JP2020164740A - Polystyrene resin composition - Google Patents

Abstract

To obtain a polystyrene resin composition having excellent mechanical physical properties without causing a deterioration of moldability.SOLUTION: A polystyrene resin composition contains (A) a polyamide resin, (B) a polystyrene resin having a syndiotactic structure, (C) a compatibilizer having a polar group that can react with (A) the polyamide resin and having compatibility with the polystyrene resin (B), and (D) a glass filler, at least part of the surface of the glass filler having a surface treatment agent, and the surface treatment agent containing a silane compound, a copolymerization compound, and a polyurethane resin.SELECTED DRAWING: None

Description

The present invention relates to polystyrene-based resin compositions.

It has already been established that polystyrene-based resins having a syndiotactic structure (hereinafter, may be abbreviated as "SPS") have excellent mechanical strength, heat resistance, electrical characteristics, water absorption dimensional stability, chemical resistance, and the like. It is known and is expected to have many uses. Among them, due to the excellent chemical resistance, heat resistance, electrical characteristics and water absorption dimensional stability of SPS, its applications in electrical / electronic equipment materials, in-vehicle / electrical parts, home appliances, various mechanical parts, industrial materials, etc. are attracting attention. I'm collecting.

It is known that a resin composition having an excellent balance of strength, toughness, heat resistance, chemical resistance, molding processability and the like can be obtained by mixing SPS and a polyamide resin. For example, Patent Document 1 discloses a styrene-based resin composition in which SPS, a polyamide resin, and a specific polyphenylene ether resin are blended in a specific ratio.

On the other hand, it is widely known to add a filler as a means for imparting or improving desired physical properties to the resin. For example, by adding glass fiber or carbon fiber to the resin, it is possible to obtain a resin having improved mechanical properties. Such a resin is called a fiber reinforced resin, and for example, a polyamide resin to which glass fibers are added (glass fiber reinforced polyamide) is used in a wide range of applications.

Japanese Patent Application Laid-Open No. 03-126744

However, when the glass fiber is added to the polystyrene resin composition containing the SPS and the polyamide resin, the desired mechanical properties cannot be obtained, for example, the rigidity is inferior to that when the glass fiber is added to the polyamide resin. There was a problem. In particular, it was found that the compatibilizer that improves the compatibility between the resin and the glass filler has a high affinity between the SPS and the glass filler, but is inferior in the affinity with the polyamide, resulting in inferior mechanical properties. .. Further, it is conceivable to increase the amount of glass fiber added in order to improve the mechanical properties, but on the other hand, there is a new problem that the moldability of the resin is deteriorated. It is required to obtain a polystyrene-based resin composition having excellent mechanical properties without such a decrease in molding processability.

As a result of diligent research conducted by the present inventor in order to solve the above problems, the filler is added by using a glass filler treated with a surface treatment agent containing a silane compound, a copolymer compound, and a polyurethane resin. We have found that the mechanical properties of the polystyrene-based resin composition can be improved without increasing the amount, and have completed the present invention. That is, the present invention relates to the following.

[1] (A) Polystyrene resin, (B) Polystyrene resin having a syndiotactic structure, (C) Polystyrene resin (A) having a polar group capable of reacting with polystyrene resin (B) A compatibilizer having solubility, (D) a glass filler is contained, and at least a part of the surface of the glass filler has a surface treatment agent, and the surface treatment agent includes a silane compound, a copolymer compound, and polyurethane. A polystyrene-based resin composition containing a resin.
[2] The polystyrene-based resin composition according to the above [1], wherein the compatibilizer (C) is a modified polyphenylene ether.
[3] The polystyrene-based resin composition according to the above [1] or [2], wherein the compatibilizer (C) contains at least one of maleic anhydride-modified polyphenylene ether and fumaric acid-modified polyphenylene ether.
[4] The copolymer compound is at least one selected from the group consisting of unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and unsaturated dicarboxylic acid anhydride, and acrylic acid-based monomer and methacrylic acid-based simple substance. The polystyrene-based resin composition according to any one of the above [1] to [3], which is a copolymer with at least one of the weights.
[5] The polystyrene-based resin composition according to any one of the above [1] to [4], wherein the content of the surface treatment agent is 0.01 to 4% by mass of the glass filler (D).
[6] The polystyrene-based resin composition according to any one of the above [1] to [5], wherein the glass filler (D) is glass fiber.
[7] The content of the polyamide resin (A) is 40 to 80% by mass in 100% by mass of the polystyrene-based resin composition, and the content of the polystyrene-based resin (B) having a syndiotactic structure is 10 to 10. The polystyrene resin composition according to any one of the above [1] to [6], which is 30% by mass.
[8] The polystyrene-based resin according to any one of the above [1] to [7], wherein the content of the compatibilizer (C) is 1 to 10% by mass in 100% by mass of the polystyrene-based resin composition. Composition.
[9] The polystyrene-based resin composition according to any one of the above [1] to [8], wherein the content of the glass filler (D) is 20 to 50% by mass in 100% by mass of the polystyrene-based resin composition. object.
[10] A molded product made of the polystyrene-based resin composition according to any one of the above [1] to [9].

According to the present invention, a polystyrene-based resin composition having excellent mechanical properties can be obtained.

Hereinafter, the present invention will be described in detail.
In the present specification, the description of "XX to YY" means "XX or more and YY or less". In the present specification, the preferred provisions can be arbitrarily adopted, and the combination of preferable ones is more preferable.

