阅读说明：本技术 苯乙烯系树脂、苯乙烯系树脂组合物及其成形品、以及苯乙烯系树脂的制造方法 (Styrene resin, styrene resin composition, molded article thereof, and method for producing styrene resin ) 是由 青山琢磨 横田清彦 于 2018-11-29 设计创作，主要内容包括：一种具有间规结构的苯乙烯系树脂,将利用差示扫描量热以20℃/分钟的升温速度进行升温而测定的总吸热量设为100％时,在175℃～260℃的范围内所得到的吸热量的比例低于30％。以及,一种苯乙烯系树脂组合物,其包含热塑性树脂组合物50质量％～95质量％和玻璃填料5质量％～50质量％,所述热塑性树脂组合物中,相对于包含具有间规结构的苯乙烯系树脂80质量％～100质量％和橡胶状弹性体0质量％～20质量％的热塑性树脂(SC<Sup>A</Sup>)100质量份,包含：选自由酚系抗氧化剂和硫系抗氧化剂组成的组中的至少1种的抗氧化剂(SC<Sup>B</Sup>)0.2质量份～2.0质量份、选自由聚苯醚和改性聚苯醚组成的组中的至少1种的化合物(SC<Sup>C</Sup>)1.5质量份～5.0质量份、和选自由成核剂和脱模剂组成的组中的至少1种。(A styrene resin having a syndiotactic structure, wherein the proportion of the amount of heat absorbed in the range of 175 to 260 ℃ is less than 30% when the total amount of heat absorbed is 100% as measured by differential scanning calorimetry at a temperature rise rate of 20 ℃/min. And a styrene resin composition comprising 50 to 95% by mass of a thermoplastic resin composition comprising 80 to 100% by mass of a styrene resin having a syndiotactic structure and 0 to 20% by mass of a rubber-like elastomer (SC) and 5 to 50% by mass of a glass filler A )100 parts by mass of: at least 1 antioxidant (SC) selected from the group consisting of phenolic antioxidants and sulfurous antioxidants B )0.2 to 2.0 parts by mass of at least 1 compound (SC) selected from the group consisting of polyphenylene ether and modified polyphenylene ether C )1.5 to 5.0 parts by mass, and at least 1 selected from the group consisting of nucleating agents and mold release agents.)

1. A styrene resin having a syndiotactic structure, wherein when the total heat absorption measured by heating with differential scanning calorimetry at a heating rate of 20 ℃/min is 100%, the proportion of the heat absorption obtained in the range of 175-260 ℃ is less than 30%.

2. A styrenic resin having a syndiotactic structure as defined in claim 1, which comprises triphenylmethane.

3. A styrene-based resin having a syndiotactic configuration as defined in claim 2, comprising triphenylmethane in an amount of 10 ppm by mass or more.

4. A styrene resin having a syndiotactic structure as defined in any one of claims 1 to 3, wherein the residual aluminum content is 800 mass ppm or less and the residual titanium content is 12 mass ppm or less.

5. A styrene resin having a syndiotactic structure as defined in claim 4, wherein the residual aluminum content is 70 ppm by mass or more and the residual titanium content is 1.5 ppm by mass or more.

6. A method for producing a styrene resin having a syndiotactic structure, which comprises the step of addition-polymerizing 1 or more species of a vinyl aromatic monomer in the presence of a catalyst,

the catalyst comprises:

a half-metallocene transition metal compound A having at least 1 kind of central metal selected from the group consisting of metals of groups 3 to 5 of the periodic Table and lanthanide transition metals,

A compound B represented by the general formula (1), and

a compound C selected from at least 1 of an oxygen-containing compound C1 and a compound C2 capable of reacting with a transition metal compound to form an ionic complex,

the styrene-based resin obtained has an endothermic heat rate of less than 30% in the range of 175 ℃ to 260 ℃ when the total endothermic heat measured by differential scanning calorimetry at a temperature rise rate of 20 ℃/min is taken as 100%,

((R¹)₃-Q-Y)_k-Z-(R²)_j-k(1)

in the formula, R¹Represents a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a thioaryloxy group having 6 to 30 carbon atoms, an amino group, an amide group or a carboxyl group, a plurality of R' s¹Are the same or different from each other, and further, a plurality of R¹Optionally bonded to form a ring structure, Q represents an element of group 14 of the periodic table, Y represents an element of group 16, Z represents a metal element of groups 2 to 13, R²Represents a hydrocarbon group, j represents an integer of valence of the metal element Z, and k represents an integer of 1 to (j-1).

7. A method for producing a styrenic resin having a syndiotactic structure in claim 6, wherein said half-metallocene transition metal compound A is represented by the following formula (2),

R³MU_a-1L_b(2)

in the formula, R³Represents a pi ligand, M represents at least 1 kind selected from the group consisting of metals of groups 3 to 5 of the periodic table and lanthanide transition metals, U represents a monoanionic ligand, a plurality of U's are the same or different from each other, and further, are optionally bonded to each other via an optional group, L represents a Lewis base, a represents the valence number of M, b represents 0, 1 or 2, and in the case that L is plural, L are the same or different from each other.

8. A method for producing a styrene-based resin having a syndiotactic structure as defined in claim 6 or 7, wherein the central metal of said half-metallocene transition metal compound A is titanium.

9. A method for producing a styrenic resin having a syndiotactic structure as defined in any one of claims 6 to 8,

also used as a catalyst is a compound D represented by the following general formula (3),

R⁴ _pAl(OR⁵)_qX¹ _2-p-qH (3)

in the formula, R⁴And R⁵Each represents an alkyl group having 1 to 8 carbon atoms, X¹Represents a halogen atom, and p and q satisfy 0 < p.ltoreq.2, 0. ltoreq.q < 2, and p + q.ltoreq.2.

10. The method for producing a styrene-based resin having a syndiotactic structure as defined in any one of claims 6 to 9, wherein a compound E represented by the following general formula (4) is further used as a catalyst,

R⁶ _mAl(OR⁷)_nX² _3-m-n(4)

in the formula, R⁶And R⁷Each represents an alkyl group having 1 to 8 carbon atoms, X²Represents a halogen atom, and m and n satisfy 0 < m < 3, 0 < n < 3, and m + n < 3.

11. A method for producing a styrenic resin having a syndiotactic structure as defined in any one of claims 6 to 10, which comprises carrying out the production by powder bed continuous polymerization.

12. The method for producing a styrene resin having a syndiotactic structure as defined in any one of claims 6 to 11,

taking the central metal of the half metallocene transition metal compound A as a reference, and adding 0-20 times of hydrogen in terms of molar ratio.

13. The method for producing a styrene resin having a syndiotactic structure in any one of claims 6 to 12, wherein no deashing treatment is performed.

14. A styrene resin composition comprising 50 to 95 mass% of a thermoplastic resin composition and 5 to 50 mass% of a glass filler,

in the thermoplastic resin composition, a thermoplastic resin,

a thermoplastic resin SC comprising 80 to 100 mass% of a styrene resin having a syndiotactic structure and 0 to 20 mass% of a rubber-like elastomer^A100 parts by mass of a water-soluble polymer,

comprises the following steps:

antioxidant SC of at least 1 selected from the group consisting of phenolic antioxidants and sulfurous antioxidants^B0.2 to 2.0 parts by mass,

At least 1 compound SC selected from the group consisting of polyphenylene ether and modified polyphenylene ether^C1.5 to 5.0 parts by mass, and

at least 1 selected from the group consisting of nucleating agents and mold release agents.

15. A styrene resin composition as claimed in claim 14, wherein the styrene resin having a syndiotactic structure is as defined in any one of claims 1 to 5.

16. The styrenic resin composition according to claim 14 or 15, wherein the amount of the surfactant is set to the amount of the surfactant in the styrenic resin compositionThe thermoplastic resin SC^A100 parts by mass of antioxidant SC^BThe amount of (B) is 0.2 to 1.5 parts by mass.

17. The styrene resin composition according to claim 14 or 15, wherein SC is a thermoplastic resin^A100 parts by mass of antioxidant SC^BThe amount of (B) is 0.3 to 1.0 part by mass.

18. The styrene resin composition according to any one of claims 14 to 17, wherein the antioxidant SC is^BIs a phenolic antioxidant.

19. The styrene resin composition according to any one of claims 14 to 18, wherein SC is the thermoplastic resin^A100 parts by mass of the nucleating agent is contained in an amount of 0.1 to 3.0 parts by mass.

20. The styrene resin composition according to any one of claims 14 to 18, wherein SC is the thermoplastic resin^A100 parts by mass of the mold release agent, and 0.1 to 3.0 parts by mass of the mold release agent.

21. A styrene resin molded article obtained by molding a styrene resin having a syndiotactic structure according to any one of claims 1 to 5 or a styrene resin composition according to any one of claims 14 to 20.

22. A styrene resin molding according to claim 21, which is used for reflow soldering.

Technical Field

The present invention relates to a styrene resin, a styrene resin composition and a molded article thereof, and a method for producing a styrene resin.

Background

Conventionally, as a method of mounting electronic components on a substrate or the like or a surface mounting method of electrical equipment components of an automobile, a reflow method has been adopted, that is: a method of temporarily fixing an electronic component or the like to a component on which solder is previously dotted at a predetermined position, and then heating the component by means of infrared rays, hot air, or the like to melt the solder to fix the electronic component or the like. The reflow method can improve the mounting density of electronic components on the component surface.

