obtained using a scanning electron microscope under the condition of an acceleration voltage of 1 kV.
The SEM image used for observation has a field of view of 3000 times magnification, and when there are glass fibers in the resin composition in the field of view, an image is selected such that the cross-sectional area of the glass fibers is 10% or less of the field of view.
Details of a specific analysis method are as described in detail in the examples.

FIG. 1 to FIG. 7 are SEM images (magnification: 3000 times) of the compacts obtained in the examples of the present application, using a scanning electron microscope.
In the figure, the black-gray part (the part with the lowest brightness) is the phase of the polybutylene terephthalate resin (A), and forms the sea as a continuous phase. In the figure, the light gray part (part having a higher brightness than the polybutylene terephthalate resin phase) is a domain containing the styrene copolymer (B), and the islands are located in the continuous sea of polybutylene terephthalate resin (A). The phase of polybutylene terephthalate resin (A) exists as a lake (pond) in the island in the island-shaped part of the styrene copolymer (B). And the island-shaped part is characterized by not having an excessively large width and a maximum value of 6 μm or less. In the drawing, a large circular or semicircular portion having a color tone between the lightest portion and the light gray portion is a glass fiber.

On the other hand, FIGS. 8 to 9 are SEM images (magnification 3000 times) of the molded body obtained in the comparative example of the present application, and the width of the island-shaped portion is FIG. 8 (Comparative Example 1). 9 (Comparative Example 2) is very large. Further, in FIG. 10 of Comparative Example 4 of the present application, the islands containing the styrene-based copolymer (B) are uniformly finely dispersed in the continuous phase of the polybutylene terephthalate resin (A). It can be seen that there is no lake (pond) of polybutylene terephthalate resin (A).

FIG. 11 is a schematic diagram for explaining the sea-island structure of the present invention. In the figure, reference numeral 1 denotes an island-like part, which is present in the continuous phase (sea) of the black-gray polybutylene terephthalate resin (A). A polybutylene terephthalate resin (A) is present as a lake 2 as indicated by 2 in the figure in the island-shaped portion 1 of the styrene copolymer (B). In this invention, it is preferable that the island-shaped part 1 is a shape which has the branch part 3 as shown to 3 in FIG. It is also preferable that the plurality of branch portions 3 are coupled to each other.

As described above, the island-shaped portion 1 has a polybutylene terephthalate resin (A) phase as a lake (pond) 2 in the island, and the island-shaped portion 1 has a maximum width d of 6 μm. It is as follows.
The width d of the island-shaped portion is defined as a width length d orthogonal to the width center line L of the island-shaped portion as shown by a broken line in FIG. The width center line L of the island-shaped portion is the width center lines L ′ and L between the lake and the outer edge of the island in the portion where the lake phase of the polybutylene terephthalate resin (A) is present (between points pp in the figure). ″, And the width d of the island-shaped portion is the width d orthogonal to L ′ and L ″.

The island portion has a maximum width d of 6 μm or less, preferably 5 μm or less, more preferably 4 μm or less, preferably 2 μm or more, more preferably 3 μm or more.
When the maximum value of the width d of the island-shaped portion exceeds 6 μm, the mechanical strength (particularly bending strength and tensile strength retention) at high temperatures, which is a feature of the sea-island structure of the present invention, is deteriorated.

In addition, when the island-shaped portion has only an island-shaped portion in which the lake of the polybutylene terephthalate resin (A) does not exist, the warpage of the molded body, which is a feature of the sea-island structure of the present invention, is deteriorated.
In the present invention, the proportion of the island-like portion where the lake of the polybutylene terephthalate resin (A) is present is expressed as [area of all island-like portions (however, this area includes the area of the lake). % Of the total area of the islands where the phase (A) exists as a lake (however, this area does not include the area of the lake)] When it shows, Preferably it is 10% or more, More preferably, it is 20% or more, More preferably, it is 25% or more, Especially 30% or more, Especially 40% or more, Especially 60% or more is preferable.
Here, the “island-like portion where the lake exists” is defined as an island-like portion having a lake having a major axis of 1 μm or more in the field of view of the SEM image (magnification 3000 times).

[TOVC amount]
Moreover, the amount of volatile organic compounds (TVOC amount) of the molded body of the polybutylene terephthalate resin composition of the present invention is 30 μg C / g or less.
In addition, the specific measuring method of the amount of volatile organic compounds (TVOC) of a polybutylene terephthalate resin composition molded body is as detailed in the examples.

It is essential that the molded article of the present invention comprises a composition containing at least a polybutylene terephthalate resin (A) and a styrene copolymer (B) in a predetermined amount.
Each component which comprises the polybutylene terephthalate resin composition used for the resin composition molded object of this invention is demonstrated below.

[Polybutylene terephthalate resin (A)]
The polybutylene terephthalate resin (A) used in the polybutylene terephthalate resin composition is a polyester resin having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded, and is a polybutylene terephthalate resin (homopolymer). In addition, a polybutylene terephthalate copolymer containing other copolymerization components other than terephthalic acid units and 1,4-butanediol units, and a mixture of a homopolymer and the copolymer are included.

The polybutylene terephthalate resin (A) may contain dicarboxylic acid units other than terephthalic acid. Specific examples of other dicarboxylic acids include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis (4,4'- Carboxyphenyl) methane, anthracene dicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-diphenyl ether dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 4,4′-dicyclohexyl dicarboxylic acid, And aliphatic such as adipic acid, sebacic acid, azelaic acid, dimer acid, etc. Carboxylic acids, and the like.

The diol unit may contain other diol units in addition to 1,4-butanediol. Specific examples of the other diol units include aliphatic or alicyclic diols having 2 to 20 carbon atoms. Bisphenol derivatives and the like. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4′-dicyclohexylhydroxymethane, 4 4,4'-dicyclohexylhydroxypropane, ethylene oxide addition diol of bisphenol A, and the like. In addition to the above-mentioned bifunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure, and fatty acids are used for molecular weight control. A small amount of a monofunctional compound can be used in combination.

As described above, the polybutylene terephthalate resin (A) is preferably a polybutylene terephthalate homopolymer obtained by polycondensation of terephthalic acid and 1,4-butanediol, but the carboxylic acid unit may be other than the above terephthalic acid. It may be a polybutylene terephthalate copolymer containing one or more dicarboxylic acids and / or one or more diols other than the 1,4-butanediol as the diol unit, and the polybutylene terephthalate resin (A) is a co-polymer. In the case of a polybutylene terephthalate resin modified by polymerization, specific preferred copolymers thereof include polyalkylene glycols, particularly polyester ether resins copolymerized with polytetramethylene glycol, and dimer acid copolymerized polybutylene terephthalate. Resin, isophthal Copolymerized polybutylene terephthalate resin. Among these, it is preferable to use a polyester ether resin copolymerized with polytetramethylene glycol. These copolymers are those having a copolymerization amount of 1 mol% or more and less than 50 mol% in all segments of the polybutylene terephthalate resin. Among them, the copolymerization amount is preferably 2 mol% or more and less than 50 mol%, more preferably 3 to 40 mol%, particularly preferably 5 to 20 mol%. By setting it as such a copolymerization ratio, it exists in the tendency for fluidity | liquidity, toughness, and tracking resistance to improve easily, and is preferable.

In the polybutylene terephthalate resin (A), the amount of terminal carboxyl groups may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and preferably 30 eq / ton or less. More preferably. If it exceeds 50 eq / ton, gas tends to be generated during melt molding of the resin composition. Although the lower limit of the amount of terminal carboxyl groups is not particularly defined, it is usually 10 eq / ton in consideration of the productivity of production of polybutylene terephthalate resin.

The amount of terminal carboxyl groups of the polybutylene terephthalate resin is a value measured by titration using a 0.01 mol / l benzyl alcohol solution of sodium hydroxide by dissolving 0.5 g of the polyalkylene terephthalate resin in 25 mL of benzyl alcohol. is there. As a method for adjusting the amount of terminal carboxyl groups, a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.

The intrinsic viscosity of the polybutylene terephthalate resin (A) is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are more preferable. If the intrinsic viscosity is lower than 0.5 dl / g, the resulting resin composition tends to have a low mechanical strength. On the other hand, if it is higher than 2 dl / g, the fluidity of the resin composition may deteriorate and the moldability may deteriorate.
The intrinsic viscosity of the polybutylene terephthalate resin (A) is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

The polybutylene terephthalate resin (A) is obtained by melt polymerization of a dicarboxylic acid component having terephthalic acid as a main component or an ester derivative thereof and a diol component having 1,4-butanediol as a main component in a batch or continuous manner. Can be manufactured. Further, after the low molecular weight polybutylene terephthalate resin is produced by melt polymerization, the degree of polymerization (or molecular weight) can be increased to a desired value by further solid-phase polymerization under a nitrogen stream or under reduced pressure.
The polybutylene terephthalate resin (A) is obtained by a production method in which a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of 1,4-butanediol are melt polycondensed in a continuous manner. Is preferred.

The catalyst used when performing the esterification reaction may be a conventionally known catalyst, and examples thereof include a titanium compound, a tin compound, a magnesium compound, and a calcium compound. Of these, titanium compounds are particularly preferred. Specific examples of the titanium compound as the esterification catalyst include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate.

[Styrene copolymer (B)]
The styrene copolymer (B) used in the polybutylene terephthalate resin composition is an acrylonitrile-styrene copolymer (B1) and / or an epoxy-modified acrylonitrile-styrene copolymer (B2).