The polystyrene-based resin composition of the present invention has (A) a polyamide resin, (B) a polystyrene-based resin having a syndiotactic structure, and (C) a polystyrene-based resin having a polar group capable of reacting with the polyamide resin (A). A compatibilizer having compatibility with the resin (B) and a glass filler (D) are contained, and at least a part of the surface of the glass filler has a surface treatment agent, and the surface treatment agent is a silane compound. , A copolymer compound and a polyurethane resin.

<Polyamide resin (A)>
As the polyamide resin, a known polyamide resin can be used.
Suitable polyamides include, for example, polyamide-4, polyamide-6, polyamide-6,6, polyamide-3,4, polyamide-12, polyamide-11, polyamide-6,10, polyamide-4T, polyamide-6T, polyamide. -9T, polyamide-10T, and polyamides obtained from adipic acid and m-xylylene diamine can be mentioned. Of these, polyamide-6 and 6 are preferable.

The content of the polyamide resin (A) in 100% by mass of the polystyrene-based resin composition of the present invention is preferably 40 to 80% by mass. When the content of the polyamide resin (A) is 40% by mass or more, excellent mechanical strength such as high tensile breaking strength and tensile breaking elongation can be obtained. When the content of the polyamide resin (A) is 80% by mass or less, the hydrolysis resistance is excellent.
The content of the polyamide resin (A) in 100% by mass of the polystyrene resin composition of the present invention is more preferably 43% by mass or more, further preferably 45% by mass or more, still more preferably 75% by mass or less, and further. It is preferably 70% by mass or less.

<Polystyrene resin (B)>
The polystyrene-based resin (B) is an SPS having a highly syndiotactic structure. As used herein, the term "syndiotactic" means that phenyl rings in adjacent styrene units are alternately arranged with respect to the plane formed by the main chain of the polymer block (hereinafter, referred to as syndiotacticity). It means that the percentage of styrene is high.
Tacticity can be quantitatively identified by the nuclear magnetic resonance method using isotope carbon ( ¹³ C-NMR method). ^{13 By the} C-NMR method, the abundance ratio can be quantified by using a plurality of consecutive structural units, for example, two consecutive monomer units as diads, three monomer units as triads, and five monomer units as pentads.

In the present invention, the "polystyrene resin having a highly syndiotactic structure" is usually 75 mol% or more, preferably 85 mol% or more, or racemipentad (rrrr), usually 30% or more. Polystyrene, poly (hydrocarbon-substituted styrene), poly (halogenated styrene), poly (alkyl halide styrene), poly (alkoxystyrene), poly (polystyrene) having syndiotacticity of mol% or more, preferably 50 mol% or more. (Vinyl benzoic acid ester), hydrides or mixtures thereof, or copolymers containing these as main components.

Poly (hydrocarbon-substituted styrene) includes poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tert-butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene) and poly (poly (vinyl naphthalene)). Vinyl styrene) and the like. Examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene) and poly (fluorostyrene), and examples of poly (alkyl halide styrene) include poly (chloromethylstyrene). it can. Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
As the comonomer component of the copolymer containing the above-mentioned structural unit, in addition to the above-mentioned styrene-based polymer monomer, an olefin monomer such as ethylene, propylene, butene, hexene and octene; a diene monomer such as butadiene and isoprene; a cyclic olefin monomer , Cyclic diene monomers, methyl methacrylate, maleic anhydride and polar vinyl monomers such as acrylonitrile.

Among the above polystyrene-based resins, polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), and poly (m) are particularly preferable. -Chlorostyrene), poly (p-fluorostyrene) can be mentioned.
Further, a copolymer of styrene and p-methylstyrene, a copolymer of styrene and p-tert-butylstyrene, a copolymer of styrene and divinylbenzene and the like can be mentioned.

The weight average molecular weight of SPS (B) is preferably 1 × 10 ⁴ or more and 1 × 10 ⁶ or less, preferably 50,000 or more and 500, from the viewpoint of the fluidity of the resin during molding and the strength of the obtained molded product. More preferably, it is 000 or less. When the weight average molecular weight is 1 × 10 ⁴ or more, a molded product having sufficient strength can be obtained. On the other hand, if the weight average molecular weight is 1 × ¹⁰⁶ or less, there is no problem in the fluidity of the resin during molding.
In the present specification, the weight average molecular weight refers to a GPC apparatus manufactured by Tosoh Corporation (HLC-8321GPC / HT) and a GPC column manufactured by Tosoh Corporation (GMHHR-H (S) HTC / HT) unless otherwise specified. It is a value measured by gel permeation chromatography measurement at 145 ° C. using 1,2,4-trichlorobenzene as an eluent, and converted using a standard polystyrene inspection line. Sometimes abbreviated simply as "molecular weight".

The SPS (B) is preferably 2 g / 10 minutes or more, preferably 4 g / 10 minutes or more, preferably within this range, when MFR measurement is performed under the conditions of a temperature of 300 ° C. and a load of 1.2 kg. , There is no problem with fluidity during molding. Further, if it is 50 g / 10 minutes or less, preferably 30 g / min or less, a molded product having sufficient mechanical properties can be obtained.

SPS (B) is a styrene-based monomer (the above-mentioned styrene-based polymer), for example, in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product (aluminoxane) of water and trialkylaluminum as a catalyst. It can be produced by polymerizing (a monomer corresponding to a polymer) (for example, JP-A-2009-068022).

