JP7336858B2 - Resin composition, molded article, and method for producing resin composition - Google Patents

Description

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

Engineering plastics such as polyamides, polycarbonates and polyesters have excellent heat and chemical resistance. Therefore, molding materials containing these engineering plastics and fillers such as glass fibers are used in various fields such as automobile parts and electronics-related parts.

On the other hand, moldings of engineering plastics have a problem of low impact resistance, particularly Charpy impact strength.

As a method for increasing the impact resistance of engineering plastic moldings, it is conceivable to blend ethylene-propylene copolymer rubber with engineering plastics. Here, engineering plastics with high polarity and ethylene-propylene copolymer rubber with low polarity do not inherently have an affinity for each other. In addition, delamination (separation at the interface of the two-phase structure) is likely to occur. Therefore, it has been proposed to blend a modified ethylene/propylene copolymer rubber obtained by introducing a vinyl monomer having an acidic group such as maleic acid into an ethylene/propylene copolymer rubber into an engineering plastic (for example, Patent Document 1 and 2).

JP-A-55-44108 JP-A-2-160813

However, the compositions of Patent Documents 1 and 2 did not have sufficient impact resistance. In addition, when the modified ethylene-propylene copolymer rubber is further added to the resin composition containing the fibrous filler, not only is the melt fluidity during molding likely to decrease, but also the bending strength is difficult to increase sufficiently. there were.

The present invention has been made in view of the above circumstances, and even if it contains a fibrous filler, it is possible to reduce the decrease in melt fluidity and bending strength during molding, and to provide a molded article excellent in impact resistance. It is an object of the present invention to provide a resin composition and a molded article that can be used, and a method for producing the resin composition.

[1] 60 to 90 parts by mass of an engineering plastic (A) having a melting point (Tm) of 150 to 350° C. measured by a differential scanning calorimeter (DSC), 5 to 35 parts by mass of a thermoplastic elastomer (B), 5 to 35 parts by mass of a fibrous filler (C) (where the total of components (A), (B) and (C) is 100 parts by mass), and the thermoplastic elastomer (B) is , a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene having one or more carbon-carbon double bonds in one molecule. and an ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) containing an ethylene/unsaturated carboxylic acid copolymer containing a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid A resin composition, which is a crosslinked product of a composition containing coalescence (B-II) and a phenolic resin-based crosslinking agent (B-III).
[2] The resin composition according to [1], wherein the ethylene/unsaturated carboxylic acid copolymer (B-II) is an ethylene/methacrylic acid copolymer.
[3] The content of structural units derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid copolymer (B-II) is 5 to 20% by mass, [1] or [2] The resin composition according to .
[4] The resin composition according to any one of [1] to [3], wherein the fibrous filler (C) is glass fiber.
[5] The resin composition according to any one of [1] to [4], wherein the engineering plastic (A) is a semi-aromatic polyamide having a melting point (Tm) of 270 to 340°C.
[6] The semi-aromatic polyamide comprises a structural unit (a1) derived from a dicarboxylic acid and a structural unit (a2) derived from a diamine, and the structural unit (a1) derived from the dicarboxylic acid is Containing structural units derived from terephthalic acid in an amount of 30 mol% or more relative to a total of 100 mol% of the structural units (a1) derived from dicarboxylic acids, and the structural units (a2) derived from the diamine are derived from the diamine. The resin composition according to [5], which contains 50 mol% or more of structural units derived from an aliphatic diamine having 4 to 18 carbon atoms with respect to the total 100 mol% of the structural units (a2).
[7] The thermoplastic elastomer (B) comprises the ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI), the ethylene/unsaturated carboxylic acid copolymer (B-II), and the When the total of the phenol resin-based cross-linking agent (B-III) is 100 parts by mass, the ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) is added in an amount of 30 to 80 parts by mass, and the ethylene/ Any of [1] to [6], containing 15 to 60 parts by mass of the unsaturated carboxylic acid copolymer (B-II) and 1 to 10 parts by mass of the phenolic resin-based cross-linking agent (B-III) The resin composition according to .
[8] A molded article obtained from the resin composition according to any one of [1] to [7].
[9] A structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structure derived from a non-conjugated polyene having one or more carbon-carbon double bonds in one molecule. an ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) containing a unit, and an ethylene/unsaturated carboxylic acid containing a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid a step of dynamically cross-linking a composition containing a copolymer (B-II) and a phenolic resin-based cross-linking agent (B-III) to obtain a thermoplastic elastomer (B); and a step of mixing an engineering plastic (A) having a melting point (Tm) of 150 to 350 ° C. measured by a differential scanning calorimeter (DSC) and a fibrous filler (C), wherein the mixing In the process, the engineering plastic (A) is blended in an amount of 60 to 90 parts by mass with respect to a total of 100 parts by mass of the engineering plastic (A), the thermoplastic elastomer (B) and the fibrous filler (C). parts, the blending amount of the thermoplastic elastomer (B) is 5 to 35 parts by mass, and the blending amount of the fibrous filler (C) is 5 to 35 parts by mass. Method.

According to the present invention, a resin composition and a molded article that can reduce the decrease in melt fluidity and bending strength during molding and can provide a molded article with excellent impact resistance even if it contains a fibrous filler, and a method for producing a resin composition can be provided.

The present inventors have found that by incorporating a thermoplastic elastomer (B) into a resin composition containing an engineering plastic (A) such as a semi-aromatic polyamide and a fibrous filler (C), the fibrous filler Despite containing (C), it was found that the decrease in melt fluidity and bending strength during molding can be significantly reduced (compared to the case where modified ethylene/propylene copolymer rubber is contained).

The reason for this is not clear, but is presumed as follows. The reason why the decrease in melt fluidity can be reduced is that the unsaturated carboxylic acid unit of the thermoplastic elastomer (B) is more suitable than the maleic anhydride unit of the modified ethylene-propylene copolymer rubber in engineering plastics such as polyamides (A ), and the viscosity does not increase excessively during melt molding. In addition, the reason why the decrease in bending strength can be reduced is that the thermoplastic elastomer (B) is crosslinked, so it is harder than the modified ethylene/propylene copolymer rubber, and can bear the stress accordingly.

1. Resin Composition The resin composition of the present invention contains an engineering plastic (A), a thermoplastic elastomer (B), and a fibrous filler (C).

1-1. Engineering plastic (A)
Engineering plastic (A) is an engineering plastic having a melting point (Tm) of 150 to 350° C. as measured by a differential scanning calorimeter (DSC).

The melting point (Tm) of engineering plastic (A) can be measured under the following conditions. Using DSC (differential scanning calorimetry), a sample of engineering plastic (A) was heated and once held at 320°C for 5 minutes, then cooled at a rate of 10°C/min to 23°C, and then 10°C. /min. The temperature of the endothermic peak based on melting at this time is defined as the melting point (Tm).

Such engineering plastic (A) is preferably an engineering plastic having a polar group such as an ether group, an amide group, a carbonyl group, a sulfonyl group, a thioether group, or a combination of one or more thereof. Such engineering plastics (A) include polyamides, polyacetals, polycarbonates, polyesters, polyphenylene ethers, polysulfones, polyethersulfones, polyphenylene sulfides, polyarylates, polyamideimides, polyetherimides, polyetheretherketones, polyimides, fluororesins , polyaminobismaleimide and polybisamidetriazole.

(polyamide)
A polyamide is a polymer containing a structural unit having an amide bond (--NH--C(=O)--), preferably a polymer obtained by co-condensation of a dicarboxylic acid and a diamine. That is, the polyamide contains a structural unit (a1) derived from dicarboxylic acid and a structural unit (a2) derived from diamine.