<Acrylonitrile-styrene copolymer (B1)>
The acrylonitrile-styrene copolymer (B1) is a copolymer of acrylonitrile and a styrene monomer, and may be a copolymer obtained by copolymerizing another copolymerizable monomer. Examples of the styrene monomer constituting the acrylonitrile-styrene copolymer (B1) include styrene, α-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl. Naphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene and the like can be mentioned. Styrene and α-methylstyrene are more preferable, and styrene is particularly preferable.

Other copolymerizable monomers other than styrene monomers and acrylonitrile include (meth) acrylic acid ester monomers and maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide , Α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, itaconic acid and their anhydrides, but containing epoxy groups such as glycidyl (meth) acrylate Polymerizable unsaturated compounds are excluded.
Among these, (meth) acrylic acid ester monomers are preferably exemplified. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, Examples include benzyl (meth) acrylate, and particularly methyl methacrylate.
The notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included.

The acrylonitrile-styrene copolymer (B1) is preferably an acrylonitrile-styrene copolymer (AS resin) or an acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), particularly an acrylonitrile-styrene copolymer (AS). Resin).

The unit derived from the acrylonitrile monomer in the acrylonitrile-styrene copolymer (B1) is preferably 5 to 50% by mass, more preferably 8 to 35% by mass. The content of units derived from the styrene monomer is preferably 50 to 95% by mass, more preferably 65 to 92% by mass.
In the present invention, the amount of acrylonitrile in the acrylonitrile-styrene copolymer (B1) is measured by the Kjeldahl method.

Further, acrylonitrile - as a melt volume rate of the styrene copolymer (B1) (MVR), 220 ℃, is preferably in the range of 5 ~ 100cm ^3/10 min under a load 10kg, 10 ~ 80cm ^3/10 minutes Is more preferable.
The mass average molecular weight (Mw) of the acrylonitrile-styrene copolymer (B1) is preferably in the range of 60,000 to 220,000, and more preferably 80,000 to 200,000.
In the present invention, the mass average molecular weight (Mw) of the acrylonitrile-styrene copolymer (B1) is measured by GPC (gel permeation chromatography) method.

The method for producing the acrylonitrile-styrene copolymer (B1) is not limited, and a known method can be employed. For example, bulk polymerization, emulsion polymerization, solution polymerization, suspension polymerization and the like can be used. Among them, the bulk polymerization is preferable because it does not use a solvent or an emulsifier and has few impurities.
The acrylonitrile-styrene copolymer (B1) is commercially available, and bulk polymerized products, emulsion polymerized products, solution polymerized products, suspension polymerized products, etc. are commercially available. Since no emulsifier or emulsifier is used, the amount of gas generated from the molded product of the polybutylene terephthalate resin composition of the present invention is small, which is preferable.

<Epoxy-modified acrylonitrile-styrene copolymer (B2)>
The epoxy-modified acrylonitrile-styrene copolymer (B2) is not particularly limited, but a copolymer of an unsaturated glycidyl compound, acrylonitrile, and a styrene monomer is preferable, and other copolymerizable monomers. A copolymer obtained by copolymerization of

The styrene monomer constituting the epoxy-modified acrylonitrile-styrene copolymer (B2) includes styrene, α-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene. Vinyl naphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, and the like. Styrene and α-methylstyrene are more preferable, and styrene is particularly preferable.

The unsaturated glycidyl compound constituting the epoxy-modified acrylonitrile-styrene copolymer (B2) is preferably an epoxy group-containing polymerizable unsaturated compound, and unsaturated glycidyl esters such as glycidyl (meth) acrylate and glycidyl itaconate. Alternatively, unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether and the like are preferable. Among them, unsaturated glycidyl esters, particularly epoxy group-containing (meth) acrylic acid esters are preferable, more preferably glycidyl (meth) acrylate, that is, glycidyl acrylate, glycidyl methacrylate (GMA), particularly glycidyl methacrylate (GMA). preferable.

In addition to the above, the epoxy-modified acrylonitrile-styrene copolymer (B2) may be copolymerized with another monomer, but the other monomer is an epoxy-modified acrylonitrile-styrene copolymer. It can be included in an amount up to less than 50% by weight, preferably less than 30% by weight, more preferably less than 10% by weight of the combined (B2).

The epoxy-modified acrylonitrile-styrene copolymer (B2) is preferably a glycidyl methacrylate (GMA) -modified acrylonitrile-styrene copolymer.

The epoxy equivalent of the epoxy-modified acrylonitrile-styrene copolymer (B2) is preferably 2000 to 30000 g / mol, more preferably 4000 to 28000 g / mol. When the epoxy equivalent exceeds 30000 g / mol, the dispersion of the epoxy-modified acrylonitrile-styrene copolymer in the composition may be insufficient. On the other hand, when the epoxy equivalent is less than 2000 g / mol, the viscosity is remarkably increased and the moldability is increased. It may be damaged.

The content of units derived from the acrylonitrile compound in the epoxy-modified acrylonitrile-styrene copolymer (B2) is usually 2 to 50% by mass, preferably 20 to 30% by mass, based on 100% by mass of the entire polymer (B2). The content of units derived from styrenic monomers is usually 50 to 98% by mass, preferably 70 to 80% by mass, and the content of units derived from unsaturated glycidyl compounds is usually 0.1 to 1.0% by mass. %, Preferably 0.2 to 0.8% by mass. In the present invention, the amount of acrylonitrile in the epoxy-modified acrylonitrile-styrene copolymer (B2) is measured by the Kjeldahl method. In addition, the measurement of unsaturated glycidyl compounds is based on JIS.
The measurement is performed in accordance with K7236.

Epoxy-modified acrylonitrile - MVR styrene copolymer (B2) is 220 ° C., under a load 10 ^kg, preferably ⁵ ~ 100cm 3 / 10min, a weight-average molecular weight (Mw), preferably at 60,000 to 220,000 More preferably, it is 70,000 to 200,000. The mass average molecular weight (Mw) is measured by GPC (gel permeation chromatography) method.

The method for producing the epoxy-modified acrylonitrile-styrene copolymer (B2) is not limited, and a known method can be adopted. For example, bulk polymerization, emulsion polymerization, solution polymerization, suspension polymerization and the like can be used. Among these, the bulk polymerization is preferable because it does not use a solvent or an emulsifier and has few impurities.
Epoxy-modified acrylonitrile-styrene copolymer (B2) is commercially available, and bulk polymer products, emulsion polymer products, solution polymer products, suspension polymer products, etc. are commercially available. However, since a solvent and an emulsifier are not used, there are few impurities and it is preferable.

In the present invention, as the styrene copolymer (B), the amount of styrene monomer and the amount of ethylbenzene are measured by analyzing the gas generated by heat treatment at 270 ° C. for 10 minutes by gas chromatography. However, it is preferable to use a styrene monomer whose amount is 600 (mass) ppm or less. When the amount of styrene monomer gas is 600 ppm or less, the amount of gas generated at the time of molding is reduced, and the amount of gas generated from the molded body is small. In addition, the appearance of the molded body is improved because of a small amount of gas during molding. On the other hand, when it exceeds 600 ppm, it becomes difficult to solve the VOC problem in the case of an interior part for a vehicle, and the appearance tends to be poor. The amount of the styrenic monomer is more preferably 550 ppm or less, further preferably 300 ppm or less, particularly preferably 200 ppm or less, and the lower limit thereof is usually 50 ppm. When the styrene copolymer (B) is used in combination with an acrylonitrile-styrene copolymer (B1) and / or an epoxy-modified acrylonitrile-styrene copolymer (B2), the respective polymers This is the total amount calculated from the amount of the styrene monomer gas and the respective mass ratios to be used, and is also calculated in the same manner when a plurality of types are used from (B1) and / or (B2). Means the amount.
The amount of styrene in the raw material styrene-based copolymer (B) or the raw material polybutylene terephthalate resin composition is the amount obtained by analyzing a gas generated by heat treatment at 270 ° C. for 10 minutes by gas chromatography. It is the amount (unit: mass ppm) converted into a value per copolymer or resin composition amount. The details of the specific measurement method are as described in the examples.

The total of the styrene monomer and ethylbenzene when the gas generated by heat treatment at 270 ° C. for 10 minutes of the raw styrene copolymer (B) is analyzed by gas chromatography is 650 (mass) ppm or less. Is preferred. Since the total gas amount of both is 650 ppm or less, the amount of gas generated at the time of molding is reduced, and the amount of gas generated from the molded body when formed into a molded body is small. The problem of VOC is solved, and the appearance of the molded body is improved because of less gas during molding. The total gas amount of both is more preferably 500 ppm or less, still more preferably 400 ppm or less, and its lower limit is usually 150 ppm. If it is less than 150 ppm, it is not preferable because it requires refining so as not to be economical.
In the case where acrylonitrile-styrene copolymer (B1) and / or epoxy-modified acrylonitrile-styrene copolymer (B2) is used in combination as styrene copolymer (B), The total amount calculated from the amount of styrene monomer and ethylbenzene generated from each polymer and the respective mass ratio used, and a plurality of types are used from (B1) and / or (B2) It also means the total amount calculated in the same way.