The content of SPS (B) in 100% by mass of the polystyrene-based resin composition of the present invention is preferably 10 to 30% by mass. When the content of SPS (B) is within the above range, it is excellent in long-term heat resistance and mechanical strength such as tensile breaking strength and tensile breaking elongation.
The content of SPS (B) in 100% by mass of the polystyrene-based resin composition of the present invention is more preferably 13% by mass or more, further preferably 15% by mass or more, still more preferably 18% by mass or more, and more. It is preferably 25% by mass or less, more preferably 20% by mass or less.

When the amount of the polyamide resin (A) contained in the polystyrene-based resin composition of the present invention is x% by mass and the amount of SPS (B) is y% by mass, it is preferable that x> y. By satisfying the above relational expression, excellent mechanical strength can be obtained. The polyamide resin (A) amount x (mass%) and the SPS (B) amount y (mass%) are as described above.

<Compatible agent (C)>
As the compatibilizer (C), a compound having a polar group capable of reacting with the polyamide resin (A) and having compatibility with SPS (B) is used. The compatibilizer (C) is blended for the purpose of improving the compatibility between the polyamide resin (A) and the SPS (B), finely dispersing the domain, and improving the interfacial strength between the components. The polar group capable of reacting with the polyamide resin (A) refers to a functional group capable of reacting with the polar group of the polyamide. Specific examples include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid halide group, a carboxylic acid amide group, a carboxylic acid base, a sulfonic acid group, a sulfonic acid ester group, and a sulfonated compound group. Examples thereof include a sulfonic acid amide group, a sulfonic acid base, an epoxy group, an amino group, an imide group and an oxazoline group.
The one having compatibility with SPS (B) refers to the one containing a chain having compatibility with SPS in the polymer chain. For example, a polymer having syndiotactic polystyrene, atactic polystyrene, isotactic polystyrene, a styrene-based polymer, polyphenylene ether, polyvinyl methyl ether and the like as a main chain, a block chain or a graft chain can be mentioned.

Specific examples of the compatibilizer (C) include styrene-maleic anhydride copolymer (SMA), styrene-glycidyl methacrylate copolymer, terminal carboxylic acid-modified polystyrene, terminal epoxy-modified polystyrene, terminal oxazoline-modified polystyrene, and terminal amine-modified. Polystyrene, sulfonated polystyrene, styrene-based ionomer, styrene-methylmethacrylate-graft polymer, (styrene-glycidylmethacrylate) -methylmethacrylate-graft copolymer, acid-modified acrylic-styrene-graft polymer, (styrene-glycidylmethacrylate) -styrene -Graft polymer, polybutylene terephthalate-polystyrene-Graft polymer, modified styrene polymer such as maleic anhydride-modified SPS, fumaric acid-modified SPS, glycidyl methacrylate-modified SPS, amine-modified SPS, (styrene-maleic anhydride) -polyphenylene ether- Examples thereof include graft polymers, modified polyphenylene ethers such as maleic anhydride-modified polyphenylene ethers, fumaric acid-modified polyphenylene ethers, glycidyl methacrylate-modified polyphenylene ethers, and amine-modified polyphenylene ethers. Of these, modified polyphenylene ether and / or modified SPS are preferable, and it is more preferable to contain at least one of maleic anhydride-modified polyphenylene ether or fumaric acid-modified polyphenylene ether as the compatibilizer (C).

The modified polyphenylene ether can be obtained by modifying a known polyphenylene ether with a modifying agent, but the method is not limited to this method as long as it can be used for the purpose of the present invention. The polyphenylene ether is a known compound, and for this purpose, U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357 and 3,257,358, respectively. You can refer to the specification. Polyphenylene ethers are usually prepared by an oxidative coupling reaction with di- or tri-substituted phenols in the presence of a copper amine complex catalyst. As the copper amine complex, copper amine complexes derived from the first, second and third amines can be used.

Examples of polyphenylene ethers include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1,4-phenylene ether), and poly (2-). Methyl-6-hydroxyethyl-1,4-phenylene ether), poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1,4-phenylene) Ether), poly (2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly [2- (4'-methyl) Phenyl) -1,4-phenylene ether], poly (2-bromo-6-phenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2) -Phenyl-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether), poly (2-chloro-6-ethyl-1) , 4-Phenylene ether), poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-di-n-propyl-1,4-phenylene ether), poly (2-methyl -6-Isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether) and poly (2) , 6-Dimethyl-1,4-phenylene ether) and the like.

For example, a copolymer derived from two or more of the phenolic compounds used in the preparation of the polyphenylene ether can also be used. Further, a graft copolymer and a block copolymer of a vinyl aromatic compound such as polystyrene and the above-mentioned polyphenylene ether can also be mentioned. Particularly preferably, poly (2,6-dimethyl-1,4-phenylene ether) is used.

Examples of the modifier used for the modification of polyphenylene ether include compounds having an ethylenic double bond and a polar group in the same molecule, and specifically, for example, maleic anhydride, maleic acid, fumaric acid, and maleic acid ester. , Fumaric acid ester, maleimide and its N-substituted product, maleate, fumarate, acrylic acid, acrylic acid ester, acrylic acid amide, acrylic acid salt, methacrylic acid, methacrylic acid ester, methacrylic acid amide, methacrylate, Examples include glycidyl methacrylate. Of these, maleic anhydride, fumaric acid and glycidyl methacrylate are particularly preferably used. The above-mentioned various denaturants may be used alone or in combination of two or more.