(Structural unit (a1) derived from dicarboxylic acid)
The structural unit (a1) derived from dicarboxylic acid preferably contains a structural unit derived from terephthalic acid. The amount of the structural unit derived from terephthalic acid is preferably 30 to 100 mol% with respect to the total number of moles (100 mol%) of the structural unit (a1) derived from the dicarboxylic acid constituting the polyamide, and 40 It is more preferably up to 90 mol %, and even more preferably 40 to 80 mol %. When the structural unit (a1) derived from dicarboxylic acid contains 30 mol% or more of the structural unit derived from terephthalic acid, it is easy to increase the heat resistance and strength of the polyamide, so that the heat resistance and strength of the resin composition are increased. Cheap.

The structural unit (a1) derived from dicarboxylic acid may further contain a structural unit derived from a dicarboxylic acid other than terephthalic acid. Examples of dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, 2-methylterephthalic acid and naphthalenedicarboxylic acid; furandicarboxylic acids such as 2,5-furandicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. , alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid; malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethyl Aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as glutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid are included. Only one type of structural unit derived from a dicarboxylic acid other than terephthalic acid may be contained, or two or more types thereof may be contained. Among them, structural units derived from dicarboxylic acid components other than structural units derived from terephthalic acid components are structural units derived from aromatic dicarboxylic acids other than terephthalic acid and/or aliphatic dicarboxylic acids having 4 to 20 carbon atoms. It is preferably a structural unit derived from, from the viewpoint of easily adjusting the glass transition temperature Tg below a certain level, more preferably a structural unit derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms, adipic acid It is more preferable that it is a structural unit derived from.

The amount of the structural unit derived from a dicarboxylic acid other than terephthalic acid is preferably 0 to 70 mol% with respect to the total number of moles (100 mol%) of the structural unit (a1) derived from the dicarboxylic acid. It is more preferably up to 60 mol %, and even more preferably 20 to 60 mol %.

(Structural unit (a2) derived from diamine)
The structural unit (a2) derived from a diamine includes a structural unit derived from an aliphatic diamine.

Structural units derived from aliphatic diamines have at least 4 to 18 carbon atoms and are derived from linear alkylenediamines having no branched substituents (hereinafter referred to as "derived from linear alkylenediamines (also referred to as "structural unit that Structural units derived from linear alkylenediamines, unlike structural units derived from branched alkylenediamines having branched substituents, do not have tertiary carbon atoms, so thermal decomposition of the polyamide during molding is easily suppressed. Therefore, it is easy to improve moldability.

The number of carbon atoms in the structural unit derived from linear alkylenediamine is more preferably 4-15, more preferably 6-12. Examples of linear alkylenediamines include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like are included. Only one type of structural unit derived from linear alkylenediamine may be contained, or two or more types thereof may be contained. Among them, it is more preferable that the structural unit derived from linear alkylenediamine contains a structural unit derived from 1,6-diaminohexane.

The amount of structural units derived from linear alkylenediamine is preferably 40 to 100 mol% relative to the total number of moles (100 mol%) of structural units derived from aliphatic diamines, and 50 to 100 mol%. is more preferable, and may be 100 mol %.

The content of structural units derived from aliphatic diamines is preferably 50 to 100 mol%, relative to the total number of moles (100 mol%) of structural units (a2) derived from diamines, and is preferably 60 to 100 mol. %, more preferably 80 to 100 mol %.

The structural unit (a2) derived from a diamine may further contain a structural unit derived from a diamine other than the structural unit derived from an aliphatic diamine. Examples of structural units derived from other diamines include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 4,4′-diamino- Structural units derived from alicyclic diamines having 4 to 15 carbon atoms such as 3,3′-dimethyldicyclohexylmethane; p-phenylenediamine, m-phenylenediamine, 4,4′-diaminobiphenyl, 2,6- Structural units derived from aromatic diamines such as diaminonaphthalene and 2,7-diaminonaphthalene are included. Structural units derived from other diamines may be contained alone, or may be contained in two or more types.

The total amount of structural units derived from other diamines is preferably 50 mol% or less, more preferably 40 mol% or less, relative to the total amount (100 mol%) of structural units (a2) derived from diamines. It is preferably 20 mol % or less, more preferably 20 mol % or less.

Preferred specific examples of polyamides include structural units (a1) derived from dicarboxylic acid, structural units derived from terephthalic acid, and structural units (a2) derived from diamine, derived from 1,6-hexanediamine. Structural unit polyamide and; Structural unit (a1) derived from dicarboxylic acid is a structural unit derived from terephthalic acid, Structural unit (a2) derived from diamine is a structural unit derived from 1,9-nonanediamine wherein the structural unit (a1) derived from dicarboxylic acid is a structural unit derived from terephthalic acid and a structural unit derived from isophthalic acid, and the structural unit (a2) derived from diamine is 1,6-hexane A polyamide that is a structural unit derived from a diamine; a structural unit (a1) derived from a dicarboxylic acid is a structural unit derived from terephthalic acid and a structural unit derived from adipic acid; and a structural unit (a2) derived from a diamine is , and polyamides, which are structural units derived from 1,6-hexanediamine.

From the viewpoint of thermal stability during compounding and molding, it is preferable that the terminal groups of at least part of the molecular chains of the polyamide are blocked with a terminal blocking agent. In particular, from the viewpoint of melt stability, heat resistance, and hydrolysis resistance, the amount of terminal amino groups of the polyamide is preferably 0.1 to 300 mmol/kg, more preferably 5 to 300 mmol/kg, More preferably 5 to 200 mmol/kg.

The terminal amino group content of polyamide can be measured by the following method. 1 g of polyamide is dissolved in 35 mL of phenol and mixed with 2 mL of methanol to obtain a sample solution. Then, using thymol blue as an indicator, the sample solution is titrated with a 0.01 N HCl aqueous solution until the color changes from blue to yellow, and the amount of terminal amino groups ([NH ₂ ], unit: mmol/kg) is obtained. identify.

The amount of terminal amino groups of polyamide is adjusted by the ratio of diamine and dicarboxylic acid used in preparation of polyamide and the amount of terminal blocking agent.

The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the molecular terminal of the polyamide. A carboxylic acid or a monoamine is preferred, and a monocarboxylic acid is more preferred from the viewpoint of ease of handling.

The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. Examples of monocarboxylic acids include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid; cyclohexanecarboxylic acid, etc. and aromatic monocarboxylic acids such as benzoic acid and toluic acid.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with carboxyl groups. Examples of monoamines include aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine and stearylamine; cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline and toluidine.

The melting point (Tm) of the polyamide as measured by differential scanning calorimetry (DSC) is preferably 270 to 340°C, more preferably 280 to 330°C. When the melting point of the polyamide is within the above range, the heat resistance and mechanical strength (flexural strength, etc.) of the resulting resin composition can be easily increased within a range that does not impair the moldability.

The glass transition temperature (Tg) of the polyamide measured by differential scanning calorimetry (DSC) is preferably 70 to 110°C, more preferably 75 to 100°C.

The glass transition temperature and melting point of polyamide can be adjusted by the type of dicarboxylic acid and diamine constituting the polyamide, the molecular weight of the polyamide, and the like.

The intrinsic viscosity [η] of the polyamide measured in 96.5% sulfuric acid at a temperature of 25 ° C. is preferably 0.7 to 1.6 dl / g, and is 0.8 to 1.2 dl / g. is more preferable. When the intrinsic viscosity [η] of the polyamide is 0.7 dl/g or more, the mechanical strength of the molded article obtained from the resin composition tends to be sufficiently increased, and when it is 1.6 dl/g or less, the resin composition Fluidity during molding is less likely to be impaired, making it easier to mold into a desired shape.

The intrinsic viscosity of polyamide can be measured by the following method. First, about 0.5 g of polyamide is dissolved in 50 ml of 96.5% concentrated sulfuric acid. Then, the number of seconds for the obtained solution to flow down under the conditions of 25° C.±0.05° C. is measured using an Ubbelohde viscometer. After that, the intrinsic viscosity is calculated based on the following formula.
[η]=ηSP/(C(1+0.205ηSP))

In the above formula, each algebra or variable represents:
[η]: Intrinsic viscosity (dl/g)
ηSP: specific viscosity C: sample concentration (g/dl)

ηSP is obtained by the following formula.
ηSP=(t−t0)/t0
t: number of seconds for the sample solution to flow down (seconds)
t0: Number of seconds for blank sulfuric acid to flow down (seconds)

Polyamides can be produced in the same manner as known polyamides, for example, by polycondensation of dicarboxylic acid and diamine in a uniform solution. Specifically, a dicarboxylic acid and a diamine are heated in the presence of a catalyst as described in WO 03/085029 to obtain a lower condensate, and then the lower condensate is It can be produced by subjecting the melt to polycondensation by applying shear stress.