In recent years, with the development of surface mounting technology in the field of electronic devices and electric device parts of automobiles, reflow solders having sufficient heat resistance have become widespread. Due to the increasing awareness of the environmental protection, attention is paid to lead-containing solder as a substitute material. Here, the resin is required to have heat resistance that can withstand the lead-free reflow soldering process.

Examples of the resin having heat resistance that can cope with the lead-free reflow step include liquid crystal polymers and aromatic polyamides. However, it is not necessarily suitable for use in electronic devices and electric device parts of automobiles for reasons such as high specific gravity and poor dimensional stability due to water absorption.

Styrenic polymers having a syndiotactic structure are known to have excellent mechanical strength, heat resistance, electrical characteristics, dimensional stability in water absorption, chemical resistance and the like, and many applications are expected. Among them, styrene-based polymers having a syndiotactic structure are attracting attention in terms of electronic devices, parts for vehicles and electric devices, transformers and coil power modules, relays, sensors, and the like, by effectively utilizing excellent chemical resistance, heat resistance, electrical characteristics, and dimensional stability of water absorption.

For example, patent document 1 discloses a styrene polymer having a syndiotactic structure, which is excellent in chemical resistance and heat resistance.

Disclosure of Invention

Problems to be solved by the invention

Patent document 1 discloses a specific styrene polymer having a syndiotactic structure, and it is considered that the styrene polymer has excellent heat resistance. However, the resin is exposed to high temperatures when the reflowed solder is attached. Therefore, the heat resistance of conventional styrenic resins having a syndiotactic structure is not sufficient in terms of "reflow heat resistance".

Means for solving the problems

The present inventors have conducted extensive studies to obtain a styrene resin having a syndiotactic structure and sufficient reflow heat resistance. As a result, they have found that the above problems can be solved by suppressing the formation of a by-product which melts in a specific temperature range. That is, the present invention relates to the following [1] to [22 ].

[1] A styrene resin having a syndiotactic structure, wherein when the total heat absorption measured by heating with differential scanning calorimetry at a heating rate of 20 ℃/min is 100%, the proportion of the heat absorption obtained in the range of 175-260 ℃ is less than 30%.

[2] A styrenic resin having a syndiotactic structure as described in the above [1], which comprises triphenylmethane.

[3] The styrene resin having a syndiotactic structure according to item [2] above, which contains triphenylmethane in an amount of 10 ppm by mass or more.

[4] A styrene resin having a syndiotactic structure as described in any one of the above [1] to [3], wherein the residual aluminum content is 800 mass ppm or less and the residual titanium content is 12 mass ppm or less.

[5] The styrene resin having a syndiotactic structure as described in the above item [4], wherein the residual aluminum component is 70 mass ppm or more and the residual titanium component is 1.5 mass ppm or more.

[6] A method for producing a styrene resin having a syndiotactic structure, which comprises the step of addition-polymerizing 1 or more species of a vinyl aromatic monomer in the presence of a catalyst,

the catalyst comprises:

a half-metallocene transition metal compound (A) having at least 1 kind of a metal selected from the group consisting of metals of groups 3 to 5 of the periodic Table and lanthanide transition metals as a central metal,

A compound (B) represented by the general formula (1), and

a compound (C) selected from at least 1 of an oxygen-containing compound (C1) and a compound (C2) capable of reacting with a transition metal compound to form an ionic complex,

the styrene-based resin obtained has an endothermic heat rate of less than 30% in the range of 175 to 260 ℃ when the total endothermic heat measured by differential scanning calorimetry at a temperature rise rate of 20 ℃/min is taken as 100%.

((R¹)₃-Q-Y)_k-Z-(R²)_j-k(1)

[ in the formula, R¹Represents halogenAn aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a thioaryloxy group having 6 to 30 carbon atoms, an amino group, an amide group or a carboxyl group. Plural R¹May be the same or different from each other. In addition, a plurality of R¹Bonding optionally occurs as necessary to form a ring structure. Q represents an element of group 14 of the periodic table, Y represents an element of group 16, and Z represents a metal element of groups 2 to 13. R²Represents a hydrocarbon group, j represents an integer of valence of the metal element Z, and k represents an integer of 1 to (j-1).]

[7] The method for producing a styrene-based resin having a syndiotactic structure according to [6], wherein the half-metallocene transition metal compound (A) is represented by the following formula (2).

R³MU_a-1L_b(2)

[ in the formula, R³M represents a pi ligand, M represents at least 1 selected from the group consisting of metals of groups 3 to 5 of the periodic Table and transition metals of lanthanides, U represents a monoanionic ligand, and a plurality of U's may be the same or different and may be bonded to each other via an optional group L represents a Lewis base, a represents the valence of M, b represents 0, 1 or 2, and when L is plural, L may be the same or different.]

[8] The method for producing a styrene-based resin having a syndiotactic structure according to item [6] or [7], wherein the central metal of the half-metallocene transition metal compound (A) is titanium.

[9] The method for producing a styrenic resin having a syndiotactic structure according to any one of the above [6] to [8],

a compound (D) represented by the following general formula (3) is also used as a catalyst.

R⁴ _pAl(OR⁵)_qX¹ _2-p-qH (3)

[ in the formula, R⁴And R⁵Each represents an alkyl group having 1 to 8 carbon atoms, X¹Represents a halogen atom. In addition, p and q satisfy 0 < p < 2, 0 < q < 2, and p + q < 2.]

[10] A process for producing a styrenic resin having a syndiotactic structure according to any one of the above [6] to [9], wherein a compound (E) represented by the following general formula (4) is further used as a catalyst,

R⁶ _mAl(OR⁷)_nX² _3-m-n(4)

[ in the formula, R⁶And R⁷Each represents an alkyl group having 1 to 8 carbon atoms, X²Represents a halogen atom. In addition, m and n satisfy 0-m-3, 0-n-3, and m + n-3.]

[11] A method for producing a styrenic resin having a syndiotactic structure according to any one of the above [6] to [10], which comprises continuous powder bed polymerization.

[12] The method for producing a styrenic resin having a syndiotactic structure according to any one of the above [6] to [11],

taking the central metal of the half metallocene transition metal compound (A) as a reference, and adding 0-20 times of hydrogen in molar ratio.

[13] The method for producing a styrenic resin having a syndiotactic structure according to any one of the above [6] to [12], wherein no deashing treatment is performed.

[14] A styrene resin composition comprising 50 to 95 mass% of a thermoplastic resin composition and 5 to 50 mass% of a glass filler,

in the thermoplastic resin composition, a thermoplastic resin,

a thermoplastic resin (SC) comprising 80 to 100 mass% of a styrene resin having a syndiotactic structure and 0 to 20 mass% of a rubber-like elastomer^A)100 parts by mass of a water-soluble polymer,

comprises the following steps:

at least 1 antioxidant (SC) selected from the group consisting of phenolic antioxidants and sulfurous antioxidants^B)0.2 to 2.0 parts by mass,

At least 1 compound (SC) selected from the group consisting of polyphenylene ether and modified polyphenylene ether^C)1.5 to 5.0 parts by mass, and

at least 1 selected from the group consisting of nucleating agents and mold release agents.

[15] The styrene resin composition according to [14], wherein the styrene resin having a syndiotactic structure is the styrene resin according to any one of [1] to [5 ].

[16]As described above [14]Or [15]]The styrene resin composition, wherein the thermoplastic resin (SC) is a thermoplastic resin^A)100 parts by mass of an antioxidant (SC)^B) The amount of (B) is 0.2 to 1.5 parts by mass.

[17]As described above [14]Or [15]]The styrene resin composition, wherein the thermoplastic resin (SC) is a thermoplastic resin^A)100 parts by mass of an antioxidant (SC)^B) The amount of (B) is 0.3 to 1.0 part by mass.

[18]As described above [14]～[17]The styrene resin composition as claimed in any one of the above, wherein the antioxidant (SC)^B) Is a phenolic antioxidant.

[19]As described above [14]～[18]The styrene resin composition according to any one of the above items, wherein the thermoplastic resin (SC) is a thermoplastic resin^A)100 parts by mass of the nucleating agent is contained in an amount of 0.1 to 3.0 parts by mass.

[20]As described above [14]～[18]The styrene resin composition according to any one of the above items, wherein the thermoplastic resin (SC) is a thermoplastic resin^A)100 parts by mass of the mold release agent, and 0.1 to 3.0 parts by mass of the mold release agent.

[21] A styrene resin molded article obtained by molding the styrene resin having a syndiotactic structure according to any one of the above items [1] to [5] or the styrene resin composition according to any one of the above items [14] to [20 ].

[22] A styrene resin molded article according to [21], which is used for reflow soldering.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the first aspect of the present invention, a styrene-based resin having a syndiotactic structure and excellent reflow heat resistance, which has electrical characteristics, dimensional stability in water absorption, chemical resistance, and the like, and a molded article thereof can be obtained. According to the second aspect of the present invention, a styrene resin having a syndiotactic structure and excellent reflow heat resistance can be mass-produced by a continuous process. According to the third aspect of the present invention, a styrene resin composition and a molded article thereof can be obtained which can achieve both excellent hot water resistance and mold release performance and low outgassing. Further, by using the styrene resin having a syndiotactic structure as the first aspect of the present invention, a styrene resin composition and a molded article thereof, which also have excellent reflow heat resistance, can be obtained.