The modified polyphenylene ether can be obtained, for example, by reacting the polyphenylene ether with a modifying agent in the presence of a solvent or another resin. The method of denaturation is not particularly limited, and a known method can be used. Specific examples thereof include a method of melt-kneading and reacting at a temperature in the range of 150 to 350 ° C. using a roll mill, a Banbury mixer, an extruder, etc., and a method of heating and reacting in a solvent such as benzene, toluene, and xylene. be able to. Further, in order to facilitate the reaction, the reaction system contains benzoyl peroxide; di-tert-butyl peroxide; dikmyl peroxide; tert-butylperoxybenzoate; azobisisobutyronitrile; azobisisovaleronitrile; It is also effective to have a radical generator such as 2,3-diphenyl-2,3-dimethylbutane. A method of melt-kneading in the presence of a radical generator is particularly preferable.

A modified SPS having a polar group can also be used as the compatibilizer (C). The modified SPS can be obtained by modifying the above-mentioned SPS with, for example, a modifying agent, but is not limited to this method as long as it can be used for the purpose of the present invention. The SPS used for the modification is not particularly limited, but a copolymer of styrene and substituted styrene is particularly preferably used in terms of compatibility with other components. The composition ratio of this copolymer is not particularly limited, but the content of the substituted styrene unit is preferably in the range of 3 to 50 mol%. If this content is 3 mol% or more, denaturation is easy, and if it is 50 mol% or less, compatibility with other components can be maintained.

Particularly preferable substituted styrenes include, for example, alkyl styrenes such as methyl styrene, ethyl styrene, isopropyl styrene, tert-butyl styrene and vinyl styrene, halogenated styrene such as chloro styrene, bromo styrene and fluoro styrene, and halogenation of chloromethyl styrene and the like. Examples thereof include alkoxystyrene such as alkylstyrene, methoxystyrene, and ethoxystyrene. One of these substituted styrenes may be used alone, or two or more thereof may be used in combination. Since the heat resistance of the composition can be maintained if the amount used is 5% by mass or less with respect to SPS, the above polymer having an atactic structure can also be used.

As the modifying agent used for the modification of SPS, a compound having an ethylenic double bond and a polar group in the same molecule can be used. Examples of such modifiers include maleic anhydride, maleic acid, fumaric acid, maleic acid ester, fumaric acid ester, maleimide and its N-substituted products, maleic anhydride, fumaric acid, acrylic acid, acrylic acid ester, and acrylic. Examples thereof include acid amide, acrylate, methacrylic acid, methacrylic acid ester, methacrylic acid amide, methacrylic acid salt, and glycidyl methacrylate. Of these, maleic anhydride, fumaric acid or glycidyl methacrylate are particularly preferably used. One of these modifiers may be used alone, or two or more thereof may be used in combination.

The modified SPS can be obtained, for example, by reacting the SPS with a modifying agent in the presence of a solvent or other resin. The modification method is not particularly limited, and a known method can be used. Specifically, a method of melt-kneading and reacting at a temperature in the range of 150 to 350 ° C. using a roll mill, a Banbury mixer, an extruder, or the like, or a method of heating and reacting in a solvent such as benzene, toluene, or xylene is used. Can be used. In order to facilitate these reactions, the reaction system includes benzoyl peroxide, di-tert-butyl peroxide, dikmyl peroxide, tert-butylperoxybenzoate, azobisisobutyronitrile, azobisisovaleronitrile, etc. The presence of a radical generator such as 2,3-diphenyl-2,3-dimethylbutane is effective. A method of melt-kneading in the presence of a radical generator is particularly preferable. Among these modified SPSs, maleic anhydride-modified SPS, fumaric acid-modified SPS, and glycidyl methacrylate-modified SPS are preferably used.

The content of the compatibilizer (C) in 100% by mass of the polystyrene-based resin composition of the present invention is preferably 1 to 10% by mass. When the content of the compatibilizer (C) is 1% by mass or more, fluffing of pellets and molded articles obtained from the composition of the present invention can be suppressed, and production stability is excellent. When the content of the compatibilizer (C) is 10% by mass or less, the fluidity of the composition can be kept high.
In the present invention, the content of the compatibilizer (C) in 100% by mass of the polystyrene-based resin composition is more preferably 1.5% by mass or more, still more preferably 2% by mass or more, still more preferably 2.5% by mass. % Or more, more preferably 8% by mass or less, still more preferably 7% by mass or less, still more preferably 5% by mass or less.

<Glass filler (D)>
As the glass filler (D), a glass filler having various existing glass compositions such as E glass, AR glass, C glass, D glass, H glass, S glass, T glass, M glass, and NE glass can be used. ..

As the glass filler (D), a known shape can be used, and examples thereof include glass filament, glass fiber, glass roving, glass mat, glass powder, glass flakes, and glass beads. Above all, it is preferable to use glass fiber.

The glass fiber may be a single fiber or a plurality of single fibers twisted together.
The form of glass fiber is "glass roving", which is a continuous winding of single fiber or multiple twisted fibers, "chopped strand", which is cut to a length of 1 to 10 mm, and "chopped strand", which is crushed to a length of about 10 to 500 μm. It may be any of "milled fiber" and the like. As the glass fiber, those having different morphologies can be used in combination.
The length of the glass fiber in the present invention is a number average fiber length, which is usually the same as the cut length.

The average diameter of the cross section of the glass fiber is preferably 3 to 50 μm, more preferably 3 to 20 μm. The average diameter of the cross section of the glass fiber is a value obtained by calculating the diameter value of the glass fiber from the measurement of the mass of the glass fiber having a length of 1000 m.