When adjusting the intrinsic viscosity of the polyamide, it is preferable to add the terminal blocking agent as a molecular weight modifier to the reaction system.

A terminal blocking agent as a molecular weight modifier is added to the reaction system of the dicarboxylic acid and the diamine. The amount of the terminal blocker to be added is preferably 0.07 mol or less, more preferably 0.05 mol or less, per 1 mol of the total dicarboxylic acid. By setting the addition amount of the terminal blocking agent within the above range, at least part of the molecular weight modifier is incorporated into the polyamide, thereby adjusting the terminal amino group content of the polyamide and increasing the molecular weight of the polyamide, that is, The limiting viscosity [η] can be adjusted within a desired range.

(Polyacetal)
Polyacetals are polymers containing oxymethylene structural units (--OCH ₂ --). Polyacetal may be a polyacetal homopolymer such as polyoxymethylene (for example, manufactured by DuPont, USA, trade name "Delrin", manufactured by Asahi Chemical Industry Co., Ltd., trade name "Tenac 4010"); A polyacetal copolymer containing a unit and a comonomer structural unit (for example, manufactured by Polyplastics Co., Ltd., trade name "Duracon") may be used.

Examples of comonomer structural units contained in the polyacetal copolymer include oxyalkylene structural units having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms (for example, an oxyethylene group (—OCH ₂ CH ₂ —), oxypropylene group, oxytetramethylene group). The content of comonomer structural units may be 0.01 to 20 mol %, preferably 0.03 to 15 mol %, more preferably 0.1 to 10 mol %, based on all structural units constituting the polyacetal.

The polyacetal copolymer may be a binary copolymer or a multicomponent copolymer having three or more components. The polyacetal copolymer may be a random copolymer or a block copolymer (for example, JP-B-2-24307, manufactured by Asahi Chemical Industry Co., Ltd., trade names "TENAC LA" and "TENAC LM"). or a graft copolymer. Moreover, the polyacetal may have not only a linear structure but also a branched structure or a crosslinked structure. Furthermore, the molecular ends of polyacetal may be stabilized by, for example, esterification with carboxylic acids such as acetic acid and propionic acid or their anhydrides, urethanization with isocyanate compounds, or etherification.

(polycarbonate)
Polycarbonate can be a polymer obtained by interfacial polycondensation of dihydric phenol and phosgene, or a polymer obtained by transesterification of dihydric phenol and a carbonate precursor such as diphenyl carbonate. Examples of dihydric phenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

(polyester)
The polyester may be a polymer obtained by polycondensation of a dihydric or higher aromatic carboxylic acid and a dihydric or higher alcohol and/or phenol. Among them, crystalline polyesters, particularly crystalline polyesters having a melting point of 200° C. or higher, are preferred. Examples of polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate. Among them, polyethylene terephthalate and polybutylene terephthalate are preferred, and polybutylene terephthalate is particularly preferred. Commercially available polyester products include NOVADURAN (manufactured by Mitsubishi Engineering-Plastics Co., Ltd.), which can be easily obtained from the market.

(polyphenylene ether)
Examples of polyphenylene ethers include poly(2,6-dimethyl-1,4-phenylene) ether.

(polyether sulfone)
Polyethersulfone can be, for example, a polymer obtained by polycondensation of bisphenol A and 4,4'-dichlorodiphenylsulfone.

The polyethersulfone can be an aromatic polyethersulfone containing structural units represented by any of the following formulas (1) to (3).
(-Ar ₁ -SO ₂ -Ar ₂ -O-) (1)
(—Ar ₃ —X—Ar ₄ —O—Ar ₅ —SO ₂ —Ar ₆ —O—) (2)
(—Ar ₇ —SO ₂ —Ar ₈ —O—Ar ₉ —O—) (3)

Ar ₁ and Ar ₂ in formula (1) are the same or different aromatic hydrocarbon groups having 6 to 12 carbon atoms (eg, arylene groups having 6 to 12 carbon atoms). Ar ₃ to Ar ₆ in formula (2) are the same or different aromatic hydrocarbon groups having 6 to 12 carbon atoms (eg, arylene groups having 6 to 12 carbon atoms), and X is 1 to 15 carbon atoms. is a divalent hydrocarbon group of Ar ₇ to Ar ₉ in formula (3) are the same or different aromatic hydrocarbon groups having 6 to 12 carbon atoms (eg, arylene groups having 6 to 12 carbon atoms).

(Polyphenylene sulfide)
Polyphenylene sulfide is a polymer containing structural units represented by the following formula.
-(Ph-S)-

Ph in the above formula is a phenylene group. Examples of phenylene groups include p-phenylene, m-phenylene, o-phenylene. S is a sulfur atom.

Polyphenylene sulfide may further contain structural units derived from monomers other than the structural units represented by the above formula. Examples of other monomers include alkyl-substituted phenylenes (preferably alkyl groups having 1 to 6 carbon atoms), phenyl-substituted phenylenes, halogen-substituted phenylenes, amino-substituted phenylenes, amide-substituted phenylenes, p,p'-diphenylenesulfone. , p,p'-biphenylene, p,p'-biphenylene ether, p,p'-biphenylenecarbonyl and naphthalene. The other monomers may be of one kind, or two or more kinds thereof may be combined.

(polyarylate)
The polyarylate may be a polymer obtained by polycondensation of a dihydric phenol compound (eg bisphenol A) and an aromatic dicarboxylic acid (eg terephthalic acid or isophthalic acid).

(polyamide imide)
Polyamideimide can be a polymer obtained by polycondensation of an aromatic dicarboxylic acid and an aromatic diisocyanate, or a polymer obtained by polycondensation of an aromatic dianhydride and an aromatic diisocyanate.

Examples of aromatic dicarboxylic acids include isophthalic acid, terephthalic acid. Examples of aromatic dianhydrides include trimellitic anhydride. Examples of aromatic diisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, orthotolylane diisocyanate, m-xylene diisocyanate.

(Polyetherimide)
Polyetherimides are polymers containing structural units containing imide groups and ether groups. Examples of polyetherimides include polymers containing structural units represented by the following formulae.

(polyether ether ketone)
Polyetheretherketone is a polymer containing a structural unit represented by the following formula.

(fluororesin)
Examples of fluororesins include polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, ethylene tetrafluoride-propylene hexafluoride copolymer, ethylene-chlorotrifluoroethylene copolymer, polyvinyl fluoride, polyethylene fluoride Propylene ether, polyfluoroalkoxyethylene, polychlorotrifluoroethylene, polytetrafluoroethylene, and the like are included.

(polyaminobismaleimide)
Polyaminobismaleimide is a polymer obtained by polymerizing a diamine compound and a bismaleimide compound, and may contain a structural unit represented by the following formula. In the formula below, P and Q are each divalent organic groups.

Examples of diamine compounds include m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1, 1-bis(4-aminophenyl)ethane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl ] ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, 2,2-bis [4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2- bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(4- aminophenyl) 1,3-dichloro-1,1-3,3-tetrafluoropropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone and the like.

Examples of bismaleimide compounds include N,N'-ethylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-hexamethylenebismaleimide, N , N′-4,4′-diphenylmethanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1,1 ,3,3,3-hexafluoro-2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, N,N'-p,p'-diphenyldimethylsilylbismaleimide, N,N'-p , p'-diphenyl ether bismaleimide, N,N'-p,p'-diphenylsulfone bismaleimide, N,N'-dicyclohexylmethane bismaleimide, N,N'-m-xylene bismaleimide, N,N'-( 3,3'-dichloro-p,p'-bisphenylene)bismaleimide, N,N'-(3,3'-diphenyloxy)bismaleimide.

