JP7061513B2 - Resin composition and molded product, and method for manufacturing the resin composition - Google Patents

Description

The present invention relates to a resin composition and a molded product, and a method for producing the resin composition.

Engineering plastics such as polyamide resin, polycarbonate resin, and polyester resin have excellent heat resistance and chemical resistance. Therefore, molding materials including these engineering plastics and reinforcing materials such as glass fibers are used in various fields such as automobile parts and electronics-related parts.

On the other hand, the engineering plastic molded product has a problem of low impact resistance, particularly Izod impact strength.

As a method of improving the impact resistance of the molded body of the engineering plastic, it is conceivable to add ethylene / propylene copolymer rubber to the engineering plastic. Here, since engineering plastics having high polarity and ethylene / propylene copolymer rubber having low polarity do not have an affinity by nature, simply mixing them enhances the impact resistance of the obtained molded product. Not only is it impossible, but layer peeling (peeling 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 in which a vinyl monomer having an acidic group such as maleic acid is introduced into an ethylene / propylene copolymer rubber in an engineering plastic (for example, Patent Document 1 and Patent Document 1 and). 2).

Japanese Unexamined Patent Publication No. 55-44108 Japanese Unexamined Patent Publication No. 2-160813

However, the compositions of Patent Documents 1 and 2 did not have sufficient impact resistance.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition and a molded body capable of imparting a molded body having particularly excellent impact resistance, and a method for producing the resin composition. ..

[1] 60 to 95 parts by mass of engineering plastic (A) having a melting point (Tm) of 150 to 350 ° C. measured by a differential scanning calorimeter (DSC) and 5 to 40 parts by mass of a thermoplastic elastomer (B). Containing (however, the total of (A) and (B) is 100 parts by mass), the thermoplastic elastomer (B) is derived from a structural unit derived from ethylene and an α-olefin having 3 to 20 carbon atoms. Ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI) containing a structural unit to be formed and a structural unit derived from a non-conjugated polyene having at least one carbon-carbon double bond in one molecule. , 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, and a phenol resin-based cross-linking agent (B-III). A resin composition that is a crosslinked product of the composition.
[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 the structural unit 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 engineering plastic (A) includes polyamide, polyacetal, polycarbonate, polyphenylene ether, polyester, polysulfone, polyether sulfone, polyphenylene sulfide, polyallylate, polyamideimide, polyetherimide, polyetheretherketone, and fluororesin. The resin composition according to any one of [1] to [3], which is one or more selected from the group consisting of polyaminobismaleimide and polybisamide triazole.
[5] The resin according to any one of [1] to [4], wherein the engineering plastic (A) is a polyamide having a melting point (Tm) of 150 to 340 ° C. as measured by a differential scanning calorimeter (DSC). Composition.
[6] The resin composition according to [5], wherein the polyamide is an aliphatic polyamide having a melting point (Tm) of 150 to 290 ° C.
[7] The aliphatic polyamide contains (i) a structural unit derived from a dicarboxylic acid and a structural unit derived from a diamine, and the structural unit derived from the dicarboxylic acid is a structural unit derived from the dicarboxylic acid. The structural unit derived from the aliphatic dicarboxylic acid having 80 mol% or more of carbon atoms of 6 to 12 is contained with respect to the total of 100 mol%, and the structural unit derived from the diamine is the total of the structural units derived from the diamine. It is an aliphatic polyamide containing 80 mol% or more of structural units derived from an aliphatic diamine having 4 to 12 carbon atoms with respect to 100 mol%, or (ii) a lactam or aminocarboxylic acid having 6 to 12 carbon atoms. The resin composition according to [6], which is an aliphatic polyamide containing a structural unit derived from an acid.
[8] The thermoplastic elastomer (B) includes the ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI), the ethylene / unsaturated carboxylic acid copolymer (B-II), and the above. When the total of the phenolic resin-based cross-linking agent (B-III) is 100 parts by mass, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI) is 30 to 80 parts by mass and the ethylene. Any of [1] to [7] containing 15 to 60 parts by mass of the unsaturated carboxylic acid copolymer (B-II) and 1 to 10 parts by mass of the phenol resin-based cross-linking agent (B-III). The resin composition described in Crab.
[9] A molded product obtained from the resin composition according to any one of [1] to [8].
[10] 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. Ethylene / unsaturated carboxylic acid containing ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI) containing units, structural units derived from ethylene, and structural units derived from unsaturated carboxylic acid. A step of dynamically cross-linking a composition containing a copolymer (B-II) and a phenol resin-based cross-linking agent (B-III) to obtain a thermoplastic elastomer (B), and the thermoplastic elastomer (B). And a step of mixing 60 to 95 parts by mass of the engineering plastic (A) having a melting point (Tm) of 150 to 350 ° C. measured by a differential scanning calorimeter (DSC) (however, (A) and (B)). A method for producing a resin composition, which comprises 100 parts by mass.