Drawings

FIG. 1 is a graph showing peaks obtained by DSC measurement.

Detailed Description

As a result of intensive studies, the present inventors have found that a component having a low melting point is produced as a by-product, and therefore adversely affects the heat resistance of a styrene resin having a syndiotactic structure, particularly the reflow heat resistance. Further, it has been found that a styrene resin composition containing a styrene resin having a syndiotactic structure and a specific antioxidant in specific amounts is excellent in hot water resistance. Among them, when a styrene-based resin having a syndiotactic structure, which has excellent heat resistance and contains a small amount of a component having a low melting point, and a specific antioxidant are contained in specific amounts, a resin composition having excellent hot water resistance and particularly excellent reflow heat resistance can be obtained. The details will be described below.

In the present specification, the expression "XX to YY" means "XX or more and YY or less". In the present specification, preferred definitions may be arbitrarily adopted, and combinations of preferred definitions with each other are more preferred.

< styrene resin >

The styrene resin of the present invention is a styrene resin having a highly syndiotactic structure (hereinafter sometimes abbreviated as SPS resin). In the present specification, "syndiotactic" means that the ratio of benzene rings in adjacent styrene units alternately arranged with respect to a plane formed by the main chain of the polymer segment (hereinafter referred to as syndiotactic tacticity) is high.

The tacticity can be adjusted byNuclear magnetic resonance method based on isotopic carbon (¹³C-NMR method) for quantitative identification. Can pass through¹³In the C-NMR method, the presence ratio of a plurality of continuous structural units, for example, 2 continuous monomer units as a dyad, 3 continuous monomer units as a triad, and 5 continuous monomer units as a quintuple, is quantified.

In the present invention, the "styrene-based resin having a highly syndiotactic structure" refers to polystyrene, poly (hydrocarbon-substituted styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinyl benzoate), a hydrogenated polymer or mixture thereof, or a copolymer mainly composed of these, which has a syndiotactic tacticity of usually 75 mol% or more, preferably 85 mol% or more in terms of syndiotactic dyad (r), or usually 30 mol% or more, preferably 50 mol% or more in terms of syndiotactic pentad (rrrr).

Examples of poly (hydrocarbon-substituted styrene) include poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (t-butylstyrene), poly (phenyl) styrene, poly (vinylnaphthalene), and poly (vinylstyrene). Examples of the poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene), and examples of the poly (halogenated alkylstyrene) include poly (chloromethylstyrene). Examples of the poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

As the comonomer component of the copolymer containing the structural unit, in addition to the monomers of the above-mentioned styrene-based polymer, there can be mentioned: olefin monomers such as ethylene, propylene, butene, hexene, and octene; diene monomers such as butadiene and isoprene; polar vinyl monomers such as cyclic olefin monomers, cyclic diene monomers, methyl methacrylate, maleic anhydride and acrylonitrile.

Among the above-mentioned styrenic polymers, particularly preferred are: polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene).

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 cited.

The weight average molecular weight of the styrene resin having a syndiotactic structure of the present invention is preferably 1 × 10 from the viewpoints of the fluidity of the resin at the time of molding and the strength of the resulting molded article⁴Above and 1 × 10⁶Hereinafter, more preferably 50000 or more and 500000 or less, if the weight average molecular weight is 1 × 10⁴As described above, a molded article having sufficient strength can be obtained, while a weight average molecular weight of 1 × 10⁶Hereinafter, there is no problem in the fluidity of the resin during molding.

In the present specification, unless otherwise specified, the weight average molecular weight refers to a value obtained by gel permeation chromatography using 1, 2, 4-trichlorobenzene as an eluent at 145 ℃ using a GPC apparatus (H L C-8321GPC/HT) manufactured by Tosoh corporation and a GPC column (GMHHR-H (S) HT) manufactured by Tosoh corporation, and converted using a calibration curve of standard polystyrene.

In the styrene-based resin having a syndiotactic structure of the present invention, when the total endothermic heat measured by heating with differential scanning calorimetry at a temperature rise rate of 20 ℃/min is taken as 100%, the proportion of the endothermic heat obtained in the range of 175 to 260 ℃ is required to be less than 30%. As described in detail below.

Measured by a Differential Scanning Calorimetry (DSC) apparatus in accordance with JIS K7121: 1987 "measurement of melting temperature after constant Heat treatment", the melting point of the resin can be measured as a value obtained under the condition of a temperature rise rate of 20 ℃/min.

The present inventors have paid attention to the fact that 2 peaks may be present in a DSC curve obtained by DSC measurement of a styrene resin having a syndiotactic structure, as shown in fig. 1. FIG. 1 is a graph showing the temperature rise at a temperature rise rate of 20 ℃ per minute in DSC measurement.

Among the 2 peaks, a styrene resin having poor reflow heat resistance is obtained when the ratio of the amount of heat absorbed in the range of 175 to 260 ℃ is large, i.e., when the total amount of heat absorbed by differential scanning calorimetry is 100%. The inventors speculate that the reason why the reflow heat resistance is reduced by the generation of a low-melting-point component showing an endothermic behavior in the range of 175 to 260 ℃ is as follows without being bound by theory.

A styrene-based resin having a syndiotactic structure is synthesized by using a combination of catalysts described later, and hydrogen is added as necessary to further improve the activity. It is considered that the state of the catalyst or the state of the catalyst site changes due to the addition of hydrogen in a specific amount or more, and therefore, a catalyst failure occurs which changes the stereoregularity of the resin, and a large amount of low-melting-point component is generated, and the reflux heat resistance of the resin is lowered.

"the proportion of the endothermic amount obtained in the range of 175 to 260 ℃ is less than 30% when the total endothermic amount is 100%" means the proportion of the low melting point component showing endothermic behavior in the range of 175 to 260 ℃. The present inventors have found that a styrene-based resin having a syndiotactic structure and excellent reflow heat resistance can be obtained by setting the ratio of the low-melting-point component, i.e., "the ratio of the amount of heat absorbed in a range of 175 to 260 ℃ when the total amount of heat absorbed by heating with differential scanning calorimetry at a temperature rise rate of 20 ℃/min is taken as 100%".

The details of the above-mentioned low melting point component are not clear, but the inventors have found that the increase in the low melting point component is due to an increase in the stereoregularity of 90 mol% or less in terms of syndiotactic pentads. It is presumed that when the stereoregularity is 90 mol% or less in terms of syndiotactic pentads, the thickness of crystals changes, and the melting point is lowered as compared with a styrene resin having a syndiotactic structure with high stereoregularity.

The low-melting-point component was found to have a weight-average molecular weight of 20000 or less. The measurement of the weight average molecular weight of the low-melting-point component described here can be performed by elution separation at an elevated temperature.

The styrene resin having a syndiotactic structure of the present invention has a proportion of an endothermic amount obtained in a range of 175 to 260 ℃, that is, a proportion of a low melting point component, of less than 30%, preferably 28% or less, more preferably 27% or less, assuming that the total endothermic amount is 100%. If the ratio of the low-melting-point component is 30% or more, the reflow heat resistance is poor.

The styrenic resin having a syndiotactic structure of the present invention may further comprise triphenylmethane. Triphenylmethane is a component derived from a catalyst in the production described later. The amount of triphenylmethane in the styrene resin of the present invention is preferably 10 mass ppm or more, more preferably 20 mass ppm or more, further preferably 30 mass ppm or more, and particularly preferably 40 mass ppm or more. On the other hand, the upper limit of the amount of triphenylmethane is preferably 250 mass ppm or less.

When the amount of triphenylmethane in the styrene-based resin of the present invention is 10 ppm by mass or more, a styrene-based resin having a syndiotactic structure with high stereoregularity can be obtained by using a sufficient amount of the catalyst.

The styrenic resin having a syndiotactic structure of the present invention may comprise aluminum and titanium derived from a catalyst at the time of manufacture. In the specific styrene resin of the present invention, it is preferable that the residual aluminum content is 800 mass ppm or less and the residual titanium content is 12 mass ppm or less. It is preferable that the residual aluminum content is 800 ppm by mass or less and the residual titanium content is 12 ppm by mass or less, since the styrene resin can have high reflow heat resistance.

The residual aluminum content in the styrene resin of the present invention is preferably 700 ppm by mass or less, more preferably 500 ppm by mass or less, and the residual titanium content is preferably 11 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 8 ppm by mass or less.

As described above, aluminum and titanium are derived from the catalyst at the time of production.

The production of styrene resins is classified into a "batch process" and a "continuous process". The "batch process" can suppress the amount of catalyst used as compared with the "continuous process", but the amount of styrene resin obtained in one-shot production is low, and the economy is poor in terms of energy. In contrast, the "continuous process" can produce a large amount of a styrene-based resin with high energy efficiency, and requires a certain amount of a catalyst as compared with the "batch process".

The specific styrene resin of the present invention can achieve both excellent heat resistance and the properties inherent in the resin even when the residual aluminum content is 70 mass ppm or more and the residual titanium content is 1.5 mass ppm or more. When the residual metal content is within this range, the styrene resin can be produced by a continuous process, and the styrene resin can be obtained commercially advantageously. For further efficient production, the residual aluminum content is 115 mass ppm or more and the residual titanium content is 2.5 mass ppm or more.

Although the amount of production varies depending on the properties of the styrene-based resin to be obtained, the styrene-based resin obtained by the batch method generally has about 16 mass ppm of residual aluminum component and about 0.025 mass ppm of residual titanium component, which are less than those obtained by the continuous method. On the other hand, it is difficult to efficiently produce the resin as in the continuous method.