The content of the glass filler (D) in 100% by mass of the polystyrene-based resin composition of the present invention is preferably 20 to 50% by mass. When the content of the glass filler (D) in the polystyrene-based resin composition is 20% by mass or more, the mechanical strength of the molded product obtained from the composition is excellent. When the content of the glass filler (D) is 50% by mass or less, the fluidity is excellent, so that the moldability can be kept good.
The content of the glass filler (D) in 100% by mass of the polystyrene-based resin composition of the present invention is more preferably 23% by mass or more, further preferably 25% by mass or more, still more preferably 28% by mass or more. It is more preferably 45% by mass or less, further preferably 40% by mass or less, and even more preferably 35% by mass or less.

At least a part of the surface of the glass filler (D) needs to have the surface treatment agent described below. The content of the surface treatment agent is preferably 0.01 to 4% by mass of the glass filler (D). When the content of the surface treatment agent is within the above range, the dispersibility of the glass filler is improved when the glass filler (D) and the polyamide resin (A) are mixed in the resin composition of the present invention. The mechanical strength can be improved. The content of the surface treatment agent is more preferably 0.1 to 2.0% by mass of the glass filler (D).
Further, the ignition loss of the glass filler (D) having the surface treatment agent is preferably 0.1 to 1.5% by mass, more preferably 0.4 to 1.2% by mass. The ignition loss is a value measured in accordance with JIS R 3420 (2006) 7.3.2.

The surface treatment agent contained in at least a part of the surface of the glass filler (D) includes a silane compound, a copolymer compound, and a polyurethane resin. The surface treatment agent may be referred to as a "focusing agent" when the glass filler (D) is glass fiber. The surface treatment agent is usually located on the surface of the glass filler.

The surface treatment agent for the glass filler (D) includes a silane compound, a so-called silane coupling agent. Silane compounds used as silane coupling agents have an alkoxy group and an alkyl group, and when the alkoxy group is hydrolyzed, they become silanol groups, some of which are bonded to the surface of the glass filler, and the rest are bonded to each other. It is considered that the mesh structure is formed on the surface of the glass filler. In addition, silanol bonds and alkyl groups are preferred because they can protect the surface of the glass filler from scratches and erosion. Specific examples of the silane compound (silane coupling agent) include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-. (1,1-Epoxycyclohexyl) Ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-amino Propyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-tris (2- Methoxy-ethoxy) silane, N-methyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-4,5-dihydroimidazolepropyltriethoxy. Examples thereof include silane, hexamethyldisilazane, N, N-bis (trimethylsilyl) urea, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine and the like. Among these, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Aminosilanes such as trimethoxysilane and epoxysilanes are preferable.

The copolymer contained in the surface treatment agent of the glass filler (D) is at least one selected from the group consisting of unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and unsaturated dicarboxylic acid anhydride, and an acrylic acid-based single amount. It is preferably a copolymer of the compound and at least one of the methacrylic acid-based monomers.
Although not bound by a specific theory, a copolymer compound obtained by copolymerizing at least one unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated dicarboxylic acid anhydride, and a (meth) acrylic acid-based monomer is a polyamide resin. It is considered to have an action of facilitating chemical (intermolecular force, ionic bond, etc.) and / or physical (entanglement of molecular chains, etc.) with (A).
As used herein, the term "(meth) acrylic acid-based monomer" means both "acrylic acid-based monomer" and "methacrylic acid-based monomer". The same applies to other similar terms (“(meth) acrylic acid”, “(meth) acrylate”, etc.).

Unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, vinyl acetate, α-cyanocinnamic acid, β-styrylacrylic acid, β-flufurylacrylic acid, oleic acid, α-chloroacrylic acid. Acrylic acid and the like can be mentioned.
Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid. Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, and unsaturated dicarboxylic acid anhydride such as dodecenyl succinic anhydride. Among these, maleic anhydride is particularly preferable because it has less steric hindrance during copolymerization and the polarity of the compound is small, and it is more preferable to copolymerize only maleic anhydride.

The proportion of at least one of the unsaturated monocarboxylic acid, the unsaturated dicarboxylic acid and the unsaturated dicarboxylic acid anhydride in the copolymer compound is preferably 20 to 60% by mass. By setting the proportion of at least one of the unsaturated monocarboxylic acid, the unsaturated dicarboxylic acid and the unsaturated dicarboxylic acid anhydride in the copolymer compound to 20% by mass or more, the chemical bond with the polyamide resin (A) is formed. It can be further improved and the mechanical strength of the polystyrene-based resin composition can be further improved. By setting the proportion of at least one of unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and unsaturated dicarboxylic acid anhydride in the copolymer compound to 60% by mass or less, the chemical bond is sufficient and the copolymerization is carried out. The weight average molecular weight of the copolymer compound can be appropriately increased. By advancing the copolymerization to some extent, the entanglement with the polyamide resin is increased and the physical bond is improved. Further, when the weight average molecular weight of the copolymer compound is increased in an appropriate range, the entanglement between the polyamide resin (A) and the copolymer compound is improved, and the mechanical strength of the polystyrene resin composition of the present invention is improved. The proportion of at least one of the unsaturated carboxylic acid, the unsaturated dicarboxylic acid and the unsaturated dicarboxylic acid anhydride in the copolymer compound is more preferably 25 to 55% by mass.

The (meth) acrylic monomer in the copolymer compound contains at least one selected from (meth) acrylic acid, alkyl (meth) acrylate, hydroxy group-containing alkyl (meth) acrylate and aryl (meth) acrylate. Is preferable.
Examples of the (meth) acrylic monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Examples thereof include butyl (meth) acrylate, phenyl (meth) acrylate, and naphthyl (meth) acrylate.