According to the present invention, it is possible to provide a resin composition and a molded product that can impart a molded product having particularly excellent impact resistance, and a method for producing the resin composition.

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

1-1. Engineering plastic (A)
The 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 the engineering plastic (A) can be measured under the following conditions. Using DSC (Differential Scanning Calorimetry), the engineering plastic (A) sample is heated and held at 320 ° C. for 5 minutes, then cooled to 23 ° C. at a rate of 10 ° C./min, and then at 10 ° C. The temperature rises at a rate of / minute. 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 group in which one or more of them are combined. Such engineering plastics (A) include polyamide, polyacetal, polycarbonate, polyester, polyphenylene ether, polysulfone, polyether sulfone, polyphenylene sulfide, polyallylate, polyamideimide, polyetherimide, polyetheretherketone, polyimide, fluororesin. , Polyaminobismaleimide and polybisamide triazole are preferably one or more selected from the group.

(polyamide)
Polyamide is a polymer containing a structural unit having an amide bond (-NH-C (= O)-), and is a polycondensation polymer of a dicarboxylic acid and a diamine, or a ring-opening polymerization of lactam (or an aminocarboxylic acid). (Polycondensation) or a combination thereof. That is, does the polyamide contain (i) a structural unit derived from a dicarboxylic acid and a structural unit derived from a diamine; (ii) a ring-opened product of lactam or a structural unit derived from an aminocarboxylic acid; (i). ) And (ii) can be included.

[Structural unit derived from dicarboxylic acid / Structural unit derived from diamine]
The dicarboxylic acid for obtaining a structural unit derived from a dicarboxylic acid can be an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid or an ester thereof.

The aliphatic dicarboxylic acid is an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of aliphatic dicarboxylic acids or esters thereof include 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid. Acids, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and the like are included. The aliphatic dicarboxylic acid or an ester thereof may be used alone or in combination of two or more.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride and the like. .. These may be used alone or in combination of two or more. The aromatic dicarboxylic acid or its ester may be one kind or a combination of two or more kinds.

The diamine for obtaining a structural unit derived from a diamine can be an aliphatic diamine or an aromatic diamine.

The aliphatic diamine is preferably an aliphatic diamine having 4 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of aliphatic diamines include linear methylene diamines, pentamethylene diamines, hexamethylene diamines, heptamethylene diamines, octamethylene diamines, nonamethylene diamines, decamethylene diamines, undecamethylene diamines, dodecamethylene diamines and the like. Aliphatic diamines; 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2, -Contains branched aliphatic diamines such as methyloctamethylenediamine and 2,4-dimethyloctamethylenediamine. The aliphatic diamine may be one kind or a combination of two or more kinds.

Examples of aromatic diamines include metaxylylenediamine and the like.

[Structural unit derived from lactam ring-opened material]
The lactam for obtaining a structural unit derived from a ring-opened product of lactam can be a lactam having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. Examples of such lactams include ε-caprolactam, undecane lactam, ω-laurolactam, ε-enantractam and the like, preferably ε-caprolactam. Only one type of lactam may be used, or two or more types may be combined.