Among these, polyamide is preferable because it has good mechanical strength, heat resistance, moldability, etc.; the structural unit (a1) derived from dicarboxylic acid includes a structural unit derived from terephthalic acid, and is derived from diamine. More preferred are semi-aromatic polyamides, such as polyamides containing structural units derived from aliphatic diamines as structural units (a2); even more preferred are semi-aromatic polyamides having a melting point (Tm) of 270-340°C.

The content of the engineering plastic (A) is preferably 60 to 90 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C). When the content of the engineering plastic (A) is 60 parts by mass or more, the heat deformation resistance of the obtained resin composition tends to be enhanced, and when it is 90 parts by mass or less, the impact resistance of the obtained resin composition is impaired. Hateful. The content of the engineering plastic (A) is more preferably 60 to 85 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C).

1-2. Thermoplastic elastomer (B)
The thermoplastic elastomer comprises an ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI), an ethylene/unsaturated carboxylic acid copolymer (B-II), and a phenol resin-based cross-linking agent (B-III ) is a crosslinked product (dynamic crosslinked product) of a composition containing A crosslinked product is a partially crosslinked product or a completely crosslinked product.

1-2-1. Ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI)
The ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) is a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. It is a copolymer containing a structural unit that

(Structural unit derived from ethylene)
The content of structural units derived from ethylene is preferably 50 to 89% by mass, more preferably 55 to 83% by mass, based on the total structural units constituting the copolymer rubber (BI). preferable.

(Structural unit derived from α-olefin having 3 to 20 carbon atoms)
Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1 -dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like. Among them, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene and 1-octene are preferred. The α-olefin may be of one kind or two or more kinds thereof may be combined. These α-olefins are preferable because they have relatively low raw material costs, are excellent in copolymerizability, and impart excellent mechanical properties and good flexibility to the copolymer rubber (BI).

The content of structural units derived from α-olefins having 3 to 20 carbon atoms is preferably 10 to 49% by mass with respect to the total structural units constituting the copolymer rubber (BI). More preferably, it is up to 43% by mass.

(Structural unit derived from non-conjugated polyene)
A non-conjugated polyene is a non-conjugated polyene having one or more carbon-carbon double bonds in one molecule, and examples thereof include aliphatic polyenes and alicyclic polyenes.

Examples of aliphatic polyenes include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene, 3-methyl- 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5- methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4- methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6- methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6- ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4- Ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6- Ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7- methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5- methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6- ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7- Ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6- α,ω-dienes such as methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, 1,7-octadiene and 1,9-decadiene are included. Among them, 7-methyl-1,6-octadiene is preferred.

Examples of cycloaliphatic polyenes include 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene-2-norbornene, 5-vinyl-2-norbornene (VNB); 5-allyl 5-alkenyl-2-norbornenes such as -2-norbornene; 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, tetracyclo[4,4,0,12.5,17.10]deca-3,8 -diene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, and the like. Among them, 5-ethylidene-2-norbornene (ENB) is preferred. The non-conjugated polyene structural unit may be of one kind, or two or more kinds thereof may be used in combination.

The content of the structural units derived from the non-conjugated polyene is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on the total structural units constituting the copolymer rubber (BI). is more preferred.

The intrinsic viscosity [η] of the copolymer rubber (BI) is preferably 0.5 to 5.0 dl/g, more preferably 1.0 to 4.5 dl/g. Particularly preferred is 5 to 4.0 dl/g. This intrinsic viscosity [η] is a value measured in decalin at a temperature of 135° C., and can be obtained by measuring according to ASTM D1601.

The content of the copolymer rubber (BI) should be 30 to 80 parts by mass per 100 parts by mass of the components (BI), (B-II) and (B-III). is preferred. When the content of the copolymer rubber (BI) is 30 parts by mass or more, the flexibility of the thermoplastic elastomer (B) can be sufficiently increased, and therefore the impact resistance of the resulting resin composition can be sufficiently increased. At the same time, since the content of the ethylene/unsaturated carboxylic acid copolymer (B-II) does not become too large, moldability, mechanical strength, and heat resistance are less likely to be impaired. When the content of the copolymer rubber (B-I) is 80 parts by mass or less, the content of the ethylene/unsaturated carboxylic acid copolymer (B-II) does not become too small. The compatibility with the thermoplastic elastomer (B) and the effect of improving the impact resistance due to it are less likely to be impaired. The content of the copolymer rubber (BI) should be 35 to 80 parts by mass per 100 parts by mass in total of the components (BI), (B-II) and (B-III). is more preferable, and 45 to 70 parts by mass is even more preferable.

1-2-2. Ethylene/unsaturated carboxylic acid copolymer (B-II)
The ethylene/unsaturated carboxylic acid copolymer (B-II) is a copolymer containing a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid. The carboxyl group of the ethylene/unsaturated carboxylic acid copolymer (B-II) is likely to interact with a polar group that the engineering plastic (A) may have (for example, in the case of polyamide, a carboxyl group, an amino group, etc.). , the compatibility between the engineering plastic (A) and the thermoplastic elastomer (B) can be enhanced, and the impact resistance can be further enhanced.

Unsaturated carboxylic acids that are copolymerized with ethylene can be unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid monoesters, and the like. Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, etc.; examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, etc.; examples of unsaturated dicarboxylic acid monoesters include: Includes monomethyl maleate, monoethyl maleate, monoisobutyl maleate. Among these, acrylic acid or methacrylic acid is preferred, and methacrylic acid is particularly preferred.

The content of structural units derived from unsaturated carboxylic acid (acid content) in the ethylene/unsaturated carboxylic acid copolymer (B-II) is preferably 5 to 20% by mass, more preferably 5 to 15% by mass. % is more preferable. When the content of structural units derived from an unsaturated carboxylic acid (acid content) is at least a certain amount, the carboxyl group of the ethylene/unsaturated carboxylic acid copolymer (B-II) becomes, for example, the engineering plastic (A). Since it easily interacts with possible polar groups and the like, the compatibility between the engineering plastic (A) and the thermoplastic elastomer (B) is likely to be enhanced, and the impact resistance is likely to be enhanced. On the other hand, when the content of structural units derived from unsaturated carboxylic acid (acid content) is below a certain level, the content of carboxyl groups in the resin composition does not become too high, so that the engineering plastic (A) and the thermoplastic It does not interact excessively with the elastomer (B) and does not easily impair fluidity. The acid content of the ethylene/unsaturated carboxylic acid copolymer (B-II) can be measured by FT-IR measurement.

The ethylene/unsaturated carboxylic acid copolymer (B-II) is not only a binary copolymer of ethylene and an unsaturated carboxylic acid, but also a multiple copolymer of ethylene, an unsaturated carboxylic acid and other monomers. It may be a coalescence.

Other monomers can be vinyl monomers and the like. Examples of vinyl monomers include vinyl esters such as vinyl acetate; methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate. , and unsaturated carboxylic acid esters such as dimethyl maleate. However, if too much of these other monomers is included, the melting point is low and the heat resistance may be impaired. Therefore, the content of structural units derived from other monomers can be 20% by weight or less, preferably 10% by weight or less, relative to the copolymer.

The melting point of the ethylene/unsaturated carboxylic acid copolymer (B-II) is preferably 60 to 120°C, more preferably 70 to 120°C. When the melting point is 60°C or higher, the heat resistance of the thermoplastic elastomer (B) is less likely to be impaired. When the melting point is 120° C. or lower, the melted viscosity of the thermoplastic elastomer (B) is less likely to become excessively high, and moldability is less likely to be impaired. The melting point of the ethylene/unsaturated carboxylic acid copolymer (B-II) is measured according to JIS K 7121:1987.