In order to make the total amount of the styrene monomer in the styrene copolymer (B) and the styrene monomer and ethylbenzene within the above range, the configuration of the devolatilization step after the polymerization of the styrene copolymer And by strengthening the operating conditions of the devolatilization process. In the case of suspension polymerization, the copolymer latex obtained at an appropriate temperature and vacuum is stripped, coagulated with high-temperature steam, or stripped under reduced pressure using high-temperature steam. And the coagulated copolymer is washed with hot water and further dried under vacuum. In bulk polymerization, it is possible to adjust the degree of vacuum, supply speed or heating temperature in a vacuum devolatilizer.
It is also possible to select a commercially available product satisfying the conditions or to further dry the commercially available product to obtain the desired amount of styrene monomer or ethylbenzene.

The total of the acrylonitrile-styrene copolymer (B1) and / or the epoxy-modified acrylonitrile-styrene copolymer (B2), that is, the content of the styrene copolymer (B) is the polybutylene terephthalate resin (A ) 45 to 100 parts by mass with respect to 100 parts by mass. If the content is less than 45 parts by mass, the ratio of the amorphous resin is low and the shrinkage ratio is large, which causes warping of the molded product. If the content exceeds 100 parts by mass, the ratio of the amorphous resin is high and the heat resistance is high. In addition to the decrease, the 85 ° C. atmosphere bending strength and weld strength decrease. The content of the styrenic copolymer (B) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, still more preferably 60 parts by mass or more, and particularly preferably more than 65 parts by mass, preferably 95 parts by mass. The amount is at most 90 parts by mass, more preferably at most 90 parts by mass.

[Epoxy-modified acrylic polymer (C)]
It is preferable that the polybutylene terephthalate resin composition further contains an epoxy-modified acrylic polymer (C). The epoxy-modified acrylic polymer (C) is not particularly limited, but an acrylic polymer composed of a (meth) acrylic acid alkyl ester and an unsaturated glycidyl compound is preferable.

Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Isobutyl, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, (Meth) acrylic acid alkyl ester having a linear or branched alkyl group such as (meth) acrylic acid decyl and (meth) acrylic acid dodecyl is preferable, and (meth) acrylic acid having 1 to 12 carbon atoms is preferred. Alkyl esters are more preferred, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Acrylate, propyl (meth) acrylate, butyl 2-ethylhexyl (meth) acrylic acid.
In the present specification, “(meth) acryl” means “acryl” and / or “methacryl”.

As the unsaturated glycidyl compound, an epoxy group-containing polymerizable unsaturated compound is preferable, unsaturated glycidyl ester such as glycidyl (meth) acrylate and glycidyl itaconate, or vinyl glycidyl ether, allyl glycidyl ether, 2-methyl Preferable examples include unsaturated glycidyl ethers such as allyl glycidyl ether and styrene-p-glycidyl ether. Among them, unsaturated glycidyl esters, particularly epoxy group-containing (meth) acrylic acid esters are preferable, more preferably glycidyl (meth) acrylate, that is, glycidyl acrylate, glycidyl methacrylate (GMA), particularly glycidyl methacrylate (GMA). preferable.

The epoxy-modified acrylic polymer (C) is preferably a copolymer obtained by copolymerizing another monomer other than those described above, and is particularly preferably a copolymer obtained by copolymerizing a styrene monomer.
Styrene monomers include styrene, α-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl naphthalene, methoxy styrene, monobromo styrene, dibromo styrene, Examples thereof include fluorostyrene and tribromostyrene, and styrene and α-methylstyrene are more preferable, and styrene is particularly preferable.

The epoxy-modified acrylic polymer (C) is a structural unit derived from a (meth) acrylic acid alkyl ester (C1), an epoxy group-containing (meth) acrylic acid ester (C2), or a styrene monomer (C3). When it is contained, the preferred content of each constituent unit is such that the C1 component is preferably 50 to 99% by mass, more preferably 55 to 95% when the mass of the epoxy-modified acrylic polymer (C) is 100% by mass. The C2 component is preferably 0.05 to 20% by mass, more preferably 0.1 to 18% by mass, and the C3 component is preferably 0 to 49.5% by mass, more preferably 0 to 45%. The mass is preferably 5% by mass, more preferably 5 to 45% by mass.

The epoxy equivalent of the epoxy-modified acrylic polymer (C) is preferably 100 to 1000 g / mol, more preferably 200 to 800 g / mol. When the epoxy equivalent exceeds 1000 g / mol, the dispersion of the acrylonitrile-styrene copolymer in the composition may be insufficient. On the other hand, when the epoxy equivalent is less than 100 g / mol, the viscosity is remarkably increased and the moldability is impaired. There is a case.

The weight average molecular weight (Mw) of the epoxy-modified acrylic polymer (C) is preferably 4000 to 13000, more preferably 5000 to 12000.

The preferable content of the epoxy-modified acrylic polymer (C) is 0.2 to 3 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). If the amount is less than 0.2 parts by mass, the cross-linkage between the polybutylene terephthalate molecules becomes insufficient, and the mechanical strength tends to decrease. It rises remarkably and the moldability tends to be impaired. The preferable content of the polymer (C) is preferably 0.25 parts by mass or more, preferably 2.8 parts by mass or less, more preferably 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). Part or less, more preferably 1.0 part by weight or less.

[Glass fiber (D)]
The polybutylene terephthalate resin composition preferably contains glass fibers (D), and the amount thereof is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). When the content is less than 10 parts by mass, the reinforcing effect may not be sufficient, and when it exceeds 100 parts by mass, the appearance and impact resistance may be inferior and the fluidity may not be sufficient. The preferable content of the glass fiber (D) is 45 parts by mass or more, more preferably 55 parts by mass or more, further preferably 65 parts by mass or more, particularly 100 parts by mass of the polybutylene terephthalate resin (A). 70 parts by mass or more is preferable, preferably 95 parts by mass or less, and more preferably 90 parts by mass or less. Thus, by containing glass fiber (D), the intensity | strength, rigidity, and dimensional stability of the molded object of this invention can be improved.

The type of glass fiber (D) is not particularly limited, and examples thereof include glass fibers such as E glass, C glass, A glass, and S glass. Among these, E glass fibers are preferred in that they do not adversely affect the thermal stability of the polybutylene terephthalate resin.

The average fiber diameter of the glass fiber (D) is not particularly limited, but is preferably selected in the range of 1 to 100 μm, more preferably 2 to 50 μm, still more preferably 3 to 30 μm, and particularly preferably 5 to 20 μm. Glass fibers having an average fiber diameter of less than 1 μm are not easy to produce and may increase costs, whereas if they exceed 100 μm, the tensile strength of the glass fibers may decrease. The fiber cross section may be circular or flat.

The glass fiber (D) may be a round fiber or a flat fiber cross section, but the cross section of the fiber cross section (major axis / minor axis) is a glass fiber having a substantially circular cross section of 1 to 1.5. Preferably there is. The flatness is preferably 1 to 1.4, more preferably 1 to 1.2, and particularly preferably 1 to 1.1.
The flatness value is determined by an image analyzer from an image obtained by observing 2000 glass fibers of filler residue collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical with an optical microscope. It is a calculated average value.

The average fiber length of the glass fiber (D) is not particularly limited, but is preferably, for example, 1 to 10 mm, more preferably 1.5 to 6 mm, and further preferably 2 to 5 mm. If the average fiber length of the glass fiber (D) is less than 1 mm, the reinforcing effect may not be sufficiently exhibited, and if it exceeds 10 mm, it may be difficult to mold the resulting resin composition.
The average fiber length is determined by using an image analyzer from an image obtained by observing 2000 glass fibers of a filler residue collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical using an optical microscope. It is a value of the calculated number average fiber length. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

The glass fiber (D) used in the present invention can be surface-treated with a coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion with the polybutylene terephthalate resin (A).
Examples of the coupling agent include chlorosilane compounds such as vinyltrichlorosilane and methylvinyldichlorosilane, alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloxypropyltrimethoxysilane. Compounds, epoxy silane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, acrylic compounds, isocyanate compounds, titanate compounds, epoxy compounds, etc. Can be mentioned.

In addition, the glass fiber (D) used in the present invention is usually preferably used as a chopped strand (chopped glass fiber) obtained by cutting a number of these fibers into a predetermined length. It is preferable to add a sizing agent to the fiber. By blending the sizing agent, good mechanical properties can be obtained in addition to the advantage that the production stability of the polybutylene terephthalate resin composition and the molded body is increased.
The sizing agent for glass fiber (D) is not particularly limited, and examples thereof include resin emulsions such as vinyl acetate resin, ethylene-vinyl acetate copolymer, acrylic resin, epoxy resin, polyurethane resin, and polyester resin. Preferably, acrylic resin, epoxy resin, and polyurethane resin are used.

The composition constituting the molded article of the present invention may be composed of a composition containing at least a predetermined amount of polybutylene terephthalate resin (A) and styrene copolymer (B) as described above. For example, it is more preferable to use other components, for example, the following composition.
Preferred composition (1):
45-100 parts by mass of acrylonitrile-styrene copolymer (B1), 0.2-3 parts by mass of epoxy-modified acrylic polymer (C), and glass fiber with respect to 100 parts by mass of polybutylene terephthalate resin (A) (D) A polybutylene terephthalate resin composition containing 10 to 100 parts by mass.
Preferred composition (2):
Polybutylene terephthalate containing acrylonitrile-styrene copolymer (B1), epoxy-modified acrylonitrile-styrene copolymer (B2), and glass fiber (D) with respect to 100 parts by mass of polybutylene terephthalate resin (A) Resin composition.