[Structural unit derived from aminocarboxylic acid]
The aminocarboxylic acid for obtaining the structural unit derived from the aminocarboxylic acid is an aminocarboxylic acid having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. The aminocarboxylic acid may be the ring-opened product of the above-mentioned lactam. Examples of such aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Only one type of aminocarboxylic acid may be used, or two or more types may be combined.

Among these, polyamide is preferable, polyamide having a melting point (Tm) of 150 to 340 ° C. is more preferable, and aliphatic polyamide having a melting point (Tm) of 150 to 290 ° C. is further preferable.

Aliphatic polyamides having a melting point (Tm) of 150 to 290 ° C. have (i) a structural unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms and a structure derived from an aliphatic diamine having 4 to 12 carbon atoms. It is preferable to use an aliphatic polyamide containing a unit, or (ii) an aliphatic polyamide containing a structural unit derived from lactam or an aminocarboxylic acid having 6 to 12 carbon atoms.

The content ratio of the structural unit derived from the aliphatic dicarboxylic acid in the aliphatic polyamide (i) may be 80 mol% or more with respect to the total number of moles of the structural unit derived from the dicarboxylic acid constituting the aliphatic polyamide. preferable. When the content ratio of the structural unit derived from the aliphatic dicarboxylic acid is 80 mol% or more, the crystallinity of the aliphatic polyamide tends to increase, and sufficient heat resistance and mechanical strength (bending strength, etc.) are imparted to the molded body. Can be done. The content ratio of the structural unit derived from the aliphatic dicarboxylic acid is more preferably 85 to 100 mol% and further preferably 90 to 100 mol% with respect to the total number of moles of the structural unit derived from the dicarboxylic acid. preferable.

The content ratio of the structural unit derived from the aliphatic diamine in the aliphatic polyamide (i) is preferably 80 mol% or more with respect to the total number of moles of the structural unit derived from the diamine constituting the aliphatic polyamide. When the content ratio of the structural unit derived from the aliphatic diamine is 80 mol% or more, the crystallinity of the aliphatic polyamide tends to increase, and sufficient heat resistance and mechanical strength (bending strength, etc.) are imparted to the molded body. sell. The content ratio of the structural unit derived from the aliphatic diamine is more preferably 85 to 100 mol% and further preferably 90 to 100 mol% with respect to the total number of moles of the structural unit derived from the diamine.

Examples of polyamides include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), and polyhexamethylene. Sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510), polytetramethylene sebacamide (polyamide 410), polyhexamethylene dodecamide (polyamide 612), polyundecaneamide (polyamide 11), polydodecane Amid (polyamide 12), polycaproamide / polyhexamethylene adipamide (polyamide 6/66), polycaproamide / polyhexamethylene terephthalamide (polyamide 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthal. Amid (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide (polyamide 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide (polyamide 66 / 6I / 6) ), Polyhexamethylene terephthalamide / polyhexamethylene isophthalamide (polyamide 6T / 6I), polyhexamethylene terephthalamide / polydecaneamide (polyamide 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / poly Hexamethylene isophthalamide (polyamide 66 / 6T / 6I), polyxylylene adipamide (polyamide XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide (polyamide 6T / M5T), polyhexamethylene terephthalamide Amid / polypentamethylene terephthalamide (polyamide 6T / 5T), polypentamethylene terephthalamide / polypentamethylene adipamide (5T / 56), polynonamethylene terephthalamide (polyamide 9T), polydecamethylene terephthalamide (polyamide 10T) ) And their copolymers. Among these, polyamide 6, polyamide 66, polyamide 610, polyamide 6/66, polyamide 66 / 6I, and polyamide 66 / 6I / 6 are preferable, and polyamide 6 and polyamide 66 are preferable from the viewpoint of further improving impact resistance and fluidity. Such as aliphatic polyamides are more preferable, and polyamide 6 is even more preferable.

From the viewpoint of thermal stability during compounding and molding, the polyamide preferably has at least a part of the terminal groups of the molecular chain sealed with an end sealant. 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. It is more preferably 5 to 200 mmol / kg.