< method for producing styrene resin >

A second aspect of the present invention relates to a method for producing a styrene resin having a syndiotactic structure. That is, there is provided a method for producing a styrene resin having a syndiotactic structure, comprising the step of addition-polymerizing 1 or more kinds of vinyl aromatic monomers in the presence of a catalyst comprising: a half-metallocene transition metal compound (A) having at least 1 kind of metal selected from the group consisting of metals of groups 3 to 5 of the periodic table and lanthanide transition metals as a central metal, a compound (B) represented by the general formula (1), and a compound (C) selected from at least 1 kind of compound (C2) selected from an oxygen-containing compound (C1) and a compound (C2) capable of reacting with the transition metal compound to form an ionic complex,

the obtained styrene resin has an endothermic amount ratio of less than 30% in the range of 175-260 ℃ when the total endothermic amount measured by heating with differential scanning calorimetry at a temperature rise rate of 20 ℃/min is 100%.

((R¹)₃-Q-Y)_k-Z-(R²)_j-k(1)

[ in the formula, R¹Represents a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a thioaryloxy group having 6 to 30 carbon atoms, an amino group, an amide group or a carboxyl group. Plural R¹The same or different from each other. In addition, a plurality of R¹Optionally bonded as necessary to form a ring structure. Q represents an element of group 14 of the periodic table, Y represents an element of group 16, and Z represents a metal element of groups 2 to 13. R²Represents a hydrocarbon group. j represents an integer of valence of the metal element Z, and k represents an integer of 1 to (j-1).]

The styrene resin having a syndiotactic structure obtained has the specific properties described in the first embodiment of the present invention.

In the production method of the present invention, it is necessary to use, as the catalyst: a half-metallocene transition metal compound (A) having at least 1 kind of metal selected from the group consisting of metals of groups 3 to 5 of the periodic table and lanthanide transition metals as a central metal, a compound (B) represented by the general formula (1), and a compound (C) selected from at least 1 kind of compound (C2) selected from an oxygen-containing compound (C1) and a compound (C2) capable of reacting with the transition metal compound to form an ionic complex. Hereinafter, the catalyst will be described in detail first.

< half metallocene-based transition Metal Compound (A) >

The half-metallocene transition metal compound (A) is a half-metallocene transition metal compound having at least 1 metal selected from the group consisting of metals of groups 3 to 5 of the periodic table and lanthanide transition metals as a central metal.

The half-metallocene transition metal compound (A) has, for example, a structure represented by the general formula (2).

R³MU_a-1L_b(2)

[ in the formula, R³M represents a pi ligand, M represents at least 1 selected from the group consisting of metals of groups 3 to 5 of the periodic Table and transition metals of lanthanides, U represents a monoanionic ligand, and a plurality of U's may be the same or different and may be bonded to each other via an optional group L represents a Lewis base, a represents the valence of M, and b representsWhen there are a plurality of 0, 1 or 2, L, L may be the same or different.]

In the general formula (2), R³It is a pi ligand, and preferably represents a substituted or unsubstituted (hereinafter sometimes referred to as "(substituted)") cyclopentadienyl group, a (substituted) indenyl group, a condensed polycyclic cyclopentadienyl group in which at least one of the polycyclic rings having a cyclopentadienyl group is a saturated ring. Examples of such a fused polycyclic cyclopentadienyl group include groups selected from among fused polycyclic cyclopentadienyl groups represented by general formulae (i) to (iii).

[ solution 1]

[ in the formula, R¹²、R¹³And R¹⁴Each represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group or an alkylsilyl group. Each R¹²Each R¹³And each R¹⁴Each may be the same or different from each other. c. d, e and f represent integers of 1 or more.]

Among them, preferred are groups selected from among the condensed polycyclic cyclopentadienyl groups represented by the following general formulae (iv) to (vi).

[ solution 2]

[ in the formula, R¹⁵、R¹⁶And R¹⁷Each represents a hydrogen atom or a methyl group, each R¹⁵Each R¹⁶And each R¹⁷May be the same or different from each other.]

Among them, 4, 5, 6, 7-tetrahydroindenyl groups are suitable from the viewpoint of catalyst activity and ease of synthesis. As the R³Specific examples of (3) include: 4, 5, 6, 7-tetrahydroindeneA group; 1-methyl-4, 5, 6, 7-tetrahydroindenyl; 2-methyl-4, 5, 6, 7-tetrahydroindenyl; 1, 2-dimethyl-4, 5, 6, 7-tetrahydroindenyl; 1, 3-dimethyl-4, 5, 6, 7-tetrahydroindenyl; 1, 2, 3-trimethyl-4, 5, 6, 7-tetrahydroindenyl; 1, 2, 3, 4, 5, 6, 7-heptamethyl-4, 5, 6, 7-tetrahydroindenyl; 1, 2, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyl; 1, 3, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyl; an octahydrofluorenyl group; 1, 2, 3, 4-tetrahydrofluorenyl; 9-methyl-1, 2, 3, 4-tetrahydrofluorenyl; 9-methyloctahydrofluorenyl group, and the like.

M is a metal of groups 3 to 5 of the periodic Table or a transition metal of the lanthanide series. Examples of such metals include: metals of group 3 of the periodic table such as scandium and yttrium; metals of group 4 of the periodic Table such as titanium, zirconium and hafnium; a lanthanide transition metal; niobium and tantalum, and the like, group 5 metals of the periodic table. From the viewpoint of catalyst activity, a metal of group 3 or group 4 of the periodic table is suitable, and scandium, yttrium, and titanium can be preferably used. Among them, titanium is more preferable from the viewpoint of workability.

U represents a monoanionic ligand, and specifically includes a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group, and an alkylsilyl group, and a plurality of U's may be the same or different from each other, and may be bonded to each other via an optional group.

As the half-metallocene-based transition metal compound (A) represented by the general formula (2), those having R exemplified above can be preferably used³M and U, respectively.

Examples of the half-metallocene transition metal compound (a) represented by the general formula (2) include: pentamethylcyclopentadienyltitanium trichloride, 1, 2, 3-trimethylindenyl titanium trichloride, 4, 5, 6, 7-tetrahydroindenyltitanium trichloride; 4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 4, 5, 6, 7-tetrahydroindenyltribenzyltitanium; 4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 1-methyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 1-methyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 1-methyl-4, 5, 6, 7-tetrahydroindenyltribenzyltitanium; 1-methyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 2-methyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 2-methyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 2-methyl-4, 5, 6, 7-tetrahydroindenyltribenzyltitanium; 2-methyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 1, 2-dimethyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 1, 2-dimethyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 1, 2-dimethyl-4, 5, 6, 7-tetrahydroindenyltribenzyltitanium; 1, 2-dimethyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 1, 3-dimethyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 1, 3-dimethyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 1, 3-dimethyl-4, 5, 6, 7-tetrahydroindenyltribenzyltitanium; 1, 3-dimethyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 1, 2, 3-trimethyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 1, 2, 3-trimethyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 1, 2, 3-trimethyl-4, 5, 6, 7-tetrahydroindenyltribenzyltitanium; 1, 2, 3-trimethyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 1, 2, 3, 4, 5, 6, 7-heptamethyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 1, 2, 3, 4, 5, 6, 7-heptamethyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 1, 2, 3, 4, 5, 6, 7-heptamethyl-4, 5, 6, 7-tetrahydroindenyltribenzyltitanium; 1, 2, 3, 4, 5, 6, 7-heptamethyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 1, 2, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 1, 2, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 1, 2, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyl titanium tribenzyl; 1, 2, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; 1, 3, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyl titanium trichloride; 1, 3, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyltrimethyltitanium; 1, 3, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyl titanium tribenzyl; 1, 3, 4, 5, 6, 7-hexamethyl-4, 5, 6, 7-tetrahydroindenyltrimethoxy titanium; octahydrofluorenyl titanium trichloride; octahydrofluorenyltrimethyltitanium; octahydrofluorenyltribenzyltitanium; octahydrofluorenyltrimethoxytitanium; 1, 2, 3, 4-tetrahydrofluorenyltitanium trichloride; 1, 2, 3, 4-tetrahydrofluorenyltrimethyltitanium; 1, 2, 3, 4-tetrahydrofluorenyltribenzyltitanium; 1, 2, 3, 4-tetrahydrofluorenyltrimethoxytitanium; 9-methyl-1, 2, 3, 4-tetrahydrofluorenyl titanium trichloride; 9-methyl-1, 2, 3, 4-tetrahydrofluorenyltrimethyltitanium; 9-methyl-1, 2, 3, 4-tetrahydrofluorenyltribenzyltitanium; 9-methyl-1, 2, 3, 4-tetrahydrofluorenyltrimethoxytitanium; 9-methyloctahydrofluorenyltitanium trichloride; 9-methyloctahydrofluorenyltrimethyltitanium; 9-methyloctahydrofluorenyltribenzyltitanium; 9-Methyloctahydrofluorenyltrimethoxytitanium, and the like, and compounds obtained by substituting titanium in these compounds with zirconium or hafnium, or analogous compounds of transition metals of other groups or lanthanoid series, but are not limited thereto. From the viewpoint of catalyst activity, an yttrium compound, a scandium compound and a titanium compound are preferable. Among them, a titanium compound is preferable from the viewpoint of handling properties.