The melt flow rate (MFR) of the ethylene/unsaturated carboxylic acid copolymer (B-II) measured under a load of 2.16 kg at 190° C. in accordance with JIS K 7210: 1999 shows that moldability is impaired. Although not particularly limited, it can be 0.5 to 1000 g/10 minutes (dl/g), preferably 1 to 500 g/10 minutes (dl/g).

The content of the ethylene/unsaturated carboxylic acid copolymer (B-II) is 15 to 60 parts per 100 parts by mass in total of the components (BI), (B-II) and (B-III). Parts by mass are preferred. When the content of the ethylene/unsaturated carboxylic acid copolymer (B-II) is 15 parts by mass or more, the compatibility between the copolymer rubber (B-I) and the engineering plastic (A), and eventually the thermoplastic elastomer The compatibility between (B) and the engineering plastic (A) can be sufficiently improved, and the resulting resin composition can be easily imparted with sufficient impact resistance. When the content of the ethylene/unsaturated carboxylic acid copolymer (B-II) is 60 parts by mass or less, the moldability, mechanical strength and heat resistance of the resulting resin composition are less likely to be impaired. The content of the ethylene/unsaturated carboxylic acid copolymer (B-II) is 15 to 55 parts per 100 parts by mass in total of the components (BI), (B-II) and (B-III). It is more preferably 20 to 50 parts by mass.

Further, the mass ratio ((B-II)/(B-I)) of the ethylene/unsaturated carboxylic acid copolymer (B-II) and the copolymer rubber (B-I) is 30/70 to 90/ It is preferably 10, more preferably 40/60 to 80/20, even more preferably 40/60 to 75/25. When the mass ratio of the ethylene/unsaturated carboxylic acid copolymer (B-II) is at least a certain value, the compatibility between the engineering plastic (A) and the copolymer rubber (BI), and furthermore the thermoplastic elastomer (B) can be easily increased, and the impact resistance of the resulting resin composition can be sufficiently increased. When the mass ratio of the ethylene/unsaturated carboxylic acid copolymer (B-II) is below a certain value, the resulting resin composition has good impact resistance and is less likely to lose its mechanical strength.

In addition, the mass ratio ((B-II)/(A)) of the ethylene/unsaturated carboxylic acid copolymer (B-II) and the engineering plastic (A) further enhances the impact resistance of the resulting resin composition. From the viewpoint of making it easier, it is preferably 5/95 to 15/85 (mass ratio), and from the viewpoint of increasing the impact resistance of the resulting resin composition, it is 5/95 to 12/88 (mass ratio). is more preferred.

1-2-3. Phenolic resin-based cross-linking agent (B-III)
The phenolic resin-based cross-linking agent (B-III) is typically a resol resin obtained by condensing an alkyl-substituted or unsubstituted phenol with an aldehyde (preferably formaldehyde) in the presence of an alkali catalyst. . The alkyl group of the alkyl-substituted phenol is preferably an alkyl group having 1 to 10 carbon atoms. That is, alkyl-substituted or unsubstituted phenols are preferably dimethylolphenols or phenols substituted with an alkyl group having 1 to 10 carbon atoms.

Examples of the phenol resin-based cross-linking agent (B-III) include compounds represented by the following formula (1).

In formula (1), R is an organic group such as an alkyl group, preferably an organic group having less than 20 carbon atoms, more preferably an organic group having 4 to 12 carbon atoms. R' is a hydrogen atom or -CH ₂ -OH. n and m are integers of 0-20, preferably integers of 0-15, more preferably integers of 0-10.

Other examples of phenolic resin-based cross-linking agents (B-III) include methylolated alkylphenol resins and halogenated alkylphenol resins. A halogenated alkylphenol resin is an alkylphenol resin in which a hydroxyl group at the end of a molecular chain is substituted with a halogen atom such as bromine, and examples thereof include compounds represented by the following formula (2).

n, m and R in formula (2) are synonymous with n, m and R in formula (1) respectively. R' in formula (2) is a hydrogen atom, -CH ₃ or -CH ₂ -Br.

Commercially available examples of the phenolic resin-based cross-linking agent (B-III) include Tackyroll 201, Tackyroll 250-I, and Tackyroll 250-III available from Taoka Chemical Co., Ltd.; SP1045, SP1055, and SP1056 available from SI Group; Shaunol CRM from Arakawa Chemical Industries, Ltd.; Tamanol 531 from Arakawa Chemical Industries, Ltd.; Sumilite Resin PR from Sumitomo Bakelite Co., Ltd.; be These may be used alone or in combination of two or more. Among them, Takkiroru 250-III (brominated alkylphenol formaldehyde resin) manufactured by Taoka Kagaku Kogyo Co., Ltd. and SP1055 (brominated alkylphenol formaldehyde resin) manufactured by SI Group are preferable.

Among these, halogenated alkylphenol resins are particularly preferred. A halogen alkylphenol resin is preferable because it has excellent compatibility with the copolymer rubber (BI), is highly reactive, and can relatively shorten the time to start the cross-linking reaction.

When the phenolic resin-based cross-linking agent (B-III) is a powdery cross-linking agent, its average particle size is preferably 0.1 μm to 3 mm, more preferably 1 μm to 1 mm, particularly preferably 5 μm to 0.5 mm. is. The flaky curing agent is preferably pulverized by a pulverizer such as a jet mill or a pulverizer with a pulverizing blade before use.

The content of the phenolic resin-based cross-linking agent (B-III) is 1 to 10 parts by mass with respect to the total of 100 parts by mass of the components (BI), (B-II), and (B-III). Preferably. When the content of the phenol resin-based cross-linking agent (B-III) is 1 part by mass or more, the component (B-I) can be sufficiently cross-linked, so that the obtained thermoplastic elastomer (B) has sufficient impact resistance. easy to give. The content of the phenol resin-based cross-linking agent (B-III) is 1 to 8 parts by mass with respect to a total of 100 parts by mass of the components (BI), (B-II), and (B-III). more preferably 2 to 6 parts by mass.

1-2-4. Other Components The composition for obtaining the thermoplastic elastomer (B) may contain components other than the components (BI), (B-II) and (B-III) within a range that does not impair the effects of the present invention. may further contain a component of Examples of other components include cross-linking agents other than the phenolic resin-based cross-linking agent (B-III), cross-linking aids, co-stabilizers (antioxidants), and the like.

Other cross-linking agents may be any cross-linking agents capable of dynamic cross-linking of the aforementioned composition, examples of which include sulfur-based cross-linking agents. However, other cross-linking agents preferably do not contain organic peroxides. This is because the temperature suitable for cross-linking the components (BI) and (B-II) is high, so that the organic peroxide does not easily function as a cross-linking agent.

Examples of coagents include magnesium hydroxide, calcium hydroxide, magnesium oxide, zinc oxide, and the like.

Examples of co-stabilizers include hindered phenol compounds, hindered amine compounds and phosphorus compounds.

The total content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and may be 0% by mass, based on the total mass of the composition.

1-2-5. Method for Producing Thermoplastic Elastomer (B) Thermoplastic elastomer (B) is obtained by dynamically crosslinking at least a portion of a composition containing component (BI), component (B-II), and component (B-III). Specifically, it can be obtained by cross-linking in a melt flow state (dynamic state).

Dynamic cross-linking is usually carried out by supplying the composition described above to a melt-kneading apparatus, heating it to a predetermined temperature, and melt-kneading it. Melt-kneading devices such as a twin-screw extruder, a single-screw extruder, a kneader, and a Banbury mixer can be used. Among them, a twin-screw extruder is preferable from the viewpoint of good shearing force and continuous productivity. The melt-kneading temperature is usually 200-320°C. The melt-kneading time is usually 0.5 to 30 minutes.

This dynamic cross-linking cross-links the ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI). That is, the thermoplastic elastomer (B) is composed of a copolymer rubber (BI) crosslinked with a phenolic resin-based crosslinking agent (B-III) and an ethylene/unsaturated carboxylic acid copolymer (B-II). can include The thermoplastic elastomer (B) comprises a sea phase (matrix phase) containing the ethylene/unsaturated carboxylic acid copolymer (B-II) and an island phase containing the crosslinked copolymer rubber (BI). (dispersed phase) and has a sea-island structure.