The terminal encapsulant is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the molecular terminal of polyamide, but from the viewpoint of reactivity and stability of the encapsulating end, it is a mono. Carboxylic acid or monoamine is preferable, and monocarboxylic acid is more preferable from the viewpoint of ease of handling.

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

The monoamine used as the terminal encapsulant is not particularly limited as long as it has reactivity with a carboxyl group. Examples of monoamines include aliphatic monoamines such as butylamines, hexylamines, octylamines, decylamines and stearylamines; alicyclic monoamines such as cyclohexylamines and dicyclohexylamines; aromatic monoamines such as aniline and toluidine.

The melting point of the aliphatic polyamide is not particularly limited, but is preferably 150 to 290 ° C. When the melting point of the aliphatic polyamide is 150 ° C. or higher, the heat resistance of the obtained resin composition can be further enhanced. When the melting point of the aliphatic polyamide is 290 ° C. or lower, thermal decomposition and deterioration of the aliphatic polyamide during the melt processing can be more effectively suppressed. The melting point of the aliphatic polyamide is more preferably 200 to 280 ° C. The melting point of the aliphatic polyamide can be measured by the same method as described above.

The melting point (Tm) of the aliphatic polyamide can be adjusted, for example, by the monomer composition. In order to increase the melting point (Tm) of the aliphatic polyamide, for example, it is preferable to set the number of carbon atoms of the dicarboxylic acid, diamine, lactam and aminocarboxylic acid constituting the aliphatic polyamide to a certain level or less.

The melt flow rate (MFR) of the aliphatic polyamide at 290 ° C. and 2.16 kg load according to ISO 1133 is 0 from the viewpoint of easy fine dispersion by matching the viscosity with the copolymer rubber (BI) at the time of compounding. .1 to 500 g / 10 minutes, more preferably 0.1 to 300 g / 10 minutes, even more preferably 0.1 to 100 g / 10 minutes, 1 to 100 g / 10 minutes. It is particularly preferable to have.

The melt flow rate (MFR) of the aliphatic polyamide can be adjusted by, for example, the molecular weight of the aliphatic polyamide, the amount of terminal amino groups, and the like. In order to lower the MFR of the aliphatic polyamide, it is preferable to increase the molecular weight and the amount of terminal amino groups.

(Polyacetal)
Polyacetal is a polymer containing an oximethylene structural unit (-OCH _2- ). The polyacetal may be a polyacetal homopolymer such as polyoxymethylene (for example, manufactured by Dupont, USA, trade name "Delrin", manufactured by Asahi Kasei Kogyo Co., Ltd., trade name "Tenac 4010"); oxymethylene structure. It may be a polyacetal copolymer containing a unit and a comonomer structural unit (for example, manufactured by Polyplastics Co., Ltd., trade name "Duracon").

Examples of the comonomer structural unit contained in the polyacetal copolymer include an oxyalkylene structural unit 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) is included. The content of the comonomer structural unit may be 0.01 to 20 mol%, preferably 0.03 to 15 mol%, and more preferably 0.1 to 10 mol% with respect to all the structural units constituting the polyacetal.

The polyacetal copolymer may be a binary copolymer or a multiple copolymer having three or more components. The polyacetal copolymer may be a random copolymer or a block copolymer (for example, Japanese Patent Publication No. 2-24307, manufactured by Asahi Kasei Kogyo Co., Ltd., trade names "Tenac LA" and "Tenac LM"). Or a graft copolymer or the like. Further, the polyacetal may have a branched structure or a crosslinked structure as well as a linear structure. Further, the molecular terminal of polyacetal may be stabilized by, for example, esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof, urethanization with an isocyanate compound, etherification or the like.

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

(polyester)
The polyester can be a polymer obtained by polycondensing a divalent or higher aromatic carboxylic acid with a divalent or higher alcohol and / or phenol. Of these, crystalline polyester, particularly crystalline polyester having a melting point of 200 ° C. or higher, is preferable. Examples of polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate. Of these, polyethylene terephthalate and polybutylene terephthalate are preferable, and polybutylene terephthalate is particularly preferable. Commercially available polyester products include Novaduran (manufactured by Mitsubishi Engineering Plastics), which can be easily obtained from the market.