< Compound (B) represented by the general formula (1) >

The general formula (1) is described below again.

((R¹)₃-Q-Y)_k-Z-(R²)_j-k(1)

[ in the formula, R¹Represents a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a thioaryloxy group having 6 to 30 carbon atoms, an amino group, an amide group or a carboxyl group. Plural R¹May be the same or different from each other. In addition, a plurality of R¹If necessary, they may be bonded to form a ring structure. Q represents an element of group 14 of the periodic table, Y represents an element of group 16, and Z represents a metal element of groups 2 to 13. R²Represents a hydrocarbon group. j represents a metal element ZAnd k represents an integer of 1 to (j-1).]

Among them, the following is preferably used:

(1) q is carbon, Y is oxygen, Z is aluminum,

(2) 3R¹At least 1 of them is an aromatic hydrocarbon group having 6 to 30 carbon atoms,

(3) 3R¹All of which are hydrocarbon groups having 1 or more carbon atoms,

(4) 3R¹All of which are aromatic hydrocarbon groups having 6 to 30 carbon atoms, preferably phenyl groups, or

(5)R²An alkyl group having 2 or more carbon atoms.

In particular, the compound (B) is preferably a compound in which Z in the general formula (1) is aluminum.

The compound (B) represented by the general formula (1) is not particularly limited as long as it has a structure represented by the general formula, and the compound (B) represented by the general formula (R) can be preferably used¹)₃-C-OR³³The compound (b1) and the general formula Z (R)²)_jA compound obtained by reacting the compound (b 2).

Here, R¹Z, j and R²As described above. R³³Represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a thioaryloxy group having 6 to 30 carbon atoms, an amino group, an amide group or a carboxyl group. R¹And R³³Each may be the same or different from each other. In addition, R¹And R³³Each of which may be bonded to form a ring structure as necessary.

As the compound of formula (1), specifically, there may be mentioned: at least 1 kind (b1) selected from alcohols, ethers, aldehydes, ketones, carboxylic acids and carboxylic acid esters and the aluminum compound (b 2). More preferably a reaction product of an alcohol (b1) and an aluminum compound (b 2). It is also preferred at this time that: (1) (R)¹)₃3 of (2)¹At least 1 of the (C6-C30) aromatic hydrocarbon groups, (2) (R)¹)₃3 of (2)¹Are all made ofA hydrocarbon group having 1 or more carbon atoms, (3) (R)¹)₃3 of (2)¹Aliphatic hydrocarbon groups each having 1 to 30 carbon atoms, (4) (R)¹)₃3 of (2)¹Aromatic hydrocarbon groups each having 6 to 30 carbon atoms, preferably phenyl group, or (5) R²An alkyl group having 2 or more carbon atoms. Specifically, R is preferably mentioned¹Are each phenyl, Q is carbon, Y is oxygen, Z is aluminum, k ═ 1, R²In the case of isobutyl. That is, most preferred is the reaction product of triphenylmethanol (b1) with triisobutylaluminum (b 2).

The reaction conditions of the compound (b1) and the compound (b2) are not particularly limited, and the following conditions are preferred. The mixing ratio of the compound (b1) to the compound (b2) is preferably 1: 0.01 to 1: 100, more preferably 1: 0.5 to 1: 50, and particularly preferably 1: 0.8 to 1: 10 in terms of molar ratio. The reaction temperature is preferably-80 ℃ to 300 ℃, more preferably-10 ℃ to 50 ℃.

The solvent used in the reaction is not limited, and a solvent used in the polymerization such as toluene or ethylbenzene is preferably used.

Further, instead of the compound (B) represented by the general formula (1), the compound (B1) and the compound (B2) may be directly introduced into the site of catalyst synthesis or the site of polymerization. That is, in this case, the catalyst components are divided into the half-metallocene-based transition metal compound (a), the compound (b1) and the compound (b 2).

< Compound (C) >

The compound (C) is at least 1 selected from the group consisting of an oxygen-containing compound (C1) and a compound (C2) capable of reacting with the transition metal compound to form an ionic complex. Among them, the oxygen-containing compound (c1) is suitable.

[ oxygen-containing Compound (c1) ]

Examples of the oxygen-containing compound include: a compound represented by the following general formula (c11) and/or general formula (c 12).

[ solution 3]

As described aboveIn the general formulae (c11) and (c12), R¹⁸～R²⁴Each represents an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include: methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various heptyl, and various octyl. R¹⁸～R²²R may be the same or different from each other²³And R²⁴May be the same or different from each other. Z¹～Z⁵Each represents a group 13 element of the periodic table, and specifically, B, Al, Ga, In and Tl are mentioned, among which B and Al are preferable, and Al is more preferable. Z¹～Z³May be the same or different from each other, Z⁴And Z⁵May be the same or different from each other. g. h, s and t are each a number of 0 to 50, and (g + h) and (s + t) are each 1 or more. The g, h, s and t are each preferably in the range of 1 to 20, particularly preferably in the range of 1 to 5.

As the above-mentioned oxygen-containing compound, alkylaluminoxane is preferable. Specifically preferred examples thereof include methylaluminoxane, methylisobutylaluminoxane and isobutylaluminoxane.

[ Compound (c2) capable of reacting with a transition metal compound to form an ionic complex ]

Examples of the compound (c2) capable of reacting with the transition metal compound to form an ionic complex include a complex formed by an anion and a cation in which a plurality of groups are bonded to the metal, and a lewis acid. As the complex formed by an anion and a cation in which a plurality of groups are bonded to a metal, there are various complexes, and examples thereof include compounds represented by the following general formula (c21) or (c 22).

([L²]ⁱ⁺)_y([M³X³ _u]^(u-v)-)_z(c21)

([L³-H]ⁱ⁺)_y([M⁴X³ _u]^(u-v)-)_z(c22)

L in the formula (c21) or (c22)²M is described later⁵、R²⁵R²⁶M⁶Or R²⁷ ₃C，L³Being a Lewis base, M³And M⁴Each is a metal selected from groups 5 to 15 of the periodic table. M⁵Is a metal selected from groups 1 and 8 to 12 of the periodic Table, M⁶Is a metal selected from groups 8 to 10 of the periodic table. X³Each represents a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metal group or a halogen atom. Wherein a plurality of X³May be the same or different from each other. R²⁵And R²⁶Each represents cyclopentadienyl, substituted cyclopentadienyl, indenyl or fluorenyl, R²⁷Represents an alkyl group or an aryl group. v represents M³、M⁴The valence of (a) is an integer of 1 to 7, u is an integer of 2 to 8, and i represents [ L ]²]And [ L³-H]The ion valence of (a) is an integer of 1 to 7, y is an integer of 1 or more, and z is y × i/(u-v).

As M³And M⁴Specific examples of (3) include B, Al, Si, P, As and Sb, and M is⁵Specific examples of (3) include Ag, Cu, Na, L i and the like, and M is⁶Specific examples of (3) include Fe, Co and Ni. As X³Specific examples of (3) include: dimethylamino group, diethylamino group, and the like as a dialkylamino group; methoxy, ethoxy, n-butoxy and the like as the alkoxy group; phenoxy group as aryloxy group, 2, 6-dimethylphenoxy group, naphthoxy group, or the like; methyl, ethyl, n-propyl, isopropyl, n-butyl, n-octyl, 2-ethylhexyl, and the like as an alkyl group having 1 to 20 carbon atoms; phenyl, p-tolyl, benzyl, pentafluorophenyl, 3, 5-bis (trifluoromethyl) phenyl, 4-tert-butylphenyl, 2, 6-dimethylphenyl, 3, 5-dimethylphenyl, 2, 4-dimethylphenyl, 1, 2-dimethylphenyl, etc., as an aryl, alkylaryl or arylalkyl group having 6 to 20 carbon atoms; f, Cl, Br, I as halogens; pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsinyl group, dicyclohexylstibyl group, diphenylboron group and the like as the organic metal (Metaloid) group. As R²⁵And R²⁶Specific examples of substituted cyclopentadienyl groupsExamples include: methylcyclopentadienyl, butylcyclopentadienyl, pentamethylcyclopentadienyl and the like.

In the present invention, as an anion in which a plurality of groups are bonded to a metal, specifically, B (C) can be mentioned₆F₅)₄ ^-、B(C₆HF₄)₄ ^-、B(C₆H₂F₃)₄ ^-、B(C₆H₃F₂)₄ ^-、B(C₆H₄F)₄ ^-、B[C₆(CF₃)F₄]₄ ^-、B(C₆H₅)₄ ^-、PF₆ ^-、P(C₆F₅)₆ ^-、Al(C₆HF₄)₄ ^-And the like. Examples of the metal cation include Cp₂Fe⁺、(MeCp)₂Fe⁺、(tBuCp)₂Fe⁺、(Me₂Cp)₂Fe⁺、(Me₃Cp)₂Fe⁺、(Me₄Cp)₂Fe⁺、(Me₅Cp)₂Fe⁺、Ag⁺、Na⁺、Li⁺And the like. In the above formula, Cp represents a cyclopentadienyl group, Me represents a methyl group, and Bu represents a butyl group, respectively. Examples of other cations include: nitrogen-containing compounds such as pyridinium, 2, 4-dinitro-N, N-diethylanilinium, diphenylammonium, p-nitroanilinium, 2, 5-dichloroanilinium, p-nitro-N, N-dimethylanilinium, quinolinium, N-dimethylanilinium, and N, N-diethylanilinium, carbonium compounds such as triphenylcarbonium, tris (4-methylphenyl) carbonium, and tris (4-methoxyphenyl) carbonium, CH, and the like₃PH₃ ⁺、C₂H₅PH₃ ⁺、C₃H₇PH₃ ⁺、(CH₃)₂PH₂ ⁺、(C₂H₅)₂PH₂ ⁺、(C₃H₇)₂PH₂ ⁺、(CH₃)₃PH⁺、(C₂H₅)₃PH⁺、(C₃H₇)₃PH⁺、(CF₃)₃PH⁺、(CH₃)₄P⁺、(C₂H₅)₄P⁺、(C₃H₇)₄P⁺Isoalkylphosphonium ion, and C₆H₅PH₃ ⁺、(C₆H₅)₂PH₂ ⁺、(C₆H₅)₃PH⁺、(C₆H₅)₄P⁺、(C₂H₅)₂(C₆H₅)PH⁺、(CH₃)(C₆H₅)PH₂ ⁺、(CH₃)₂(C₆H₅)PH⁺、(C₂H₅)₂(C₆H₅)₂P⁺And the like arylphosphonium ions.