The copolymer compound is preferably a copolymer of an acrylic acid-based monomer and a methacrylic acid-based monomer and the unsaturated carboxylic acid-based compound described above.
The proportion of acrylic acid-based monomer in the copolymer compound is preferably 20 to 75% by mass. When the proportion of the acrylic acid-based monomer in the copolymer compound is 20% by mass or more, the copolymerization easily proceeds and the weight average molecular weight of the copolymer compound can be increased. By advancing the copolymerization and increasing the weight average molecular weight, the entanglement with the polyamide resin (A) increases, and the physical bond is improved. By setting the proportion of the acrylic acid-based monomer in the copolymer compound to 75% by mass or less, the proportion of at least one of the unsaturated monocarboxylic acid, the unsaturated dicarboxylic acid and the unsaturated dicarboxylic acid anhydride to be copolymerized can be adjusted. It can be increased, the chemical bond with the polyamide resin is improved, and the mechanical strength of the polystyrene-based resin composition of the present invention is improved. The proportion of the acrylic acid-based monomer in the copolymer compound is more preferably 30 to 65% by mass.

The proportion of the methacrylic acid-based monomer in the copolymer compound is preferably 5 to 20% by mass. By setting the proportion of the methacrylic acid-based monomer in the copolymer compound to 5% by mass or more, the copolymerization easily proceeds, the weight average molecular weight of the copolymer compound increases, and the entanglement with the polyamide resin increases. Physical coupling is improved. By setting the proportion of the methacrylic acid-based monomer in the copolymer compound to 20% by mass or less, the proportion of the unsaturated monocarboxylic acid, the unsaturated dicarboxylic acid or the unsaturated dicarboxylic acid anhydride to be copolymerized increases, and the polyamide The chemical bond with the resin is improved, and the mechanical strength of the polystyrene-based resin composition of the present invention is improved. The proportion of the methacrylic acid-based monomer in the copolymer compound is more preferably 7 to 17% by mass.

The above copolymer compound may also be copolymerized with other components such as styrene, ethylene and acetylene. The proportion of the other components in the copolymer compound is preferably 10% by mass or less, more preferably 1% by mass or less.

The weight average molecular weight of the copolymer compound is preferably 10,000 to 60,000. By setting the weight average molecular weight of the copolymer compound to 10,000 or more, the entanglement with the polyamide resin (A) becomes good, and the mechanical strength of the polystyrene-based resin composition of the present invention tends to improve. By setting the weight average molecular weight of the copolymer compound to 60,000 or less, the dispersibility of the glass filler in the polyamide resin (A) can be further improved. The weight average molecular weight of the copolymer compound is more preferably 20,000 to 50,000. The weight average molecular weight of the copolymer compound is the molecular weight measured by gas permeation chromatography (GPC).

The polyurethane resin contained in the surface treatment agent for the glass filler (D) has good chemical bonding properties with the silane compound and the polyamide resin (A). When the surface treatment agent contains a polyurethane resin, the polyamide resin (A) can be bonded to a functional group at the terminal of an alkyl group of a silane compound (for example, an aminosilane compound) via the polyurethane resin. As a result, the mechanical strength is considered to be improved.

Polyurethane is obtained by reacting a polyol component and a polyisocyanate component with urethane. Among urethane raw materials, polyester polyols (condensation polyester polyols, lactone-based polyester polyols, polycarbonate polyols, etc.), polyether polyols, and the like are used.

Among these, as the condensation polyester polyol, dicarboxylic acids such as adipic acid, succinic acid, azelaic acid, pimelli acid, sebacic acid and phthalic acid or lower alkyl esters thereof, ethylene glycol, 1,4-butanediol and 1,6 Aliphatic diols such as −hexanediol and 1,10-decamethylene glycol that do not have side chains, 1,2-propylene glycol, 1,3-butanediol, 2,5-dimethyl-2,5-hexanediol, Examples thereof include those obtained by reacting an aliphatic diol having a side chain such as 2,2-diethyl-1,3-propanediol and neopentyl glycol.

As the lactone-based polyester polyol, short-chain lactone compounds such as β-propiolactone, pivalolactone, δ-valerolactone, ε-caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, and trimethyl-ε-caprolactone are used. Examples thereof include those reacted with a hydroxy compound such as a polyol.

As the polycarbonate polyol, a hydroxy compound such as a short-chain polyol and a polycarbonate polyol obtained from a diallyl carbonate, a dialkyl carbonate or an ethylene carbonate by a transesterification reaction is used. For example, poly-1,6-hexamethylene carbonate, poly-2,2'-bis (4-hydroxycyclohexyl) propane carbonate and the like are industrially produced and easily available. As another method for obtaining the polycarbonate polyol, the so-called phosgene method (or solvent method) can be used.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxypropylene glycol, glycerin-based polyalkylene ether glycol and the like. In addition to the above, various polyurethane polyols can also be used.

Among the urethane raw materials, polyisocyanates include, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexylmethane diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, and isopropyridenebis. (4-Cyclohexyl isocyanate), methylcyclohexane diisocyanate, isophorone diisocyanate and other aliphatic or alicyclic diisocyanates, 2,4- or 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane With -4,4'-diisocyanate, m- or p-phenylenediocyanate, chlorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, polyhydric alcohol and polyisocyanate Adduct and so on.
In the urethane reaction, a chain extender such as a polyhydric alcohol or a polyvalent amine can also be used.