In the preferable composition (2), the contents of the acrylonitrile-styrene copolymer (B1) and the epoxy-modified acrylonitrile-styrene copolymer (B2) are the sum of both, and the polybutylene terephthalate resin (A) It is preferably 45 to 100 parts by mass with respect to 100 parts by mass, and the mass ratio (B1) / (B2) of the content of (B1) to the content of (B2) is preferably 6 or less. The content of (D) is preferably 10 to 100 mass.

In the preferable composition (2) described above, if the total content of (B1) and (B2) is less than 45 parts by mass, the ratio of the amorphous resin is low, so the shrinkage ratio is increased, and the molded product is warped. When the amount exceeds 100 parts by mass, the ratio of the amorphous resin is high, so that the heat resistance tends to be lowered, and the 85 ° C. atmosphere bending strength and the weld strength are likely to be lowered. The total content of (B1) and (B2) is more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more, particularly preferably 60 parts by mass or more, and most preferably more than 65 parts by mass. Preferably it is 95 mass parts or less, More preferably, it is 90 mass parts or less. On the other hand, when the mass ratio (B1) / (B2) exceeds 6, the dispersion of the epoxy-modified acrylonitrile-styrene copolymer becomes insufficient, and the mechanical properties in a high temperature environment are likely to deteriorate. (B1) / (B2) is more preferably 5 or less, further preferably 4 or less, especially 3 or less, particularly 2 or less, and the lower limit thereof is preferably 0.5.

The content of the acrylonitrile-styrene copolymer (B1) alone is preferably 5 with respect to 100 parts by mass of the polybutylene terephthalate resin (A) on condition that the mass ratio (B1) / (B2) is satisfied. It is preferably selected from the range of ~ 85 parts by mass.
The content of the epoxy-modified acrylonitrile-styrene copolymer (B2) alone is preferably based on 100 parts by mass of the polybutylene terephthalate resin (A) on condition that the above mass ratio (B1) / (B2) is satisfied. Is preferably selected from the range of 5 to 90 parts by mass.

The second invention of the present application is based on 100 parts by mass of the polybutylene terephthalate resin (A), 45-100 parts by mass of the acrylonitrile-styrene copolymer (B1), 0.2% of the epoxy-modified acrylic polymer (C). A polybutylene terephthalate resin composition comprising ˜3 parts by mass and 10 to 100 parts by mass of glass fiber (D).

In the second invention, the polybutylene terephthalate resin (A), the acrylonitrile-styrene copolymer (B1), the epoxy-modified acrylic polymer (C), and the glass fiber (D) are as described above.

In the second invention, the content of the acrylonitrile-styrene copolymer (B1) is 45 to 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A), but the content is less than 45 parts by mass. Then, since the proportion of the amorphous resin is low and the shrinkage rate is large, the molded product is warped. When the amount exceeds 100 parts by mass, the proportion of the amorphous resin is high and the heat resistance is lowered. Decrease in bending strength and weld strength at ℃ atmosphere. The content of the acrylonitrile-styrene copolymer (B1) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, further preferably 60 parts by mass or more, and particularly preferably 65 parts by mass or more. Is 95 parts by mass or less, more preferably 90 parts by mass or less.

In the second invention, the acrylonitrile-styrene copolymer (B1) is obtained by analyzing the gas generated by heat treatment at 270 ° C. for 10 minutes by gas chromatography, thereby determining the amount of styrene monomer and the amount of ethylbenzene. However, it is preferable to use a styrene monomer having an amount of 600 ppm by mass or less. When the amount of styrene-based monomer gas is 600 ppm or less, the amount of gas generated during molding is reduced, and the amount of gas generated from the molded body when molded is small. The VOC problem is solved, and the appearance of the molded body is improved because of a small amount of gas during molding. On the other hand, when it exceeds 600 ppm, it becomes difficult to solve the VOC problem in the case of an interior part for a vehicle, and the appearance tends to be poor. The amount of the styrenic monomer is more preferably 550 ppm or less, further preferably 300 ppm or less, particularly preferably 200 ppm or less, and the lower limit thereof is usually 50 ppm. If it is less than 50 ppm, it is not preferable because it requires refining so as not to be economical. When a plurality of types are used as the acrylonitrile-styrene copolymer (B1), the total amount calculated from the amount of styrene monomer gas from each polymer and the respective mass ratios used. is there.
The amount of the styrene monomer can be obtained by analyzing the gas generated by heat treatment at 270 ° C. for 10 minutes by gas chromatography, but the measured value is converted into a value per mass of the copolymer. The amount to be obtained (unit: mass ppm), and the specific conditions are as detailed in the examples.

The total of the styrene monomer and ethylbenzene when the gas generated by heat treatment at 270 ° C. for 10 minutes is analyzed by gas chromatography is preferably 650 (mass) ppm or less. Since the total gas amount of both is 650 ppm or less, the amount of gas generated at the time of molding is reduced, and the amount of gas generated from the molded body when formed into a molded body is small. The problem of VOC is solved, and the appearance of the molded body is improved because of less gas during molding. The total gas amount of both is more preferably 500 ppm or less, still more preferably 400 ppm or less, and its lower limit is usually 150 ppm. If it is less than 150 ppm, it is not preferable because it requires refining so as not to be economical.
When a plurality of types are used as the acrylonitrile-styrene copolymer (B1), the amount of styrene monomer and ethylbenzene generated from each polymer and the mass ratio used are the same as above. Is the total amount calculated.

In order to make the total amount of the styrene monomer and the styrene monomer and ethylbenzene in the acrylonitrile-styrene copolymer (B1) within the above range, a devolatilization step after the polymerization of the styrene copolymer is performed. This can be achieved by strengthening the configuration and operating conditions of the devolatilization process. In the case of suspension polymerization, the copolymer latex obtained at an appropriate temperature and vacuum is stripped, coagulated with high-temperature steam, or stripped under reduced pressure using high-temperature steam. And the coagulated copolymer is washed with hot water and further dried under vacuum. In bulk polymerization, it is possible to adjust the degree of vacuum, supply speed or heating temperature in a vacuum devolatilizer.
It is also possible to select a commercially available product satisfying the conditions or to further dry the commercially available product to obtain the desired amount of styrene monomer or ethylbenzene.

The content of the epoxy-modified acrylic polymer (C) is 0.2 to 3 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). Crosslinks between butylene terephthalate molecules become insufficient and mechanical strength tends to decrease. When the amount exceeds 3 parts by mass, the crosslinks between polybutylene terephthalate molecules excessively increase, resulting in a marked increase in viscosity and impaired moldability. It will be. The preferable content of the polymer (C) is preferably 0.25 parts by mass or more, preferably 2.8 parts by mass or less, more preferably 2.10 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). 0 parts by mass or less, more preferably 1.0 parts by mass or less.

The content of the glass fiber (D) is 10 to 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A), but if the content is less than 10 parts by mass, the reinforcing effect may not be sufficient. In addition, when it exceeds 100 parts by mass, the appearance and impact resistance may be inferior, and the fluidity may not be sufficient. The preferable content of the glass fiber (D) is 45 parts by mass or more, more preferably 55 parts by mass or more, further preferably 65 parts by mass or more, particularly 100 parts by mass of the polybutylene terephthalate resin (A). 70 parts by mass or more is preferable, preferably 95 parts by mass or less, and more preferably 90 parts by mass or less. Thus, by containing glass fiber (D), the strength, rigidity, and dimensional stability of the polybutylene terephthalate resin composition can be improved.

The third invention of the present application is based on 100 parts by mass of the polybutylene terephthalate resin (A), and the total amount of the acrylonitrile-styrene copolymer (B1) and the epoxy-modified acrylonitrile-styrene copolymer (B2). 45 to 100 parts by mass, the mass ratio (B1) / (B2) of the contents of (B1) and (B2) is 6 or less, and further contains 10 to 100 parts by mass of glass fiber (D). It is a polybutylene terephthalate resin composition characterized.

In the third invention, the polybutylene terephthalate resin (A), the acrylonitrile-styrene copolymer (B1), the epoxy-modified acrylonitrile-styrene copolymer (B2), and the glass fiber (D) are as described above. . Here, the acrylonitrile-styrene copolymer (B1) is defined as not containing the epoxy-modified acrylonitrile-styrene copolymer (B2).

In the third invention, the total content of the acrylonitrile-styrene copolymer (B1) and the epoxy-modified acrylonitrile-styrene copolymer (B2) is 100 parts by mass of the polybutylene terephthalate resin (A). On the other hand, the mass ratio (B1) / (B2) between the content of (B1) and the content of (B2) is 45 or less, and the sum of (B1) and (B2). If the content of is less than 45 parts by mass, the proportion of the amorphous resin is low, so the shrinkage rate is increased, resulting in warping of the molded product, and if it exceeds 100 parts by mass, the proportion of the amorphous resin is high. In addition to the reduction in heat resistance, the 85 ° C. atmosphere bending strength and weld strength are reduced. The total content of (B1) and (B2) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, still more preferably 60 parts by mass or more, particularly preferably more than 65 parts by mass, preferably It is 95 mass parts or less, More preferably, it is 90 mass parts or less. On the other hand, when the mass ratio (B1) / (B2) exceeds 6, the dispersion of the epoxy-modified acrylonitrile-styrene copolymer becomes insufficient, and the mechanical properties in a high temperature environment are deteriorated. (B1) / (B2) is preferably 5 or less, more preferably 4 or less, especially 3 or less, particularly 2 or less, and its lower limit is preferably 0.5.