Among the compounds of the general formulae (c21) and (c22), the following compounds can be particularly suitably used.

Examples of the compound of the general formula (c21) include: ferrocene tetraphenyl borate, dimethylferrocene tetrakis (pentafluorophenyl) borate, ferrocene tetrakis (pentafluorophenyl) borate, decamethylferrocene tetrakis (pentafluorophenyl) borate, acetylferrocene tetrakis (pentafluorophenyl) borate, formylferrocene tetrakis (pentafluorophenyl) borate, cyanoferrocene tetrakis (pentafluorophenyl) borate, silver tetraphenyl borate, silver tetrakis (pentafluorophenyl) borate, trityl tetraphenyl borate, trityl tetrakis (pentafluorophenyl) borate, silver hexafluoroarsenate, silver hexafluoroantimonate, silver tetrafluoroborate, and the like.

Examples of the compound of the general formula (c22) include: triethylammonium tetraphenylborate, tri (N-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolinium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, and the like.

As Lewis acid, for example, B (C) may also be used₆F₅)₃、B(C₆HF₄)₃、B(C₆H₂F₃)₃、B(C₆H₃F₂)₃、B(C₆H₄F)₃、B(C₆H₅)₃、BF₃、B[C₆(CF₃)F₄]₃、PF₅、P(C₆F₅)₅、Al(C₆HF₄)₃And the like.

In the second embodiment of the present invention, the following compound (D) and/or compound (E) may be used as a catalyst in addition to the above-mentioned compound (a), compound (B) and compound (C).

< Compound (D) >

The compound (D) is a compound represented by the following general formula (3).

R⁴ _pAl(OR⁵)_qX¹ _2-p-qH (3)

[ in the formula, R⁴And R⁵Each represents an alkyl group having 1 to 8 carbon atoms, X¹Represents a halogen atom. In addition, p and q are 0-2, and p + q-2.]

The compound (D) represented by the general formula (3) is preferably a dialkylaluminum hydride compound or a monoalkylaluminum hydride compound.

Specifically, there may be mentioned: dialkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride and diisobutylaluminum hydride; alkyl aluminum halide hydrides such as methyl aluminum chloride hydride, ethyl aluminum chloride hydride, n-propyl aluminum chloride hydride, isopropyl aluminum chloride hydride, n-butyl aluminum chloride hydride, and isobutyl aluminum chloride hydride; and alkylalkoxyaluminum hydrides such as ethylaluminummethoxyhydride and ethylaluminumethoxyhydride. Among them, diisobutylaluminum hydride is preferable from the viewpoint of catalyst activity.

< Compound (E) >

The compound (E) is a compound represented by the following general formula (4).

R⁶ _mAl(OR⁷)_nX² _3-m-n(4)

[ in the formula, R⁶And R⁷Each represents an alkyl group having 1 to 8 carbon atoms, X²Represents a halogen atom. In addition, m and n are more than 0 and less than or equal to 3, more than or equal to 0 and less than or equal to 3, and m + n is less than or equal to 3.]

The compound (E) represented by the general formula (4) is preferably a trialkylaluminum or a dialkylaluminum compound from the viewpoint of catalyst activity.

Specifically, there may be mentioned: trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, and triisobutylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride and diisobutylaluminum chloride; and dialkylaluminum alkoxides such as diethylaluminum methoxide and diethylaluminum ethoxide, and triisobutylaluminum is preferable among them.

In the production method of the present invention, as described above, the half-metallocene-based transition metal compound (a), the compound (B) and the compound (C) represented by the general formula (1), and if necessary, the compound (D) and/or the compound (E) may be used in combination as a catalyst. The method for preparing the catalyst to be used is not particularly limited, and the catalyst preparation may be carried out in the following order.

(1) The order of contacting the components

(i) When the half-metallocene-based transition metal compound (a), the compound (B) and the compound (C) are used, for example, there are: a method in which a half-metallocene-based transition metal compound (A) is contacted with a compound (C), and then contacted with a compound (B); a method in which a half-metallocene-based transition metal compound (A) is contacted with a compound (B), and then contacted with a compound (C); a method of contacting the compound (B) with the compound (C) and, at the same time, contacting the half-metallocene transition metal compound (A) component with the compound (B); alternatively, the above-mentioned 3 components are simultaneously contacted.

(ii) Further, when a combination of the compound (D) and/or the compound (E) is used in addition to the above 3 components, the order of contacting the compound (D) and/or the compound (E) is not particularly required. That is, the compound (D) and/or the compound (E) may be used after being brought into contact with the half-metallocene transition metal compound (A), the compound (D) and/or the compound (E) may be used after being brought into contact with the compound (B), and the compound (D) and/or the compound (E) may be used after being brought into contact with the compound (C). Alternatively, the half-metallocene transition metal compound (A), the compound (C), the compound (D) and/or the compound (E) may be contacted in advance with the component (B).

(iii) When the compound (B1) and the compound (B2) are used as the compound (B), the order of contacting the components is not particularly required as in the cases (i) to (ii), and it is preferable that the component (B1) and the component (B2) are contacted in advance before contacting the other components.

(2) The proportion of each component

(i) When the half-metallocene transition metal compound (A), the compound (B) and the compound (C) are used

The compound (B) is selected in the range of 0.5 to 1000, preferably 1 to 100 in terms of the molar ratio of aluminum atoms when the compound (B) is an aluminum compound, based on 1 mol of the half-metallocene transition metal compound (A) component.

The molar ratio of the half-metallocene transition metal compound (a) component to the compound (C) is selected in the range of 1 to 10000, preferably 10 to 1000 in terms of the molar ratio of aluminum atoms when the compound (C) is an organoaluminum compound, based on 1 mol of the half-metallocene transition metal compound (a) when the oxygen-containing compound is used as the compound (C). When a compound capable of reacting with a transition metal compound to form an ionic complex is used as the component (C), the molar ratio of boron atoms in the case where the compound (C) is a boron compound is selected from the range of 0.5 to 10, preferably 0.8 to 5, based on 1 mole of the half-metallocene-based transition metal compound (a).

(ii) When the compound (B1) and the compound (B2) are used as the compound (B), the molar ratio of the compound (B1) to the compound (B2) is preferably 1: 0.01 to 1: 100, more preferably 1: 0.5 to 1: 50, and particularly preferably 1: 0.8 to 1: 10. The component (b2) is preferably selected from the range of 0.5 to 10000, more preferably 0.5 to 1000, and most preferably 1 to 1000 in terms of the molar ratio of aluminum atoms when the component (b2) is an aluminum compound, based on 1 mol of the half metallocene-based transition metal compound (A).

(iii) When the compound (D) and/or the compound (E) is used in addition to the above-mentioned 3 components

The amount of the compound (D) and/or the compound (E) is selected in the range of 0.5 to 1000, preferably 1 to 100 in terms of the molar ratio of aluminum atoms when the compound (D) and/or the compound (E) is an aluminum compound, based on 1 mol of the half-metallocene transition metal compound (A).

(3) Contact conditions of the respective components

The contact of the catalyst component may be carried out in an inert gas such as nitrogen at a polymerization temperature or lower. For example, the reaction can be carried out at a temperature in the range of-30 to 200 ℃.

Next, a process for actually producing a styrene polymer using the above catalyst will be described in detail. In the method for producing a styrene-based polymer of the present invention, homopolymerization of a styrene-based polymer and copolymerization of a styrene-based polymer with another styrene-based polymer (i.e., copolymerization of different types of styrene-based polymers with each other) can be carried out as appropriate by using the above-mentioned polymerization catalyst.

< monomer >

The styrene is not particularly limited, and examples thereof include: alkylstyrenes such as styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, 2, 4-dimethylstyrene, 2, 5-dimethylstyrene, and 3, 5-dimethylstyrene; alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene and m-methoxystyrene; halogenated styrenes such as p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, and o-methyl-p-fluorostyrene; and mesitylene styrene, trimethylsilyl styrene, vinyl benzoate, divinylbenzene, and the like.

Among them, styrene, alkylstyrene and divinylbenzene are preferable, and styrene, p-methylstyrene and divinylbenzene are more preferable.

In the present invention, the above styrenes may be used singly or in any combination of two or more.