The content of the silane compound in 100% by mass of the surface treatment agent of the glass filler (D) is preferably 0.3 to 2% by mass. By setting the content of the silane compound in the above range, when the glass filler (D) and the polyamide resin (A) are mixed, the dispersibility of the glass filler is improved and the mechanical strength tends to be improved. Yes preferred. The content of the silane compound in 100% by mass of the surface treatment agent is more preferably 0.4 to 1% by mass.

The content of the copolymer compound in 100% by mass of the surface treatment agent of the glass filler (D) is preferably 0.5 to 10% by mass. By setting the content of the copolymer compound to 0.5% by mass or more, the amount of the component that chemically bonds with the polyamide resin (A) becomes sufficient, and the mechanical strength of the polystyrene resin composition of the present invention becomes high. It tends to improve. By setting the content of the copolymer compound to 10% by mass or less, the dispersibility of the glass filler (D) in the polyamide resin (A) tends to be improved. The content of the copolymer compound in 100% by mass of the surface treatment agent is more preferably 1 to 8% by mass, still more preferably 2 to 5% by mass.

The content of the polyurethane resin in 100% by mass of the surface treatment agent of the glass filler (D) is preferably 0.5 to 5% by mass. By setting the content of the polyurethane resin in the above range, the polyurethane resin is sufficiently contained in the entire glass filler, the mechanical strength of the resin composition is improved, and the decomposition gas at the time of extrusion molding can be effectively suppressed. The content of the polyurethane resin in 100% by mass of the surface treatment agent is more preferably 1 to 4% by mass.

In addition to the above components, the surface treatment agent for the glass filler (D) includes bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, biphenyl type bifunctional epoxy resin, biphenyl modified novolac type epoxy resin, and bisphenol A type epoxy. Resin, bisphenol F type epoxy resin, naphthol-cresol cocondensation novolac type epoxy resin, naphthol-phenol cocondensation novolac type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy Epoxy resins such as resins, cresol novolac type epoxy resins, tetraphenylethane type epoxy resins, naphthol novolac type epoxy resins, acrylic acid ester polymers, acrylic acid ester-vinyl acetate copolymers, acrylic acid ester-styrene copolymers, etc. Other binders such as acrylic resins, lubricants such as fatty acid amides and quaternary ammonium salts, nonionic surfactants such as synthetic alcohols, natural alcohols and fatty acid esters, and antistatic agents. Each component can be contained in an appropriate amount, and the blending ratio of each component can be determined as needed. The description of the glass fiber sizing agent described in JP-A-2014-231452 can be referred to, and these contents are incorporated in the present specification.

<Other ingredients>
The polystyrene-based resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired. Other components include fillers other than glass fillers, light stabilizers, antioxidants, heat stabilizers, flame retardants, UV absorbers, dye pigments, optical brighteners, dripping inhibitors, antistatic agents, antifogging agents. , Lubricants, anti-blocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. Only one of these components may be used, or two or more of these components may be used in combination. When these components are blended, it is preferable to adjust the blending amount between 0.001 to 5% by mass, respectively.

<Manufacturing method of polystyrene resin composition>
The polystyrene-based resin composition of the present invention is obtained by blending and kneading the components (A) to (D) including SPS and the above-mentioned various components as necessary. Formulation and kneading are performed by premixing with commonly used equipment such as ribbon blenders, drum tumblers, Henschel mixers, etc., and then using a Banbury mixer, single-screw screw extruder, twin-screw screw extruder, multi-screw screw extruder and the like. This can be done by a method using a conider or the like.

<Molded body>
A molded product made of the polystyrene-based resin composition of the present invention can be obtained. Specifically, using the polystyrene-based resin composition of the present invention or the obtained pellets obtained by melt-kneading as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, or a vacuum. Various molded bodies can be manufactured by a molding method, a foam molding method, or the like. In particular, pellets obtained by melt-kneading can be suitably used for producing an injection-molded article by injection molding and injection compression molding.

The shape of the molded body is not particularly limited, and examples thereof include a sheet, a film, a textile, a non-woven fabric, a container, an injection molded body, and a blow molded body. The molded product obtained by molding the polystyrene-based resin composition of the present invention includes electrical / electronic materials (connectors, printed circuit boards, etc.), industrial structural materials, automobile parts (vehicle mounting connectors, wheel caps, cylinder head covers, etc.), home appliances. It is suitable as an industrial material such as goods, various mechanical parts, pipes, sheets, trays, and films.

The present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

<Molding conditions>
Each component was blended in the proportions (% by mass) shown in the table and dry-blended with a Henschel mixer. Subsequently, using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM35B) having a cylinder diameter of 37 mm, the glass filler 30% by mass is side-fed at a screw rotation speed of 220 rpm and a barrel temperature of 290 ° C. The resin composition was kneaded under the kneading conditions described to prepare pellets. The obtained pellets were dried at 80 ° C. for 5 hours using a hot air dryer.
Using an injection molding machine [SH100A manufactured by Sumitomo Heavy Industries, Ltd.], a dumbbell type tensile test piece (type A) was created in accordance with JIS K 7139: 2015 at a cylinder temperature of 290 ° C and a mold temperature of 80 ° C. did.
Physical property evaluations in Examples and Comparative Examples were carried out as follows.