The island phase (dispersed phase) containing the crosslinked copolymer rubber (BI) can exhibit rubber elasticity. The sea phase (matrix phase) containing the ethylene/unsaturated carboxylic acid copolymer (B-II) is combined with the island phase (dispersed phase) containing the copolymer rubber (B-I) crosslinked with the engineering plastic (A). can increase the compatibility of The island phase (dispersed phase) has a relatively small average particle size and is finely dispersed. Such thermoplastic elastomers (B) may have good flexibility or impact resistance and good compatibility with engineering plastics (A). Thereby, the resulting resin composition can have good impact resistance without causing delamination or the like.

The content of the thermoplastic elastomer (B) is preferably 5 to 35 parts by mass per 100 parts by mass of components (A), (B) and (C). When the content of the thermoplastic elastomer (B) is 5 parts by mass or more, the impact resistance of the resulting resin composition tends to be increased, and when it is 35 parts by mass or less, the heat deformation resistance and mechanical properties of the resulting resin composition are improved. It is hard to lose the physical strength. The content of the thermoplastic elastomer (B) is more preferably 5 to 30 parts by mass per 100 parts by mass of the total of components (A), (B) and (C).

The mass ratio of the thermoplastic elastomer (B) to the engineering plastic (A) ((B)/(A)) is from the viewpoint of improving the balance between the impact resistance, melt fluidity, and bending strength of the resulting resin composition. Then, it is preferably 43/57 to 7/93 (mass ratio), more preferably 29/71 to 7/93 (mass ratio).

1-3. Fibrous filler (C)
The fibrous filler (C) improves the moldability of the resin composition, and can improve mechanical properties such as tensile strength, flexural strength, and flexural modulus of the molded product, and heat resistance such as heat distortion temperature. .

Examples of the fibrous filler (C) include glass fiber (glass fiber), potassium titanate fiber, metal-coated glass fiber, ceramic fiber, wollastonite, carbon fiber, metal carbide fiber, hardened metal fiber, and asbestos fiber. and inorganic fibers such as boron fibers; and organic fibers such as aramid fibers and carbon fibers. Among them, glass fiber is preferable because it can significantly improve the mechanical strength of the molded article.

The average length of the fibrous filler (C) is usually in the range of 0.1-20 mm, preferably 0.2-6 mm. Furthermore, the aspect ratio (L (average length of glass fiber)/C (average outer diameter of glass fiber)) of the fibrous filler (C) is usually in the range of 10 to 5000, preferably 100 to 3000. .

The average length and aspect ratio of the fibrous filler (C) are obtained by cutting out a part of the resin composition or its molded body by argon ion beam processing and observing it with a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.). can be asked for.

Furthermore, for the purpose of preventing warping of the molded body, the ratio of different diameters (ratio between the major axis and the minor axis) of the fiber cross section of the fibrous filler (C) is preferably greater than 1, 1.5 to 6.0. is more preferable.

The fibrous filler (C) can be used after being treated with a silane coupling agent, a titanium coupling agent, or the like. For example, the fibrous filler (C) may be surface-treated with a silane coupling agent such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltriethoxysilane. good.

The fibrous filler (C) may be coated with a sizing agent. Examples of sizing agents include acrylic compounds represented by (meth)acrylic acid and (meth)acrylic acid esters, carboxylic acid compounds other than methacrylic acid such as maleic anhydride, which have a carbon-carbon double bond, epoxy compounds, urethane compounds, amine compounds and combinations thereof. Examples of preferred combinations include acrylic compound/carboxylic acid compound, urethane compound/carboxylic acid compound, and urethane compound/amine compound. Moreover, the surface treatment agent may be used in combination with a sizing agent. As a result, the bonding between the fibrous filler (C) and other components in the resin composition is improved, and the appearance and mechanical strength are likely to be improved.

The content of the fibrous filler (C) is preferably 5 to 35 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C). When the content of the fibrous filler (C) is 5 parts by mass or more, it is easy to impart good mechanical strength to the molded article, and when it is 35 parts by mass or less, the fluidity during molding is less likely to be impaired. More preferably, the content of the fibrous filler (C) is 10 to 35 parts by weight per 100 parts by weight of the components (A), (B) and (C) combined.

1-4. Other Components The resin composition of the present invention may further contain components other than components (A), (B) and (C). Examples of other ingredients include compatibilizers (D).

(Compatibilizer (D))
The compatibilizer (D) is not particularly limited, but in order to better compatibilize the engineering plastic (A) and the thermoplastic elastomer (B), a polar group-containing compound such as a hydroxyl group, a carbonyl group, an epoxy Polar group, acid hydride, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanate ester, amino group, imide group, oxazoline group, thiol group, etc. as a polar group It can be a polymer or copolymer of group-containing compounds.

Examples of polar group-containing compounds include epoxy group-containing ethylene-based copolymers, maleic acid-modified styrene-based copolymers, and maleic acid-modified olefin-based resins.

Examples of epoxy group-containing ethylene-based copolymers include copolymers of ethylene and glycidyl dimethacrylate. Moreover, the epoxy group-containing ethylene-based copolymer may be a copolymer with other monomers such as vinyl acetate and methyl acrylate. The glycidyl group content of the epoxy group-containing ethylene copolymer is preferably, for example, 1 to 20% by mass.

Examples of maleic acid-modified styrenic copolymers include maleic anhydride-modified SEBS. Examples of maleic acid-modified olefin resins include maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene. The maleic acid modification rate of the maleic acid-modified olefin resin and the maleic acid-modified styrene copolymer is preferably, for example, 0.1 to 20% by mass.

Commercially available examples of the compatibilizer (D) include Bondfast 2C, E, 2B, 7B, 7L, 7M, VC40 (manufactured by Sumitomo Chemical Co., Ltd.), Kraton FG1901, FG1924 (Krayton Polymer Japan Co., Ltd. ), Tuftec M1911, M1913, M1943, MP10 (manufactured by Asahi Kasei Chemicals Corp.), and the like.

When the resin composition of the present invention contains a compatibilizer (D), the content of the compatibilizer (D) is 100 parts by mass in total of the components (A), (B) and (C). It is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 mass %. When the content of the compatibilizer (D) is 0.1 parts by mass or more, the compatibility between the engineering plastic (A) and the thermoplastic elastomer (B) can be easily improved without impairing moldability. When the content of the compatibilizer (D) is 20 parts by mass or less, the heat deformation resistance is less likely to be impaired.

The resin composition of the present invention includes, for example, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a crystal nucleating agent, an antiblocking agent, a seal improving agent, and a plasticizer, as long as the objects of the present invention are not impaired. (e.g. stearic acid, silicone oil, etc.), lubricants (polyethylene wax, etc.), coloring agents, pigments, flame retardants (e.g., magnesium hydroxide, aluminum hydroxide), foaming agents (e.g., organic, inorganic), etc. You can

2. Production method of resin composition The resin composition of the present invention can be produced by any method. , and a step of mixing the engineering plastic (A) and the fibrous filler (C) by a known method. After the above mixing, the mixture may be further melt-kneaded using an extruder. The blending amount of each component is as described above.

Optionally used cross-linking aids and compatibilizers (D) may be mixed in advance with any of the components, or may be mixed with the copolymer rubber (BI) and the ethylene/unsaturated carboxylic acid copolymer ( B-II) or when mixing the thermoplastic elastomer (B) with the engineering plastic (A) and the fibrous filler (C).

3. Molded article and its use The molded article obtained by molding the resin composition of the present invention can be used in various applications, such as automobile parts, building material parts, sporting goods, medical equipment parts, and industrial parts. It is useful as a molded product of

Among them, the molded article obtained from the resin composition of the present invention has good moldability and impact resistance, so it can be used as a hollow molded article (industrial tube) or by a specific molding method (blow molding, two-color molding, etc.) ) is suitable for the molded body obtained in.