In the third invention, the content of the acrylonitrile-styrene copolymer (B1) alone satisfies the above mass ratio (B1) / (B2), and 100 parts by mass of the polybutylene terephthalate resin (A). On the other hand, it is preferably selected from the range of 5 to 85 parts by mass.
The content of the epoxy-modified acrylonitrile-styrene copolymer (B2) alone is preferably based on 100 parts by mass of the polybutylene terephthalate resin (A) on condition that the above mass ratio (B1) / (B2) is satisfied. Is preferably selected from the range of 5 to 90 parts by mass.

In the third invention, acrylonitrile-styrene copolymer (B1) and / or epoxy-modified acrylonitrile-styrene copolymer (B2) is analyzed by gas chromatograph for gas generated by heat treatment at 270 ° C. for 10 minutes. In this case, it is preferable to use a styrenic monomer having an amount of 600 (mass) ppm or less. The total of the styrene monomers from (B1) and (B2) is more preferably 600 (mass) ppm or less.
When the amount of styrenic monomer gas is 600 ppm or less, the amount of gas generated during molding is reduced, and the amount of gas generated from the molded body when molded is small. The problem of VOC is solved, and the appearance of the molded body is improved because of a small amount of gas during molding. On the other hand, when it exceeds 600 ppm, it becomes difficult to solve the VOC problem in the case of an interior part for a vehicle, and the appearance tends to be poor. The amount of the styrenic monomer is more preferably 550 ppm or less, further preferably 300 ppm or less, particularly preferably 200 ppm or less, and the lower limit thereof is usually 50 ppm. If it is less than 50 ppm, it is not preferable because it requires refining so as not to be economical.
When one or each of (B1) and (B2) is used as the acrylonitrile-styrene copolymer (B1) or the epoxy-modified acrylonitrile-styrene copolymer (B2), a styrene polymer from each polymer is used. This is the total amount calculated from the amount of monomer gas and the respective mass ratios used.
The amount of the styrene monomer and the amount of ethylbenzene described later can be obtained by analyzing a gas generated by heat treatment at 270 ° C. for 10 minutes by gas chromatography. The amount (unit: ppm by mass) obtained by converting to the value of, and the specific conditions are as detailed in the examples.

Further, the total of the styrene monomer and ethylbenzene when the gas generated by heat treatment at 270 ° C. for 10 minutes is analyzed by gas chromatography is preferably 650 (mass) ppm or less. Since the total gas amount of both is 650 ppm or less, the amount of gas generated at the time of molding is reduced, and the amount of gas generated from the molded body when formed into a molded body is small. The problem of VOC is solved, and the appearance of the molded body is improved because of less gas during molding. The total gas amount of both is more preferably 500 ppm or less, still more preferably 400 ppm or less, and its lower limit is usually 150 ppm. If it is less than 150 ppm, it is not preferable because it requires refining so as not to be economical.

To bring the total amount of the styrene monomer in the acrylonitrile-styrene copolymer (B1) and / or the epoxy-modified acrylonitrile-styrene copolymer, and the total amount of the styrene monomer and ethylbenzene into the above range, This can be achieved by strengthening the configuration of the devolatilization step after the polymerization of the acrylonitrile-styrene copolymer and the operating conditions of the devolatilization step. In the case of suspension polymerization, the copolymer latex obtained at an appropriate temperature and vacuum is stripped, coagulated with high-temperature steam, or stripped under reduced pressure using high-temperature steam. And the coagulated copolymer is washed with hot water and further dried under vacuum. In bulk polymerization, it is possible to adjust the degree of vacuum, supply speed or heating temperature in a vacuum devolatilizer.
It is also possible to select a commercially available product satisfying the conditions or to further dry the commercially available product to obtain the desired amount of styrene monomer or ethylbenzene.

In the third invention, the content of the glass fiber (D) is 10 to 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). When the content is less than 10 parts by mass, the reinforcing effect may not be sufficient, and when it exceeds 100 parts by mass, the appearance and impact resistance may be inferior and the fluidity may not be sufficient. The preferable content of the glass fiber (D) is 45 parts by mass or more, more preferably 55 parts by mass or more, further preferably 65 parts by mass or more, particularly 100 parts by mass of the polybutylene terephthalate resin (A). 70 parts by mass or more is preferable, preferably 95 parts by mass or less, and more preferably 90 parts by mass or less. Thus, by containing glass fiber (D), the strength, rigidity, and dimensional stability of the polybutylene terephthalate resin composition can be improved.

[Other ingredients]
The polybutylene terephthalate resin composition described above preferably used in the resin composition molded article of the present invention, or the polybutylene terephthalate resin composition of the second and third inventions described above is a thermoplastic resin other than essential components, It can contain in the range which does not impair the effect of this invention. As other thermoplastic resins, specifically, for example, polyethylene terephthalate resin, polycarbonate resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, Examples include polyether ketone resins and polyolefin resins.
However, when the resin other than the essential components is contained, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts with respect to 100 parts by mass of the polybutylene terephthalate resin (A). It is preferable that the amount be 3 parts by mass or less, particularly 3 parts by mass or less.

In addition, various additives other than those described above may be contained. Examples of such additives include stabilizers, carbon black, mold release agents, flame retardants, flame retardant aids, anti-dripping agents, and ultraviolet absorption. Agents, antistatic agents, antifogging agents, antiblocking agents, plasticizers, dispersants, antibacterial agents, colorants and the like.

[Stabilizer]
It is preferable that the polybutylene terephthalate resin composition contains a stabilizer because it has effects of improving thermal stability and preventing deterioration of mechanical strength and hue. As the stabilizer, a phosphorus stabilizer, a sulfur stabilizer, and a phenol stabilizer are preferable, and a phenol stabilizer is particularly preferable.

Phosphorous stabilizers include phosphorous acid, phosphoric acid, phosphite ester (phosphite), trivalent phosphate ester (phosphonite), and pentavalent phosphate ester (phosphate). Phyto, phosphonite and phosphate compounds are preferred.

The organic phosphate compound is preferably the following general formula:
(R ¹ O) _3-n P (═O) OH _n
(Wherein R ¹ is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2)
It is a compound represented by these. More preferably, R ¹ is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group, etc. are mentioned.

Examples of the long-chain alkyl acid phosphate include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid cyclophosphate, nonyl phenyl cyclo acid phosphate Acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, di Chi le acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and a bis-nonylphenyl acid phosphate, or the like. Among these, octadecyl acid phosphate is preferable, and this is commercially available under the trade name “ADEKA STAB AX-71” of ADEKA.

As the organic phosphite compound, preferably, the following general formula:
R ² O—P (OR ³ ) (OR ⁴ )
(Wherein R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ² , R ³ and R ⁴ , At least one of them is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4'-butylidene-bis (3-methyl-6- ert-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Sufaito, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like. Among these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable.

The organic phosphonite compound is preferably the following general formula:
R ⁵ -P (OR ⁶ ) (OR ⁷ )
(Wherein R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ⁵ , R ⁶ and R ⁷ , At least one of them is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2 6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, and tetrakis (2,6 -Di-tert-butylphenyl) -3,3'-biphenylenediphosphonite and the like.

As the sulfur stabilizer, any conventionally known sulfur atom-containing compound can be used, and among these, thioethers are preferred. Specifically, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis (N-phenyl-β-naphthylamine) ), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite. Among these, pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable.

Examples of the phenol-based stabilizer include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like. Among these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate is preferred.

Among them, it is preferable to use a hindered phenol stabilizer having a melting point of 150 ° C. or higher. When the melting point is 150 ° C. or higher, the thermal stability of the stabilizer itself is increased, so that the stabilizer is altered and loses its stabilizing effect, or during the production of a resin composition such as melt kneading or in a high temperature environment such as injection molding. But it becomes difficult to produce gas. The melting point is more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher. The upper limit of the melting point is usually 350 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower.

One type of stabilizer may be contained, or two or more types may be contained in any combination and ratio.
The content of the stabilizer is preferably 0.001 to 1.5 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect an improvement in the thermal stability and compatibility of the resin composition, and a decrease in molecular weight and hue deterioration during molding are likely to occur. When it exceeds the part, it becomes an excessive amount, and there is a tendency that silver streak and hue deterioration are more likely to occur. The content of the stabilizer is more preferably 0.005 to 1.2 parts by mass, still more preferably 0.01 to 1.0 parts by mass.

[Carbon black]
It is also preferable that the polybutylene terephthalate resin composition contains carbon black. By containing carbon black, the weather resistance and appearance of the molded body are improved.
There are no restrictions on the type, raw material type, and manufacturing method of carbon black, and any of furnace black, channel black, acetylene black, ketjen black, and the like can be used. The number average particle diameter is not particularly limited, but is preferably 5 to 60 nm. As described above, by using carbon black having a number average particle diameter in a predetermined range, a composition in which blisters are hardly generated at a high temperature can be obtained.
The number average particle size was determined by obtaining an enlarged aggregate image according to the procedure described in the ASTM D3849 standard (standard test method for carbon black—morphological characterization by electron microscopy). 3,000 particle diameters can be measured and arithmetically averaged.

The nitrogen adsorption specific surface area (unit: m ² / g) of carbon black is usually preferably less than 1,000 m ² / g, and more preferably 50 to 400 m ² / g. Setting the nitrogen adsorption specific surface area to less than 1,000 m ² / g is preferable because the fluidity of the polybutylene terephthalate resin composition and the appearance of the molded body tend to be improved. The nitrogen adsorption specific surface area can be measured according to JIS K6217.