< polymerization conditions >

1. Pre-polymerization

In the method for producing a styrene-based polymer of the present invention, the above-mentioned catalyst for polymerization can be used to carry out preliminary polymerization. The prepolymerization can be carried out by bringing a small amount of styrene into contact with the catalyst, and the method is not particularly limited and can be carried out by a known method.

The styrene used in the preliminary polymerization is not particularly limited, and the above styrene can be used. The temperature of the prepolymerization is usually-20 to 200 ℃ and preferably-1 to 130 ℃. In the preliminary polymerization, as a solvent, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used.

2. Formal polymerization

The polymerization method in the main polymerization is not particularly limited, and a continuous polymerization method using any method such as a slurry polymerization method, a powder bed polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, or a suspension polymerization method can be used. Among them, from the viewpoint of production on an industrial scale, it is preferable to carry out powder bed continuous polymerization.

There is no limitation on the order of contacting the components of the catalyst with the monomer. That is, as described above, the respective components of the catalyst may be mixed in advance to prepare a catalyst, and then the monomer may be charged. Alternatively, the catalyst may be prepared by not mixing the components of the catalyst in advance, but may be prepared by introducing the components of the catalyst and the monomer into the polymerization site in an arbitrary order.

A preferred embodiment includes a method in which: the polymerization is carried out by previously mixing components other than the compound (B) or the compound (B1) and the compound (B2), that is, the component (a), the component (C), the component (D), and the component (E), while separately previously mixing a monomer with the compound (B) or the compound (B1) and the compound (B2), and mixing both immediately before the polymerization.

In the present invention, it is more preferable to carry out polymerization of styrene monomer in the presence of the above catalyst by using a powder bed continuous polymerization apparatus. Here, hydrogen may be added to the polymerization site in order to improve the catalyst activity. The half-metallocene transition metal compound (A) may be added with hydrogen in a molar ratio of, for example, 0 to 20 times, preferably 0 to 15 times, more preferably 0 to 10 times, and still more preferably 0.1 to 10 times, based on the central metal of the half-metallocene transition metal compound (A). Since the amount of the residual metal, for example, the residual aluminum component and the residual titanium component in the styrene resin to be produced can be reduced by supplying hydrogen to the reaction system during polymerization to increase the activity of the polymerization catalyst and to suppress the amount of the catalyst used.

However, if the amount of hydrogen added exceeds 20 times based on the central metal of the half-metallocene-based transition metal compound (a), the ratio of the low-melting-point component described above is increased, and the reflux heat resistance is not good, which is not preferable.

In the method for producing a styrene-based resin of the present invention, the catalyst activity is high due to the combination of catalysts and/or hydrogenation, and therefore the residual metal content in the resulting styrene-based resin is low. Therefore, the method does not require a separate deliming treatment, is advantageous in terms of energy, and is suitable for mass production.

When a solvent is used in the polymerization, hydrocarbons such as benzene, toluene, ethylbenzene, n-hexane, n-heptane, cyclohexane, dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, and halogenated hydrocarbons can be used as the solvent. These may be used alone or in combination of two or more. Further, depending on the kind, the monomer itself used for polymerization may be used as a polymerization solvent.

The amount of the catalyst used in the polymerization reaction is preferably selected in the range of usually 0.1 to 500. mu. mol, preferably 0.5 to 100. mu. mol, of the half-metallocene-based transition metal compound (A) per 1 mol of the monomer, from the viewpoint of polymerization activity and reactor efficiency.

The pressure during the polymerization is usually selected in the range of atmospheric pressure to 196MPa as an apparent pressure gauge. The reaction temperature is usually in the range of-50 to 150 ℃.

Examples of the method for adjusting the molecular weight of the polymer include the type, amount used, selection of polymerization temperature, introduction of hydrogen, and the like of each catalyst component.

< styrene resin composition >

According to a third aspect of the present invention, there is provided a styrene resin composition comprising 50 to 95% by mass of a thermoplastic resin composition comprising 80 to 100% by mass of a styrene resin having a syndiotactic structure and 0 to 20% by mass of a rubber-like elastomer (SC) and 5 to 50% by mass of a glass filler^A)100 parts by mass of: at least 1 antioxidant (SC) selected from the group consisting of phenolic antioxidants and sulfurous antioxidants^B)0.2 to 2.0 parts by mass of at least 1 compound (SC) selected from the group consisting of polyphenylene ether and modified polyphenylene ether^C)1.5 to 5.0 parts by mass, and at least 1 selected from the group consisting of nucleating agents and mold release agents.

[ thermoplastic resin (SC)^A)]

Thermoplastic resin (SC) in the present embodiment^A) The styrene resin to be contained is not limited as long as it has a syndiotactic structure, and specifically, the styrene resin of the first aspect and the styrene resin obtained by the second aspect can be preferably used. The other components are described in detail.

As the rubber-like elastic body, various rubber-like elastic bodies can be used. For example, there may be mentioned: natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene rubber, polysulfide rubber, Thiokol rubber, acrylate rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, chloroprene rubber, polysulfide rubber, Thiokol rubber, styrene-butadiene-styrene block copolymer (SBR), styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer (SBS), styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer (S), styrene-isoprene-, Hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butene random copolymer, ethylene-propylene rubber (EPR), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), octyl acrylate-butadiene-styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), a silicone-containing core-shell rubber typified by methyl methacrylate-butyl acrylate silicone, and the like core-shell elastomer, a particulate elastomer, a rubber, or a rubber obtained by modifying the above-mentioned compounds.

Among them, SBR, SBS, SEB, SEBs, SIR, SEP, SIS, SEPs, core-shell rubber, and rubber obtained by modifying these are particularly preferably used.

Examples of the modified rubber-like elastic material include: styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, styrene-butadiene random copolymer, styrene, And rubbers modified with a modifier having a polar group, such as ethylene-propylene rubber (EPR) and ethylene-propylene diene rubber (EPDM).

Among them, particularly preferably used are rubbers obtained by modifying SEB, SEBS, SEP, SEPS, EPR, and EPDM. Specifically, maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, maleic anhydride-modified EPR, maleic anhydride-modified EPDM, epoxy-modified SEBS, epoxy-modified SEPS, and the like can be mentioned. These rubber-like elastomers may be used in 1 or 2 kinds.

Thermoplastic resin (SC) in the above thermoplastic resin composition^A) Comprises 80 to 100 mass% of the styrene resin and 0 to 20 mass% of the rubber-like elastomer, the total being 100 mass%. Thermoplastic resin (SC)^A) When the styrene resin (SPS) content is less than 80% by mass, the mechanical strength of the resulting molded article is undesirably reduced. Thermoplastic resin (SC)^A) The styrene resin in (b) is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass. The compound (SC) to be described later^C) And the exemplified compounds are not included in the above-mentioned rubbery elastomers.

[ antioxidant (SC)^B)]

Antioxidant (SC)^B) Is at least 1 antioxidant selected from the group consisting of phenol-based antioxidants and sulfur-based antioxidants. The styrene resin composition of the present embodiment does not contain a phosphorus antioxidant. If a phosphorus antioxidant is present in the composition, an acid is generated in a high humidity environment or an impregnated water environment. Due to the acid generated, thermoplastic resin (SC)^A) The compatibility with the glass filler described later is lowered, and the mechanical strength of the resulting molded article is lowered, which is not preferable.

As the phenolic antioxidant, known phenolic antioxidants can be used, and specific examples thereof include 2, 6-di-tert-butyl-4-methylphenol, 2, 6-diphenyl-4-methoxyphenol, 2 '-methylenebis (6-tert-butyl-4-methylphenol), 2' -methylenebis [ 4-methyl-6- (α -methylcyclohexyl) phenol ], 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2 '-methylenebis (4-methyl-6-cyclohexylphenol), 2' -methylenebis (4-methyl-6-nonylphenol), 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, ethyleneglycol bis [3, 3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate ], 1, 3-bis (3-tert-butyl-4-hydroxyphenyl) butane, 2-n-dodecylmercaptobutane, ethylene glycol bis [3, 3-di-tert-butyl-4-hydroxyphenyl ] propionate, 3-bis (3-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 5-bis (3-di-tert-butyl-4-hydroxy-4-dodecylmercaptobutane), pentaerythritol tetrakis (3, 5-4-butyl-4-hydroxy-4-dimethylbenzyl) propionate, and the like.

As the sulfur-based antioxidant, various sulfur-based antioxidants can be used. Specifically, there may be mentioned: dilauryl 3, 3 '-thiodipropionate, ditridecyl 3, 3' -thiodipropionate, dimyristyl 3, 3 '-thiodipropionate, distearyl 3, 3' -thiodipropionate, di-2-methyl-4- (3-n-alkyl) (C)₁₂Or C₁₄) Thiopropionyloxy) -5-tert-butylphenyl sulfide, pentaerythritol tetrakis (3-laurylthiopropionate), 2-thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]4, 4' -thiobis (3-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and bis [3- (dodecylthio) propionic acid]2, 2-bis [ [3- (dodecylthio) -1-oxopropoxy group]Methyl radical]-1, 3-propanediyl and the like.