<Blow molding (industrial tube)>
The industrial tube includes at least a layer containing the resin composition described above. Industrial tubing means tubing that is used in particular for industrial equipment. Examples of industrial tubes include tubes through which fluids (fuels, solvents, chemicals, gases, etc.) necessary for industrial equipment such as vehicles (eg, automobiles), pneumatic/hydraulic equipment, coating equipment, and medical equipment pass. In particular, it is very useful in applications such as vehicle plumbing tubes (eg, fuel system tubes, intake system tubes, cooling system tubes), pneumatic tubes, hydraulic tubes, paint spray tubes, medical tubes (eg, catheters), and the like.

<Molded product obtained by injection molding, blow molding or two-color molding>
Molded articles obtained by injection molding, blow molding or two-color molding can be widely used in various applications (for example, automobiles and electric appliances) that require such physical properties. Examples of molded products obtained by injection molding, blow molding or two-color molding include boot parts such as constant velocity joint boots and dust covers, oil seals, gaskets, packings, dust covers, valves, stoppers, precision seal rubbers, and weather strips. etc. Among them, constant velocity joint boots for automobiles are preferable. Known methods such as injection molding and blow molding (injection blow molding and press blow molding) can be used as methods for manufacturing constant velocity joint boots for automobiles.

Among these, the molded product of the present invention is preferably used as a material for resin flexible boots such as intake/exhaust system parts, constant velocity joint boots for automobiles, dust covers, and various boot parts, which are automobile-related parts. It is particularly useful as a system component.

Examples of intake/exhaust system components include air hoses, air ducts, turbo ducts, turbo hoses, intake manifolds, exhaust manifolds, and the like.

In the following, the invention is explained in more detail with reference to examples. These examples are not intended to limit the scope of the present invention.

1. Material of resin composition <Engineering plastic (A)>
(Preparation of polyamide)
1787 g (10.8 mol) of terephthalic acid, 2800 g (24.9 mol) of 1,6-hexanediamine, 1921 g (13.1 mol) of adipic acid, 36.6 g (0.30 mol) of benzoic acid, hypophosphorous acid 5.7 g of sodium monohydrate and 554 g of distilled water were placed in an autoclave having an internal volume of 13.6 L, and the autoclave was purged with nitrogen. Stirring was started from 190° C., and the internal temperature was raised to 250° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.01 MPa. After continuing the reaction for 1 hour, the autoclave was vented to the atmosphere from a spray nozzle installed at the bottom of the autoclave to extract a low condensate. Thereafter, the low condensate was cooled to room temperature, pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110° C. for 24 hours. The resulting low condensate had a water content of 3600 ppm and an intrinsic viscosity [η] of 0.48 dl/g.
Next, this low condensate was placed in a tray-type solid-phase polymerization apparatus, and after purging with nitrogen, the temperature was raised to 220° C. over about 1 hour and 30 minutes. After that, the mixture was allowed to react for 1 hour and cooled to room temperature. Thereafter, the prepolymer is melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and L/D = 36 at a barrel setting temperature of 330°C, a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg/h to obtain a polyamide. Obtained.

The intrinsic viscosity [η], terminal amino group content, melting point (Tm) and glass transition temperature (Tg) of the obtained polyamide were measured by the following methods.

(Intrinsic viscosity [η])
First, about 0.5 g of polyamide was dissolved in 50 ml of 96.5% concentrated sulfuric acid. Then, the number of seconds for the obtained solution to flow down under the condition of 25° C.±0.05° C. was measured using an Ubbelohde viscometer. After that, the intrinsic viscosity was calculated based on the following formula.
[η]=ηSP/(C(1+0.205ηSP))

In the above formula, each algebra or variable represents:
[η]: Intrinsic viscosity (dl/g)
ηSP: specific viscosity C: sample concentration (g/dl)

ηSP is obtained by the following formula.
ηSP=(t−t0)/t0
t: number of seconds for the sample solution to flow down (seconds)
t0: Number of seconds for blank sulfuric acid to flow down (seconds)

(Amount of terminal amino group)
1 g of polyamide was dissolved in 35 mL of phenol and mixed with 2 mL of methanol to prepare a sample solution. Then, using thymol blue as an indicator, the sample solution is titrated with a 0.01 N HCl aqueous solution until the color changes from blue to yellow, and the amount of terminal amino groups ([NH ₂ ], unit: mmol/kg) is obtained. asked for

(melting point and glass transition temperature)
Using DSC (Differential Scanning Calorimetry), a sample of the polyamide was heated once at 320° C. and held for 5 minutes, then cooled at a rate of 10° C./min to 23° C., then 10° C./min. The temperature was raised at a rate of The temperature of the endothermic peak based on melting at this time was defined as the melting point (Tm), and the temperature based on the glass transition was defined as the glass transition temperature (Tg).

The resulting polyamide had an intrinsic viscosity [η] of 0.8 dl/g, a terminal amino group content of 195 mmol/kg, a melting point Tm of 295°C, and a glass transition temperature Tg of 75°C.

<Thermoplastic elastomer (B)>
As the thermoplastic elastomer (B), the following thermoplastic elastomer (B-1) was prepared.

(Preparation of thermoplastic elastomer (B-1))
Ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) is ethylene/propylene/5-ethylidene-2-norbornene copolymer rubber (ethylene content 65% by mass, diene content 4.6% by mass, [ η]=2.4 dl/g) is 55% by mass, and ethylene/methacrylic acid copolymer (trade name: Nucrel AN4213C (trademark), Mitsui/DuPont Poly Chemical Co., Ltd. Density (JIS K 7112: 1999): 940 kg/m ³ Melting point: 88°C Acid content: 11% by mass MFR (JIS K 7210: 1999 (190°C, 2.16 kg load) 10 g/10 40% by mass, and flaky brominated alkylphenol formaldehyde resin (trade name: Tackroll 250-III, manufactured by Taoka Kagaku Kogyo Co., Ltd.) as a phenolic resin-based cross-linking agent (B-III) was stirred for 10 seconds in a Henschel mixer. 5% by mass of the powdered material and a small amount of two types of zinc oxide (manufactured by Hakusui Tech Co., Ltd.) as a cross-linking aid are premixed, and this is subjected to a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX-30 ), and melt-kneaded at a cylinder temperature of 200° C. and a screw rotation speed of 300 rpm, and the strand extruded from this twin-screw extruder was cut to obtain pellets of the thermoplastic elastomer (B-1).

Table 1 shows the composition of the obtained thermoplastic elastomer (B-1).

<Resin for comparison>
As a comparative resin, the following modified ethylene/1-butene copolymer (b) was prepared.

(Preparation of modified ethylene/1-butene copolymer (b))
0.63 mg of bis(1,3-dimethylcyclopentadienyl)zirconium dichloride was placed in a sufficiently nitrogen-substituted glass flask, and 1.57 ml of a toluene solution of methylaluminoxane (Al; 0.13 mmol/liter) was added. , and 2.43 ml of toluene were added to obtain a catalyst solution.
Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a 2-liter stainless steel autoclave which was sufficiently purged with nitrogen, and the temperature in the system was raised to 80°C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml of the catalyst solution prepared above (0.0005 mmol as Zr) were injected into the system with ethylene to initiate the polymerization reaction. The total pressure was maintained at 8.0 kg/cm ² -G by continuously supplying ethylene, and polymerization was carried out at 80° C. for 30 minutes.
A small amount of ethanol was introduced into the system to terminate the polymerization of the polymer, and then unreacted ethylene was purged. The resulting solution was poured into a large excess of methanol to precipitate a white solid. The white solid was collected by filtration and dried overnight under reduced pressure to obtain a white solid (ethylene/1-butene copolymer). The resulting ethylene/1-butene copolymer had a density of 0.865 g/cm ³ , an MFR (ASTM D1238 standard, 190°C: 2160 g load) of 0.5 g/10 minutes, and a 1-butene structural unit content of 4 mol. %was.
100 parts by mass of the obtained ethylene/1-butene copolymer was mixed with 1.0 parts by mass of maleic anhydride and 0.04 parts by mass of peroxide (Perhexine 25B, manufactured by NOF Corporation, registered trademark). did. The resulting mixture was subjected to melt graft modification in a single-screw extruder set at 230° C. to obtain a modified ethylene/1-butene copolymer (b).