Further, the carbon black DBP (dibutyl phthalate) absorption ^is preferably less than 300 cm 3/100 g, is preferably Among them, 30 ^~ 200cm 3 / 100g. The DBP absorption amount by less than 300 cm ^3/100 g, there is a tendency that appearance of fluidity and molding of polybutylene terephthalate resin composition is improved preferably. Incidentally, DBP absorption ^(unit: cm 3 / 100g) can be measured according to JIS K6217.
The carbon black to be used is not particularly limited in pH, but is usually 2 to 10, preferably 3 to 9, and more preferably 4 to 8.

Carbon black can be used alone or in combination of two or more. Furthermore, carbon black can be granulated using a binder, and can also be used in a masterbatch that is melt-kneaded at a high concentration in another resin. By using the melt-kneaded master batch, the handling property during extrusion and the dispersibility improvement in the resin composition can be achieved. Examples of the resin include polystyrene resin, polyester resin, and acrylic resin.
The content of carbon black in the master batch is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 60% by mass.

The content of carbon black is preferably 0.01 to 5 parts by mass, more preferably 0.05 parts by mass or more, and still more preferably 0.08 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). As mentioned above, it is 0.1 mass part or more especially, More preferably, it is 2 mass parts or less, More preferably, it is 1.5 mass parts or less, Most preferably, it is 1.0 mass part or less. When the content is less than 0.01 parts by mass, the weather resistance may be insufficient. When the content exceeds 5 parts by mass, mechanical properties such as moldability and impact resistance tend to be deteriorated.

[Release agent]
The polybutylene terephthalate resin composition preferably contains a release agent.
Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds, polysiloxane silicone oils, and the like.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, for example, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acids and alcohols include montanic acid ester wax, beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmi Tate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc. .

Examples of the aliphatic hydrocarbon compound include liquid wax, paraffin wax, microcrystalline wax, polyolefin wax such as polyethylene wax, Fischer-Tropsch wax, α-olefin oligomer having 3 to 12 carbon atoms, and the like. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized. The number average molecular weight is preferably 200 to 30000, more preferably 1000 to 15000, still more preferably 1500 to 10,000, and particularly preferably 2000 to 5000. The aliphatic hydrocarbon compound may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

In the present invention, the release agent is preferably a polyolefin wax from the viewpoint of heat resistance. As the polyolefin wax, any conventionally known wax can be used. For example, the polyolefin wax preferably has 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, and further preferably 2 to 10 carbon atoms. (Co) polymers (meaning polymerization or copolymerization; the same shall apply hereinafter) containing at least species.

Examples of the olefin having 2 to 30 carbon atoms include ethylene, propylene, α-olefin having 4 to 30 carbon atoms (preferably 4 to 12, more preferably 4 to 10), and 4 to 30 carbon atoms (preferably 4). -18, more preferably 4-8) dienes. Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene. Examples of the diene include butadiene, isoprene, cyclopentadiene, 11-dodecadiene, and the like.

As the polyolefin wax, polyethylene wax is preferable from the viewpoint of releasability and heat resistance.
The manufacturing method of polyethylene wax is arbitrary, for example, can be manufactured by polymerization of ethylene or thermal decomposition of polyethylene.

As the mold release agent, those having an acid value of 10 to 40 mgKOH / g are preferred from the viewpoint that the mold release resistance is small, the effect of improving the mold release property is remarkable, and the volatile content is small. The acid value is more preferably 11 to 35 mgKOH / g, still more preferably 12 to 32 mgKOH / g. If the acid value is in the range of 10 to 40 mgKOH / g, those having an acid value of less than 10 mgKOH / g and those having an acid value of more than 40 mgKOH / g may be used in combination. It may be 10 to 40 mg KOH / g.

As the release agent having an acid value of 10 to 40 mgKOH / g, an ester of the above aliphatic carboxylic acid and alcohol having an acid value of 10 to 40 mgKOH / g, the above-mentioned aliphatic hydrocarbon compound, Represents a carboxyl group (a carboxylic acid (anhydride) group, that is, a carboxylic acid group and / or a carboxylic anhydride group), a haloformyl group, an ester group, a carboxylic acid metal base, a hydroxyl group, and an alcohol. A modified polyolefin wax provided with a functional group having an affinity for a polyester resin such as a group, an epoxy group, an amino group, or an amide group is preferred.

Examples of the carboxyl group used for modifying the polyolefin wax include low molecular weight compounds containing carboxylic acid groups such as maleic acid, maleic anhydride, acrylic acid, and methacrylic acid, low molecular weight compounds containing sulfo groups such as sulfonic acid, and phosphones. Examples thereof include a low molecular weight compound containing a phospho group such as an acid. Among these, low molecular weight compounds containing a carboxylic acid group are preferable, and maleic acid, maleic anhydride, acrylic acid, methacrylic acid, and the like are particularly preferable. These carboxylic acids may be used alone or in combination of two or more in any proportion.
The amount of acid added to the modified polyolefin wax is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the modified polyolefin wax.

Specific examples of the haloformyl group include a chloroformyl group and a bromoformyl group. Means for imparting these functional groups to the polyolefin wax may be any conventionally known method. Specifically, for example, copolymerization with a compound having a functional group, post-processing such as oxidation, etc. The method may be used.

The type of functional group is preferably a carboxyl group because it has a moderate affinity with the polyester resin. The concentration of the carboxyl group in the modified polyolefin wax may be appropriately selected and determined, but if it is too low, the affinity with the polyester resin is small, the effect of suppressing volatile matter is reduced, and the mold release effect is reduced. There is. On the other hand, if the concentration is too high, for example, the polymer main chain constituting the polyolefin wax is excessively cleaved during modification, and the molecular weight of the modified polyolefin wax is excessively reduced, resulting in increased generation of volatile matter, and polyester resin. Cloudiness may occur on the surface of the molded body.
As the modified polyolefin wax, an oxidized polyethylene wax is preferable.

In addition, 1 type may contain the mold release agent and 2 or more types may contain it by arbitrary combinations and a ratio.
The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 100 parts by mass of the polybutylene terephthalate resin (A). 1.5 parts by mass or less. When the content of the release agent is less than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[Method for Producing Resin Composition]
As a method for producing a polybutylene terephthalate resin composition, it can be carried out according to a conventional method for preparing a polybutylene terephthalate resin composition. That is, polybutylene terephthalate resin (A), acrylonitrile-styrene copolymer (B1), epoxy-modified acrylonitrile-styrene copolymer (B2), or epoxy-modified acrylic polymer (C), and optionally Other resin components to be added and various additives are mixed together and then melt-kneaded in a single or twin screw extruder. The glass fiber (D) is preferably side fed. Further, a part of which is made into a master batch may be blended and melt-kneaded. Furthermore, it is also possible to produce various molded products by supplying a mixture obtained by mixing each component in advance to a molding machine such as an injection molding machine without melt-kneading.

The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause poor appearance. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. In order to suppress decomposition during kneading or molding in the subsequent process, it is desirable to use an antioxidant or a heat stabilizer.

The raw polybutylene terephthalate resin composition has a styrene monomer content of 45 (mass) ppm or less detected when a gas generated by heat treatment at 270 ° C. for 10 minutes is analyzed by gas chromatography. preferable. When the amount of the styrene monomer gas in the resin composition is 45 ppm or less, the VOC problem is solved even when used as a vehicle interior part, and the appearance at the time of molding is also improved. On the other hand, if it exceeds 45 ppm, cleanliness as an interior part for a vehicle is deteriorated, it becomes difficult to solve the VOC problem, and the appearance at the time of molding tends to be poor. The amount of the styrene monomer gas in the resin composition is preferably 30 ppm or less, more preferably 20 ppm or less, and the lower limit thereof is usually 2 ppm.
The amount of the styrenic monomer gas in the resin composition can be obtained by analyzing a gas generated by heat treatment at 270 ° C. for 10 minutes using a gas chromatograph. The amount (unit: ppm by mass) obtained by converting to the value of, and the specific conditions are as detailed in the examples.

The raw polybutylene terephthalate resin composition is preferably 3 (mass) ppm or less in the amount of ethylbenzene detected when a gas generated by heat treatment at 270 ° C. for 10 minutes is analyzed by gas chromatography. preferable. By doing so, the VOC problem is solved even when the molded product is used as a vehicle interior part, and the appearance of the molded product is also improved.
The amount of styrene and ethylbenzene in the resin composition is the amount obtained by analyzing the gas generated by heat treatment at 270 ° C. for 10 minutes by gas chromatography as described above. It is the amount (unit: mass ppm) converted to a value per substance amount. The specific assumption method and conditions are as detailed in the examples.

In addition, the polybutylene terephthalate resin composition has a total amount of styrene monomer and ethylbenzene detected when a gas generated by heat treatment at 270 ° C. for 10 minutes is analyzed by gas chromatography is 45 (mass) ppm or less. It is preferable that By doing in this way, the VOC problem is solved even when used as a vehicle interior part, and the appearance at the time of molding is also improved. The total amount of the styrene monomer and ethylbenzene in the resin composition is preferably 30 ppm or less, more preferably 20 ppm or less, and the lower limit is usually 3 ppm.

In order to reduce the amount of styrene monomer gas in the resin composition to 45 ppm or less, is the above styrene copolymer (B) used to have a styrene monomer gas amount of 600 ppm or less, preferably 550 ppm or less? Furthermore, it is possible by blending the above-described phosphite stabilizer, hindered phenol stabilizer and the like.
The amount of ethylbenzene gas in the resin composition can be reduced to 3 ppm or less by, for example, blending the above-described phosphite stabilizer, hindered phenol stabilizer, or the like.