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

(Polyether salhon)
The polyether sulfone can be, for example, a polymer obtained by polycondensing bisphenol A and 4,4'-dichlorodiphenyl sulfone.

The polyethersulfon may be an aromatic polyethersulfon containing a structural unit 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 of the formula (1) are aromatic hydrocarbon groups having the same or different carbon atoms of 6 to 12 (for example, an arylene group having 6 to 12 carbon atoms). Ar ₃ to Ar ₆ in the formula (2) are aromatic hydrocarbon groups having the same or different carbon atoms 6 to 12 (for example, an arylene group having 6 to 12 carbon atoms), and X is an arylene group having 1 to 15 carbon atoms. It is a divalent carbon hydrogen group. Ars ₇ to Ar ₉ of the formula (3) are aromatic hydrocarbon groups having the same or different carbon atoms of 6 to 12 (for example, an arylene group having 6 to 12 carbon atoms).

(Polyphenylene sulfide)
Polyphenylene sulfide is a polymer containing a structural unit 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 and o-phenylene. S is a sulfur atom.

The polyphenylene sulfide may further contain a structural unit derived from a monomer other than the structural unit represented by the above formula. Examples of other monomers include alkyl substituted phenylene (preferably an alkyl group having 1 to 6 carbon atoms), phenyl substituted phenylene, halogen substituted phenylene, amino substituted phenylene, amide substituted phenylene, p, p'-diphenylensulphon. , P, p'-biphenylene, p, p'-biphenylene ether, p, p'-biphenylene carbonyl and naphthalene. The other monomer may be one kind or a combination of two or more kinds.

(Polyarylate)
The polyarylate may be a polymer obtained by polycondensing a divalent phenol compound (for example, bisphenol A) and an aromatic dicarboxylic acid (for example, terephthalic acid or isophthalic acid).

(Polyamide-imide)
The polyamide-imide can be a polymer obtained by polycondensing an aromatic dicarboxylic acid and an aromatic diisocyanate, or a polymer obtained by polycondensing an aromatic diacid anhydride and an aromatic diisocyanate.

Examples of aromatic dicarboxylic acids include isophthalic acid and terephthalic acid. Examples of aromatic diacid anhydrides include trimellitic anhydride. Examples of aromatic diisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, orthotrilene diisocyanate, and m-xylene diisocyanate.

(Polyetherimide)
Polyetherimide is a polymer containing a structural unit containing an imide group and an ether group. Examples of polyetherimides include polymers containing structural units represented by the following formulas.

(Polyetheretherketone)
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, and ethylene polyfluoride. Includes propylene ether, polyfluoroalkoxyethylene, polychlorotrifluoroethylene, polytetrafluoroethylene and the like.

(Polyaminobismaleimide)
The 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 following formula, P and Q are divalent organic groups, respectively.

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, Includes 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone and the like.

Examples of bismaleimide compounds include N, N'-ethylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-hexamethylene bismaleimide, N. , N'-4,4'-diphenylmethanebismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, bis [4- (4-maleimidephenoxy) phenyl] methane, 1,1,1 , 3,3,3-Hexafluoro-2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, N, N'-p, p'-diphenyldimethylsilylbismaleimide, N, N'-p , P'-diphenyl ether bismaleimide, N, N'-p, p'-diphenylsulfone bismaleimide, N, N'-dicyclohexylmethanebismaleimide, N, N'-m-xylene bismaleimide, N, N'-( Includes 3,3'-dichloro-p, p'-bismaleimide) bismaleimide, N, N'-(3,3'-diphenyloxy) bismaleimide.

Among these, polyamides are preferable, and the above-mentioned aliphatic polyamides are more preferable because they have good mechanical properties, heat resistance, moldability, and the like.

The content of the engineering plastic (A) is preferably 60 to 95 parts by mass with respect to 100 parts by mass in total of the engineering plastic (A) and the thermoplastic elastomer (B). When the content of the engineering plastic (A) is 60 parts by mass or more, the heat-resistant deformability of the obtained resin composition is likely to be enhanced, and when it is 95 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 70 to 90 parts by mass, more preferably 75 to 85 parts by mass with respect to 100 parts by mass of the total of the engineering plastic (A) and the thermoplastic elastomer (B). Is more preferable.