The resulting modified ethylene/1-butene copolymer (b) had a maleic anhydride graft modification amount of 0.98% by mass. Moreover, the intrinsic viscosity [η] measured in a decalin solution at 135° C. was 1.90 dl/g.

<Fibrous filler (C)>
Chopped strand of glass fiber (ECS03T-251H manufactured by Nippon Electric Glass Co., Ltd., glass fiber (single fiber) fiber diameter 10.5 μm, average length 3 mm, aminosilane-based compound treatment product (attachment amount 0.45% by mass))

2. Preparation of resin composition <Example 1>
The semi-aromatic polyamide (A-1) as the engineering plastic (A), the thermoplastic elastomer (B-1) as the thermoplastic elastomer (B), and the chopped strands of the glass fiber as the fibrous filler (C). and are premixed at the composition ratio shown in Table 2, supplied to a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX-30), and melted at a cylinder temperature of 280 ° C. and a screw rotation speed of 300 rpm. Kneaded. The strand extruded from this twin-screw extruder was cut to obtain pellets of the resin composition.

<Comparative Example 1>
Pellets of a resin composition were obtained in the same manner as in Example 1, except that the resin for comparison shown in Table 2 was used instead of the thermoplastic elastomer (B).

<Comparative Example 2>
Pellets of a resin composition were obtained in the same manner as in Example 1 except that the thermoplastic elastomer (B) was not included and the composition was changed to that shown in Table 2.

<Evaluation>
The bending strength, injection flow length and Charpy impact strength of the resin compositions of Example 1 and Comparative Examples 1 and 2 were evaluated by the following methods.

(bending strength)
The obtained resin composition was injection molded under the following molding conditions to prepare a test piece having a length of 80 mm, a width of 10 mm and a thickness of 4 mm.
Molding machine: EC75N manufactured by Toshiba Machine Co., Ltd.
Molding machine cylinder temperature: Polyamide melting point (Tm) + 15°C
Mold temperature: 120°C
The obtained test piece was left at a temperature of 23° C. under a nitrogen atmosphere for 24 hours. Next, a bending test was performed at a temperature of 23° C. and a relative humidity of 50% with a bending tester AB5 manufactured by NTESCO, a span of 64 mm, and a bending speed of 2.0 mm/min to measure the bending strength (MPa).

(Injection flow length)
The obtained resin composition was injected under the following conditions using a bar flow mold with a width of 10 mm and a thickness of 0.5 mm, and the flow length (mm) of the resin composition in the mold was measured. It should be noted that the longer the flow length, the better the injection fluidity.
Molding machine: Sodick plastic, Tupal TR40S3A
Injection set pressure: 2000 kg/cm ²
Molding machine cylinder temperature: Polyamide melting point (Tm) + 15°C
Mold temperature: 120°C

(Charpy impact strength)
The resulting resin composition was injection molded under the following molding conditions to prepare a notched test piece with a thickness of 4 mm.
Molding machine: EC75N manufactured by Toshiba Machine Co., Ltd.
Molding machine cylinder temperature: Polyamide melting point (Tm) + 15°C
Mold temperature: 80°C
The Charpy impact strength of the obtained test piece was measured in accordance with ISO 179, 1) in an atmosphere of 23°C and 50% relative humidity, and 2) in an atmosphere of -40°C and 50% relative humidity. .

Evaluation results of Example 1 and Comparative Examples 1 and 2 are shown in Table 2.

As shown in Table 2, a thermoplastic elastomer (B), which is a dynamically crosslinked product of a composition containing a copolymer rubber (BI) and an ethylene/unsaturated carboxylic acid copolymer (B-II), was prepared. The resin composition of Example 1 containing modified ethylene/1-butene copolymer (b) as a comparative resin has a longer flow length (while maintaining impact strength) than the resin composition of Comparative Example 1 containing It can be seen that the bending strength can be increased. Moreover, it can be seen that the resin composition of Example 1 has a higher Charpy impact strength (impact resistance) than the resin composition of Comparative Example 2.

According to the present invention, a resin composition and a molded article that can reduce the decrease in melt fluidity and bending strength during molding and can provide a molded article with excellent impact resistance even if it contains a fibrous filler, and a method for producing a resin composition can be provided.

Claims (9)

60 to 90 parts by mass of an engineering plastic (A) having a melting point (Tm) of 150 to 350° C. measured by a differential scanning calorimeter (DSC);
5 to 35 parts by mass of a thermoplastic elastomer (B);
5 to 35 parts by mass of fibrous filler (C) (provided that the total of components (A), (B) and (C) is 100 parts by mass),
The thermoplastic elastomer (B) is
A structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene having two or more carbon-carbon double bonds in one molecule. an ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) containing
an ethylene/unsaturated carboxylic acid copolymer (B-II) containing a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid;
A crosslinked product of a composition containing a phenolic resin-based crosslinking agent (B-III),
The unsaturated carboxylic acid is an unsaturated monocarboxylic acid,
The content of structural units derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid copolymer (B-II) is 5 to 20% by mass.
Resin composition. The ethylene/unsaturated carboxylic acid copolymer (B-II) is an ethylene/methacrylic acid copolymer,
The resin composition according to claim 1. Mass ratio of the ethylene/unsaturated carboxylic acid copolymer (B-II) to the ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) (B-II)/(BI) is 41/59 to 90/10,
The resin composition according to claim 1 or 2. The fibrous filler (C) is glass fiber,
The resin composition according to any one of claims 1 to 3. The engineering plastic (A) is a semi-aromatic polyamide having a melting point (Tm) of 270 to 340° C.
The resin composition according to any one of claims 1-4. The semi-aromatic polyamide comprises a structural unit (a1) derived from a dicarboxylic acid and a structural unit (a2) derived from a diamine, and the structural unit (a1) derived from the dicarboxylic acid is Containing structural units derived from terephthalic acid in an amount of 30 mol% or more relative to a total of 100 mol% of the derived structural units (a1),
The structural unit (a2) derived from the diamine is a structural unit derived from an aliphatic diamine having 50 mol% or more of 4 to 18 carbon atoms with respect to the total 100 mol% of the structural units (a2) derived from the diamine. including,
The resin composition according to claim 5. The thermoplastic elastomer (B) comprises the ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI), the ethylene/unsaturated carboxylic acid copolymer (B-II), and the phenol resin-based When the total of the cross-linking agent (B-III) is 100 parts by mass,
30 to 80 parts by mass of the ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI),
15 to 60 parts by mass of the ethylene/unsaturated carboxylic acid copolymer (B-II),
1 to 10 parts by mass of the phenolic resin-based cross-linking agent (B-III),
The resin composition according to any one of claims 1-6. A molded article obtained from the resin composition according to any one of claims 1 to 7. A structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene having two or more carbon-carbon double bonds in one molecule. an ethylene/α-olefin/non-conjugated polyene copolymer rubber (BI) containing
an ethylene/unsaturated carboxylic acid copolymer (B-II) containing a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid;
a step of dynamically cross-linking a composition containing a phenolic resin-based cross-linking agent (B-III) to obtain a thermoplastic elastomer (B);
A step of mixing the thermoplastic elastomer (B), an engineering plastic (A) having a melting point (Tm) of 150 to 350° C. as measured by a differential scanning calorimeter (DSC), and a fibrous filler (C). and
In the mixing step,
With respect to a total of 100 parts by mass of the engineering plastic (A), the thermoplastic elastomer (B) and the fibrous filler (C),
The blending amount of the engineering plastic (A) is 60 to 90 parts by mass,
The content of the thermoplastic elastomer (B) is 5 to 35 parts by mass,
The amount of the fibrous filler (C) is 5 to 35 parts by mass,
A method for producing a resin composition.