[Molded body]
The method for producing a molded body using the polybutylene terephthalate resin composition described above is not particularly limited, and any molding method generally employed for the polybutylene terephthalate resin composition can be arbitrarily adopted. Injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, molding method using rapid heating mold, foam molding (including supercritical fluid) , Insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, blow molding method, etc., injection molding method Is preferred.

As described above, the molded body of the present invention has a sea-island structure, and the polybutylene terephthalate resin (A) forms a continuous phase.
The domain containing the styrene copolymer (B) is dispersed in islands in the continuous phase of the polybutylene terephthalate resin (A), and the phase of the polybutylene terephthalate resin (A) is in the islands. Exists as a lake, and has a morphology in which the maximum width of the island-shaped part is 6 μm or less.

As a preferred method for producing such a molded article having a morphology, for example, it contains 45 to 100 parts by mass of a styrene copolymer (B) with respect to 100 parts by mass of a polybutylene terephthalate resin (A), and more preferably May be injection-molded using a resin composition in which the epoxy-modified acrylic polymer (C) is blended. By using the epoxy-modified acrylic polymer (C), the familiarity of the styrene copolymer (B) with the polybutylene terephthalate resin (A) is improved, so that a high degree of dispersion proceeds and the morphology of the present invention. It can be.

In order to achieve the above morphology, the blending composition of the polybutylene terephthalate resin composition is particularly preferably 45 to 100 parts by mass of the acrylonitrile-styrene copolymer (B1) with respect to 100 parts by mass of the polybutylene terephthalate resin (A). The epoxy-modified acrylic polymer (C) is 0.2 to 3 parts by mass, and the glass fiber (D) is 10 to 100 parts by mass.

Further, as another preferable method for producing a molded article having the above morphology, acrylonitrile-styrene copolymer (B1) and epoxy-modified acrylonitrile-styrene copolymer can be used with respect to 100 parts by mass of polybutylene terephthalate resin (A). Injection molding may be performed using a resin composition in which the combined (B2) is added in a total amount of 45 to 100 parts by mass and the mass ratio (B1) / (B2) of the content of (B1) and (B2) is 6 or less. Can be mentioned. By using the epoxy-modified acrylonitrile-styrene copolymer (B2), the familiarity of the acrylonitrile-styrene copolymer (B1) with the polybutylene terephthalate resin (A) is improved. The morphology of the present invention can be obtained.

The injection molding conditions are preferably that the pellets of the polybutylene terephthalate resin composition are sufficiently dried by increasing the drying temperature or extending the drying time, the cylinder temperature is about 250 to 270 ° C., the mold temperature It is preferable that the temperature is 70 to 90 ° C., the cooling time is 15 to 25 seconds, the filling time is 0.5 to 1.5 seconds, and the pressure holding value is about 40 to 80% of the injection peak pressure.

The TVOC amount of the molded article of the present invention is 30 μg C / g or less, more preferably 20 μg C / g or less.
In order to make the TVOC amount of the molded body as described above, the above-mentioned styrene copolymer (B) is one having a styrene monomer gas amount of 600 ppm or less, preferably 550 ppm or less, or a phosphor. It is possible by blending a phyto-based stabilizer or a hindered phenol-based stabilizer.
In addition, the specific measuring method of the TVOC amount of a molded object is as describing in detail in the Example.

The shape of the molded body is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, Examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape.

Since the molded article of the present invention has low warpage, a small amount of gas generation, excellent mechanical properties at high temperatures, and low specific gravity, it can be particularly suitably used as a vehicle interior part that requires these characteristics.

As vehicle interior parts, interior parts for vehicles such as automobiles, trains, trains, etc., for example, inner mirror stays, wave louvers for air conditioners, door handles, handles, doors, sunroofs, seat belts, register blades, Preferred examples include a washer lever, a window regulator handle, a knob of the window regulator handle, a passing light lever, a sun visor bracket, various housings, a switch, and a clip.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
In the following Examples and Comparative Examples, the components used are as shown in Table 1 below.

[Production Example of Acrylonitrile-Styrene Copolymer (B1-1)]
Connect the first reactor, which is a complete mixing tank, and the second reactor, which is a tower-type plug flow reactor with a stirrer, and connect two devolatilizer tanks with preheaters in series. Configured. To 85 parts by mass of a monomer solution containing 30% by mass of acrylonitrile and 70% by mass of styrene, 15 parts by mass of ethylbenzene, 0.01 parts by mass of t-butylperoxyisopropyl monocarbonate and 0.25 parts by mass of t-dodecyl mercaptan are mixed. A raw material solution was prepared. This raw material solution was introduced into a first reactor controlled at 130 ° C. at 6.0 kg per hour. The reaction solution was continuously extracted from the first reactor and introduced into the second reactor. Next, after heating to 160 ° C. with a preheater, it was introduced into the first devolatilization tank reduced to 65 kPa, and further heated to 220 ° C. with a preheater and then introduced into the second devolatilization tank reduced to 1.0 kPa. Residual monomer and solvent were removed. This was extruded and cut into strands to obtain pellet-shaped acrylonitrile-styrene copolymer (B1-1). As shown in Table 1, the composition of copolymer (B1-1) (mass ratio of monomer units) was 30% by mass of acrylonitrile units and 70% by mass of styrene units.

[Production Example of Epoxy-Modified Acrylonitrile-Styrene Copolymer (B2)]
Acrylonitrile, styrene and glycidyl methacrylate were subjected to suspension polymerization to prepare a bead-like glycidyl methacrylate-modified acrylonitrile-styrene copolymer (B2). The ratio of each component of this copolymer was 25/75 / 0.4 mass% in mass ratio of acrylonitrile / styrene / glycidyl methacrylate.

The mass average molecular weight (Mw) and acrylonitrile copolymerization amount (mass%, “PAN ratio”) of the acrylonitrile-styrene copolymer in Table 1 above were measured by the methods described above. MVR was measured using a melt indexer manufactured by Takara Industries Co., Ltd., and the melt flow volume MVR per unit time (unit: cm ³ / unit) measured on the pellets obtained above at 220 ° C. under a load of 2.16 kgf. 10 min).

[Measurement of styrene content and ethylbenzene content]
The amount of styrene and the amount of ethylbenzene in the acrylonitrile-styrene copolymer used were measured by placing 0.002 g of a sample in a glass collecting tube having an outer diameter of 6.35 mm and a length of 90 mm and heat-treating at 270 ° C. for 10 minutes (Thermal The gas generated by the Desorption method was performed by the following chromatograph.
Measuring instrument: GCMS-QP2010 (manufactured by Shimadzu Corporation)
Column: UA-1701 ID 0.25mm
Carrier gas: He
Pressure: 80kPa
Column flow rate: 1.4 mL / min
Column oven temperature: 50 ° C
Vaporization chamber temperature: 25 ° C
Detector: Secondary electron multiplier with conversion dynode Ion source temperature: 250 ° C

(Examples 1 to 12, Comparative Examples 1 to 5)
After uniformly mixing the components shown in Table 1 above in the proportions (all parts by mass) shown in Table 2 using a tumbler mixer, a twin screw extruder (“TEX30α” manufactured by Nippon Steel Works) was used, The resin composition melt-kneaded under conditions of a cylinder set temperature of 260 ° C. and a screw rotation speed of 200 rpm was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of a polybutylene terephthalate resin composition.
Next, the pellets of the obtained polybutylene terephthalate resin composition were dried at 120 ° C. for 8 hours using a hot air dryer, and a flat plate having a length of 100 mm × width of 100 mm × thickness of 3 mm was formed by an injection molding machine (Nissei Plastic Industrial Co., Ltd.). "NEX80"), using a film gate mold, cylinder temperature 260 ° C, mold temperature 80 ° C, cooling time 20 seconds, filling time 1.0 seconds, 50% of injection peak pressure The injection molding was performed under the following conditions.
Note that Comparative Example 3 could not be molded because the viscosity was too high.

[Morphological observation]
From the cross section parallel to the flow direction at the time of molding including the center point of 50 mm in length and 50 mm in width of the flat plate obtained above and having a thickness of 1.5 mm, “UC7” manufactured by Leica was used. Using a diamond knife, a block-shaped sample having an observation surface length of 500 μm × width of 500 μm and a thickness of about 1 cm was cut out. The observation surface of the obtained sample was stained with ruthenium tetroxide for 120 minutes in the gas phase at room temperature, and then using a scanning electron microscope (manufactured by Hitachi High-Tech, “SU8020”), acceleration voltage 1 kV, signal LA100 (U), An SEM image with a magnification of 3000 times was obtained under the conditions of an emission current of 10 μA and a probe current of Normal.
From the obtained SEM image, for the island-shaped portion containing the styrene copolymer (B), the presence or absence of a lake of polybutylene terephthalate resin, whether the island-shaped portion has a plurality of branches, The maximum width of the island portion was measured by the method described above.
Further, from the obtained SEM image, the [(A) phase exists as a lake with respect to [the total area of all islands (this area does not include the area of the lake)]. Area ratio (the total of this area does not include the area of the lake)]. As described above, as the “island-like portion where the lake exists”, an island having a lake having a major axis of 1 μm or more in the island-like portion was adopted in the field of view of the SEM image (magnification 3000 times).
The SEM image used for the analysis had a field of view of 3000 times magnification, and when the glass fiber in the resin composition was in the field of view, an image was selected such that the cross-sectional area of the glass fiber was 10% or less of the field of view.