The above-mentioned at least 1 antioxidant selected from the group consisting of phenol-based antioxidants and sulfur-based antioxidants may be used alone, or 2 or more antioxidants may be used in combination. Although the sulfur-based antioxidant has excellent heat resistance for a long period of time, it also has a problem of odor, and therefore it is more preferable to use a phenol-based antioxidant as the antioxidant (SC)^B). In the above thermoplastic resin composition, an antioxidant (SC)^B) With respect to the above thermoplastic resin (SC)^A)100 parts by mass, including 0.2 to 2.0 parts by mass. If the amount of the antioxidant is less than 0.2 part by mass, the effect of preventing decomposition of the resin or the like is not preferable. If the amount of the antioxidant is more than 2.0 parts by mass, gas is generated during molding, and appearance defects such as gas scorching of the molded article are caused. As antioxidant (SC)^B) When two or more antioxidants are contained in the composition, the total amount is preferably adjusted so as to fall within the above range. Antioxidant (SC)^B) The amount of (c) is based on the amount of the thermoplastic resin (SC)^A)100 parts by mass is preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. Further, it is preferably 1.5 parts by mass or less, more preferably 1.0 part by mass or less, and further preferably 0.8 part by mass or less.

[ polyphenylene Ether/modified polyphenylene Ether (SC)^C)]

The thermoplastic resin composition comprises at least 1 compound (SC) selected from the group consisting of polyphenylene ether and modified polyphenylene ether^C). The compound (SC)^C) Has a function as a compatibilizer between the resin component and the glass filler described later.

As the compound (SC)^C) Examples thereof include: maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, maleic anhydride-modified SEB, maleic anhydride-modified SEP, maleic anhydride-modified EPR, styrene-maleic anhydride copolymer (SMA), styrene-glycidyl methacrylate copolymer, terminal carboxylic acid-modified polystyrene, terminal epoxy-modified polystyrene, terminal oxazoline-modified polystyrene, terminal amine-modified polystyrene, sulfonated polystyrene, styrene-based ionomer, styrene-methyl methacrylate graft polymer, (styrene-glycidyl methacrylate) -methyl methacrylate graft polymer, acid-modified acrylic-styrene-graft polymer, (styrene-glycidyl methacrylate) -styrene graft polymer, polybutylene terephthalate-polystyrene graft polymer, maleic anhydride modified syndiotactic polystyrene, fumaric acid modified syndiotactic polystyrene, and glycidyl methacrylate modified syndiotactic polystyreneModified styrene polymers such as ethylene and amine-modified syndiotactic polystyrene, (styrene-maleic anhydride) -polyphenylene ether graft polymers, maleic anhydride-modified polyphenylene ether (PPE), fumaric acid-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, and amine-modified polyphenylene ether. Among them, maleic anhydride-modified polyphenylene ether (PPE) and fumaric acid-modified polyphenylene ether are particularly preferable.

At least 1 compound (SC) selected from the group consisting of polyphenylene ether and modified polyphenylene ether in the thermoplastic resin composition^C) With respect to the above thermoplastic resin (SC)^A)100 parts by mass, including 1.5 to 5.0 parts by mass. If the compound (SC)^C) Less than 1.5 parts by mass, thermoplastic resin (SC)^A) The compatibility with a glass filler described later is poor, and the mechanical strength of the resulting molded article is lowered, which is not preferable. If the compound (SC)^C) An amount of more than 5.0 parts by mass is not preferable because the crystallinity of the composition is lowered, which causes problems such as lowering of heat resistance and mold release property at the time of molding. As the compound (SC)^c) When two or more kinds are contained in the composition, the total amount is preferably adjusted so as to fall within the above range. Compound (SC)^c) The amount of (c) is based on the amount of the thermoplastic resin (SC)^A)100 parts by mass, preferably 1.5 to 4.5 parts by mass, more preferably 1.8 to 4.0 parts by mass, and still more preferably 2.0 to 4.0 parts by mass.

The thermoplastic resin composition further contains at least 1 selected from the group consisting of a nucleating agent and a release agent, and preferably contains both the nucleating agent and the release agent.

Specific trade names of the nucleating agents include ADEKA STAB NA-10, ADEKA STAB NA-11, ADEKA STAB NA-21, ADEKA STAB NA-30, ADEKA STAB NA-35, ADEKA STAB NA-70, and PTBBA-A L available from Dainippon ink chemical industry Co., LtdThe nucleating agents may be used singly or in combination of two or more. The amount of the nucleating agent to be blended is not particularly limited, and may be added to the thermoplastic resin (SC)^A)100 parts by mass, preferably 0.1 to 3.0 parts by mass, more preferably 0.2 to 2.0 parts by mass, still more preferably 0.3 to 2.0 parts by mass, and still more preferably 0.3 to 1.5 parts by mass. By including the nucleating agent, the crystallization rate is thereby increased, and thus the relative crystallinity of, for example, a connector or the like using the styrene-based resin composition can be increased. In addition, excellent reflow heat resistance can be obtained.

The release agent may be any one selected from known release agents such as polyethylene wax, silicone oil, long-chain carboxylic acid, and metal salt of long-chain carboxylic acid. These release agents may be used alone or in combination of two or more. The amount of the release agent to be blended is not particularly limited, and may be blended with the thermoplastic resin (SC)^A)100 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.2 to 1 part by mass. The inclusion of the release agent can improve the release performance in the production of molded articles using the styrene resin composition, for example, connectors and the like.

[ glass Filler ]

The styrene resin composition of the present embodiment contains a glass filler.

As the glass filler, commercially available chopped strands or rovings can be used. The fiber diameter is preferably 1 to 30 μm, and more preferably 3 to 20 μm. When the fiber diameter is in the above range, the moldability and the product appearance are not adversely affected. When chopped strands are used, the fiber length is not particularly limited, but is preferably 1 to 10mm from the viewpoint of workability.

The glass filler is preferably surface-treated with an aminosilane. Examples of the aminosilane used for the treatment include monoaminosilane, diaminosilane, and triaminosilane.

Specific examples of the aminosilane include N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane, γ -aminopropyltriethoxysilane, N-phenyl- γ -aminopropyltrimethoxysilane, γ -aminopropyltris (2-methoxy-ethoxy) silane, N-methyl- γ -aminopropyltrimethoxysilane, N-vinylbenzyl- γ -aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, hexamethyldisilazane, N-bis (trimethylsilyl) urea, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, and the like.

The treatment with a monoaminosilane or a diaminosilane is preferable, and the treatment with a diaminosilane is more preferable. When the glass surface is treated with diaminosilane, the resin composition has a further excellent effect of maintaining hot water resistance.

The styrene resin composition of the present embodiment comprises the thermoplastic resin composition and a glass filler, and the styrene resin composition contains 5 to 50 mass% of the glass filler. If the amount of the glass filler is less than 5% by mass, the resulting molded article is not preferable because it has poor mechanical strength, and if it exceeds 50% by mass, the dispersibility of the glass filler in the composition is poor, and the moldability is difficult.

The amount of the glass filler is preferably 8 to 45 mass%, more preferably 10 to 40 mass%, and still more preferably 15 to 35 mass%.

In the styrene resin composition of the present embodiment, a crosslinking agent, a crosslinking assistant, a flame retardant, an inorganic filler and an organic filler other than the glass filler, a plasticizer, a colorant, an antistatic agent, and the like, which are generally used, may be added in addition to the above components within a range not to impair the object of the present invention. However, polyamide synthetic resins such as nylon are not included in the styrene resin composition of the present embodiment because they lower the hot water resistance of the composition.

As the inorganic filler other than the glass filler, fillers having various shapes such as a fiber shape, a granular shape, and a powder shape can be used. Examples of the fibrous filler include carbon fibers, whiskers, ceramic fibers, and metal fibers. Specifically, the whiskers include boron, alumina, silica, silicon carbide, and the like, the ceramic fibers include gypsum, potassium titanate, magnesium sulfate, magnesium oxide, and the like, and the metal fibers include copper, aluminum, steel, and the like. The fibrous filler may be in the form of a fiber cloth, a mat, a bundle cut, a short fiber, a filament, or a whisker. In the case of the strand cut shape, the length is preferably 0.05 to 50mm and the fiber diameter is preferably 5 to 20 μm. In the case of a fiber cloth-like or mat-like shape, the length is preferably 1mm or more, preferably 5mm or more. Examples of the particulate or powdery filler include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, and metal powder.

The inorganic filler may be surface-treated with a coupling agent generally used for surface treatment, for example, a silane coupling agent, a titanium coupling agent, or the like.

Examples of the organic filler include organic synthetic fibers and natural plant fibers. Specific examples of the organic synthetic fiber include wholly aromatic polyamide fiber and polyimide fiber.

As the method for producing the styrene resin molded product of the present invention, any method can be applied.

For example, a composition containing the above components is first molded to prepare a molded article for hot water treatment evaluation. In the injection molding, the molding may be performed using a die having a predetermined shape, and in the extrusion molding, the film and the sheet may be subjected to T-die molding, and the obtained film and sheet may be heated and melted and then extruded to have a predetermined shape.

< shaped article >

In the present invention, the styrene-based resin according to the first embodiment, the styrene-based resin obtained by the production method according to the second embodiment, and the styrene-based resin composition according to the third embodiment can be molded to obtain a molded body. The shape of the molded article is not particularly limited, and examples thereof include sheets, films, fibers, nonwoven fabrics, containers, injection molded articles, blow molded articles, and the like, and particularly, the styrene-based resin and styrene-based resin composition of the present invention are preferably used as a molded article for reflow soldering, for example, a connector material for reflow soldering, by effectively utilizing the heat resistance and hot water resistance thereof.