(1) Tensile Strength / Tensile Elongation Using the above molding conditions, a dumbbell type tensile test piece (type A) was obtained in accordance with JIS K 7139: 2015.
Next, this test piece is pulled by a tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph AG5000B) with an initial chuck distance of 100 mm in accordance with ISO 527-1: 2012 (2nd edition). A tensile test was performed at a speed of 5 mm / min at room temperature to measure the tensile strength at break (MPa) and the elongation at break (%).

(2) Flexural strength Using a test piece having a thickness of 4 mm obtained by using the above molding conditions, the flexural strength (bending strength) under the conditions of a temperature of 23 ° C. and a bending speed of 2 mm / min in accordance with ISO 178: 2010. MPa) was measured. The larger the value, the better the bending characteristics.

(3) Izod Impact Strength Using the above molding conditions, a test piece of 100 mm × 10 mm × thickness 4 mm was molded. The above test piece was notched with a notching machine to prepare a notched test piece. The Izod impact strength was measured for each of the notched test piece and the notched test piece in accordance with ISO 180: 2000.

Example 1 and Comparative Examples 1-2
Each component was blended at the ratio (mass%) shown in Table 1, and various evaluations were performed according to the above molding conditions. In Example 1 and Comparative Examples 1 and 2, the components (A) to (C) are the same and are as follows.
Polyamide resin (A): Nylon 6,6 [manufactured by Ascend Performance Materials, Vydyne (registered trademark) 50BWFS]
SPS (B): [Manufactured by Idemitsu Kosan Co., Ltd., weight average molecular weight 200,000, MFR 9.0 g / 10 minutes (temperature 300 ° C, load 1.2 kg), Zarek 90ZC]
Compatibility agent (C): Fumaric acid-modified polyphenylene ether [manufactured by Idemitsu Kosan Co., Ltd., CX-1]

As the glass filler (D), the following was used.
<Surface treatment agent>
The surface treatment agent was prepared as follows.
40% by mass of maleic anhydride, 50% by mass of methyl acrylate, and 10% by mass of methyl methacrylate were copolymerized to obtain a copolymer compound having a weight average molecular weight of 20,000.
The obtained copolymer compound was blended with γ-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and a polyurethane resin (Y65-55, manufactured by ADEKA Corporation), and further blended with deionized water. To obtain a surface treatment agent. The amount of the copolymer compound in the surface treatment agent was 3% by mass, the amount of γ-aminopropyltriethoxysilane was 0.5% by mass, and the amount of the polyurethane resin was 2% by mass.
<Glass filler (D)>
Various glass raw materials weighed and prepared so as to have the glass composition of E glass are heated and melted, and the molten glass is drawn from a large number of heat-resistant nozzles formed in a platinum bushing to make a glass having an average diameter of 10.5 μm. Fiber monofilaments were made. The above-mentioned surface treatment agent is applied to the glass fiber monofilament with an applicator so that the strong heat loss is 1.0% by mass, and 6000 glass fiber monofilaments are focused into one to be a surface treatment agent (focusing agent). A glass fiber containing the above was obtained. The obtained glass fiber having a surface treatment agent was cut into a length of 3 mm and dried.

Other glass filler Glass filler (d1): EC03ST-249H: Made by Nippon Electric Glass Co., Ltd., E glass, fibrous (chopped strand length 3 mm), fiber cross section approximately perfect circular shape (φ10.5 μm), silane coupling agent Treatment (does not correspond to the glass filler (D) of the present invention).
Glass filler (d2): ECS03CT-222H: E-glass manufactured by Nippon Electric Glass Co., Ltd., fibrous (chopped strand length 3 mm), fiber cross section substantially perfect circular shape (φ10.5 μm) (glass filler (D) of the present invention) Does not correspond to).

Claims (10)

(A) Polyamide resin,
(B) Polystyrene resin having a syndiotactic structure,
(C) A compatibilizer having a polar group capable of reacting with the polyamide resin (A) and having compatibility with the polystyrene resin (B).
(D) Contains glass filler
At least a part of the surface of the glass filler has a surface treatment agent.
The surface treatment agent is a polystyrene-based resin composition containing a silane-based compound, a copolymer compound, and a polyurethane resin. The polystyrene-based resin composition according to claim 1, wherein the compatibilizer (C) is a modified polyphenylene ether. The polystyrene-based resin composition according to claim 1 or 2, wherein the compatibilizer (C) contains at least one of maleic anhydride-modified polyphenylene ether and fumaric acid-modified polyphenylene ether. The copolymer compound is at least one selected from the group consisting of unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and unsaturated dicarboxylic acid anhydride, and acrylic acid-based monomer and methacrylic acid-based monomer. The polystyrene-based resin composition according to any one of claims 1 to 3, which is a copolymer with at least one kind. The polystyrene resin composition according to any one of claims 1 to 4, wherein the content of the surface treatment agent is 0.01 to 4% by mass of the glass filler (D). The polystyrene-based resin composition according to any one of claims 1 to 5, wherein the glass filler (D) is glass fiber. The content of the polyamide resin (A) is 40 to 80% by mass in 100% by mass of the polystyrene resin composition, and the content of the polystyrene resin (B) having a syndiotactic structure is 10 to 30% by mass. The polystyrene-based resin composition according to any one of claims 1 to 6. The polystyrene resin composition according to any one of claims 1 to 7, wherein the content of the compatibilizer (C) is 1 to 10% by mass in 100% by mass of the polystyrene resin composition. The polystyrene resin composition according to any one of claims 1 to 8, wherein the content of the glass filler (D) is 20 to 50% by mass in 100% by mass of the polystyrene resin composition. A molded product made of the polystyrene-based resin composition according to any one of claims 1 to 9.