SEM images (magnification 3000 times) of the molded products of Examples 1 to 4, 7, 9, and 11 are shown in FIGS. 1 to 7.
8 to 10 show SEM images (magnification 3000 times) of the molded bodies of Comparative Examples 1, 2, and 4 using a scanning electron microscope.

[Measurement of TVOC of molded body]
The molded body obtained above is cut into 10 to 25 mg, and about 2 g of each sample is put in a 22 ml vial, sealed, and HS-GC (head space gas chromatograph mass spectrometer) at 120 ° C. for 5 hours. Heat treatment was performed. And the peak integration area of the volatile organic substance component detected with the gas chromatograph was calculated, weight-converted into acetone as a standard, and TVOC (unit: microgram C / g) per 1g of compacts was calculated.

<Evaluation of resin composition>
[Measurement of styrene content and ethylbenzene content]
Measurement of the amount of styrene and the amount of ethylbenzene in the obtained polybutylene terephthalate resin composition was carried out by placing 0.02 g of a sample in a glass collecting tube having an outer diameter of 6.35 mm and a length of 90 mm, and heat treatment at 270 ° C. for 10 minutes ( The gas generated by the Thermal Desorption method was measured by the following chromatograph. The measured value was converted to a value per copolymer or resin composition substance amount, and the amount of styrene and ethylbenzene generated (unit: mass ppm) was used.
Measuring instrument: GCMS-QP2010 (manufactured by Shimadzu Corporation)
Column: UA-1701 ID 0.25mm
Carrier gas: He
Pressure: 80kPa
Column flow rate: 1.4 mL / min
Column oven temperature: 50 ° C
Vaporization chamber temperature: 25 ° C
Detector: Secondary electron multiplier with conversion dynode Ion source temperature: 250 ° C

[Retention thickening (appearance evaluation of staying strand)]
Using a capillograph (Capillograph 1C manufactured by Toyo Seiki Co., Ltd.), using a flat capillary with a measurement temperature of 270 ° C. and 1φ × 30 mm, the pellets obtained above were charged and retained for 30 minutes at a shear rate of 91.2 sec ⁻¹ . Strands produced by extrusion (retaining strands) were obtained, and the quality of the appearance was judged in the following four stages AD.
A: Gloss is observed on the strand surface and appearance is good B: Gloss is slightly observed on the strand surface and appearance is slightly poor C: No gloss is found on the strand surface and appearance is poor D: Strand cannot be produced and appearance Impossible to evaluate

<Evaluation of molded body>
[85 ℃ ambient bending strength]
The pellets obtained above are dried at 120 ° C. for 5 hours, and then subjected to an ISO multipurpose test using an injection molding machine (“NEX80” manufactured by Nissei Plastic Industry Co., Ltd.) under conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. A piece (4 mm thick) was injection molded.
The bending strength (maximum bending stress, unit: MPa) was measured at a temperature of 85 ° C. in accordance with ISO 178 using an ISO multipurpose test piece (4 mm thickness).

[Warpage amount]
Using an injection molding machine (“NEX80” manufactured by Nissei Plastic Industry Co., Ltd.), a circular plate having a diameter of 100 mm and a thickness of 1.6 mm was molded with a side gate mold under conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. The amount of warpage (unit: mm) of the plate was determined.

[Comprehensive evaluation]
Comprehensive evaluation is judged by the following criteria
A: Evaluation of molded product “warping amount is 5.0 mm or less”, “85 ° C. atmosphere bending strength is 120 MPa or more”, evaluation of resin composition “generation amount of styrene and ethylbenzene is 55 ppm or less”, “residual thickening is All conditions of “A or B” are satisfied.
B: None of A and C below.
C: Evaluation of molded product “warping amount is 6.0 mm or more”, “85 ° C. atmosphere bending strength is less than 120 MPa”, evaluation of resin composition “generation amount of styrene and ethylbenzene exceeds 55 ppm”, “retention thickening is D ”.
The above evaluation results are shown in the following table.

(Examples 13 to 24 relating to the second invention, Comparative Examples 6 to 12)
The same procedure as described above was conducted except that the components shown in Table 1 were used in the proportions shown in Table 4-5 below.
The results are shown below.

(Examples 25 to 35 relating to the third invention, Comparative Examples 13 to 16)
The same procedure as described above was conducted except that the components shown in Table 1 were used in the proportions shown in Table 4-5 below.
The results are shown below.

The molded article of the polybutylene terephthalate resin composition of the present invention is less warped, has less gas generation, can satisfy VOC regulations, and has excellent bending strength at high temperatures, so it can be used for various molded products, especially automobiles. It can use suitably as interior parts for vehicles, such as.

Claims

Acrylonitrile-styrene copolymer (B1) and / or epoxy-modified acrylonitrile-styrene copolymer (B2) as styrene copolymer (B) with respect to 100 parts by mass of polybutylene terephthalate resin (A) A molded body having a sea-island structure and a minimum thickness of more than 1 mm, comprising a polybutylene terephthalate resin composition containing a total of 45 to 100 parts by mass of
The polybutylene terephthalate resin (A) forms a continuous phase,
The domain containing the styrene copolymer (B) is dispersed in an island shape in the continuous phase of the polybutylene terephthalate resin (A), and at least a part of the domain is in the island-shaped portion. The phase of A) exists as a lake, and has a morphology in which the maximum width of the island-shaped part measured by the following method is 6 μm or less,
The amount of volatile organic compounds (TVOC) detected when a gas generated by heat-treating the molded body at 120 ° C. for 5 hours is analyzed by gas chromatography is 30 μg C / g or less.
A molded article of polybutylene terephthalate resin composition characterized by the above.
How to measure the maximum width of islands:
The maximum value of the width of the island portion is measured from the SEM image (magnification is 3000 times) in the cross section including the center point in the thickness direction of the portion where the thickness of the molded body is maximum.
The polybutylene terephthalate resin composition molded body according to claim 1, wherein at least a part of the island-shaped portion of the polybutylene terephthalate resin (A) is an island-shaped portion having a branched portion.
3. The polybutylene terephthalate resin composition molded body according to claim 1, wherein the TVOC amount from the molded body is 20 μg C / g or less.
The amount of a styrene monomer detected when a gas generated by heat-treating a polybutylene terephthalate resin composition at 270 ° C for 10 minutes is analyzed by gas chromatography is 45 ppm by mass or less. The polybutylene terephthalate resin composition molded article according to any one of the above.
The polybutylene terephthalate resin composition molded article according to any one of claims 1 to 4, wherein the polybutylene terephthalate resin composition further contains an epoxy-modified acrylic polymer (C).
The polybutylene terephthalate resin composition is used in an amount of 45 to 100 parts by mass of the acrylonitrile-styrene copolymer (B1), 100 parts by mass of the polybutylene terephthalate resin (A), 0.2% of the epoxy-modified acrylic polymer (C). The molded product of polybutylene terephthalate resin composition according to any one of claims 1 to 5, which contains 3 to 3 parts by mass and 10 to 100 parts by mass of glass fiber (D).
The polybutylene terephthalate resin composition comprises 45 to 45 total parts of the acrylonitrile-styrene copolymer (B1) and the epoxy-modified acrylonitrile-styrene copolymer (B2) with respect to 100 parts by mass of the polybutylene terephthalate resin (A). 100 parts by mass, the mass ratio (B1) / (B2) of the contents of (B1) and (B2) is 6 or less, and further contains 10 to 100 parts by mass of glass fiber (D). 5. A molded article of the polybutylene terephthalate resin composition according to any one of 4 above.
The molded body according to any one of claims 1 to 7, which is a vehicle interior part.
45-100 parts by mass of acrylonitrile-styrene copolymer (B1), 0.2-3 parts by mass of epoxy-modified acrylic polymer (C), and glass fiber with respect to 100 parts by mass of polybutylene terephthalate resin (A) (D) A polybutylene terephthalate resin composition containing 10 to 100 parts by mass.
10. The polybutylene according to claim 9, wherein the amount of styrene monomer detected when a gas generated by heat-treating the polybutylene terephthalate resin composition at 270 ° C. for 10 minutes is analyzed by gas chromatography is 45 ppm or less. A terephthalate resin composition.
The polybutylene terephthalate resin composition according to claim 9 or 10, wherein the acrylonitrile-styrene copolymer (B1) is a bulk polymer.
Containing 45 to 100 parts by mass of the total of acrylonitrile-styrene copolymer (B1) and epoxy-modified acrylonitrile-styrene copolymer (B2) with respect to 100 parts by mass of polybutylene terephthalate resin (A), (B1 ) And (B2) content ratio (B1) / (B2) is 6 or less, and further contains 10 to 100 parts by mass of glass fiber (D), a polybutylene terephthalate resin composition.
The polybutylene terephthalate resin composition according to claim 12, wherein the mass ratio (B1) / (B2) of the contents of (B1) and (B2) is 0.5 to 6.
The amount of the styrene monomer detected when the gas generated by heat-treating the polybutylene terephthalate resin composition at 270 ° C for 10 minutes is analyzed by gas chromatography is 45 ppm or less. The polybutylene terephthalate resin composition described.
The polybutylene terephthalate resin composition according to any one of claims 12 to 14, wherein the acrylonitrile-styrene copolymer (B1) is a bulk polymer.