1-2. Thermoplastic elastomer (B)
The thermoplastic elastomers are ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI), ethylene / unsaturated carboxylic acid copolymer (B-II), and a phenol resin-based cross-linking agent (B-III). ) And a crosslinked product (dynamic crosslinked product). The 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 derived from 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 thereof.

(Structural unit derived from ethylene)
The content ratio of the structural unit derived from ethylene is preferably 50 to 89% by mass, more preferably 55 to 83% by mass with respect to all the 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-eikosen and the like are included. Of these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferable. The α-olefin may be one kind or a combination of two or more kinds. These α-olefins are preferable because the raw material cost is relatively low and the copolymerizability is excellent, and the copolymer rubber (BI) is imparted with excellent mechanical properties and good flexibility.

The content ratio of the structural unit derived from the α-olefin having 3 to 20 carbon atoms is preferably 10 to 49% by mass, preferably 10 to 49% by mass, based on all the structural units constituting the copolymer rubber (BI). More preferably, it is ~ 43% by mass.

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

Examples of aliphatic polyenes are 1,4-hexadiene, 1,5-heptadiene, 1,6-octadien, 1,7-nonadien, 1,8-decadien, 1,12-tetradecadien, 3-methyl- 1,4-Hexadien, 4-Methyl-1,4-Hexadien, 5-Methyl-1,4-Hexadien, 4-Ethyl-1,4-Hexadien, 3,3-Dimethyl-1,4-Hexadien, 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-octadien, 5-methyl-1,4-octadien, 4-ethyl-1,4-octadien, 5-ethyl-1,4-octadien, 5-methyl-1,5-octadien, 6- Methyl-1,5-octadien, 5-ethyl-1,5-octadien, 6-ethyl-1,5-octadien, 6-methyl-1,6-octadien, 7-methyl-1,6-octadien, 6- Ethyl-1,6-octadien, 6-propyl-1,6-octadien, 6-butyl-1,6-octadien, 4-methyl-1,4-nonadien, 5-methyl-1,4-nonadien, 4- Ethyl-1,4-nonadien, 5-ethyl-1,4-nonadien, 5-methyl-1,5-nonadien, 6-methyl-1,5-nonadien, 5-ethyl-1,5-nonadien, 6- Ethyl-1,5-nonadien, 6-methyl-1,6-nonadien, 7-methyl-1,6-nonadien, 6-ethyl-1,6-nonadien, 7-ethyl-1,6-nonadien, 7- Methyl-1,7-nonadien, 8-methyl-1,7-nonadien, 7-ethyl-1,7-nonadien, 5-methyl-1,4-decadien, 5-ethyl-1,4-decadien, 5- Methyl-1,5-decadien, 6-methyl-1,5-decadien, 5-ethyl-1,5-decadien, 6-ethyl-1,5-decadien, 6-methyl-1,6-decadien, 6- Ethyl-1,6-decadien, 7-methyl-1,6-decadien, 7-ethyl-1,6-decadien, 7-methyl-1,7-decadien, 8-methyl-1,7-decadien, 7- Ethyl-1,7-decadien, 8-ethyl-1,7-decadien, 8-methyl-1,8-decadien, 9-methyl-1,8-decadien, 8-ethyl-1,8-decadien, 6- Methyl-1,6-Undeca Includes α, ω-diene such as diene, 9-methyl-1,8-undecadien, and further 1,7-octadien, 1,9-decadien. Of these, 7-methyl-1,6-octadien is preferred.

Examples of alicyclic polyenes include 5-ethylidene-2-norbornene (ENB), 5-propyriden-2-norbornene, 5-butylidene-2-norbornene, 5-vinyl-2-norbornene (VNB); 5-allyl. 5-Alkenyl-2-norbornene 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-norbornene, 2-ethyl-2,5-norbornene and the like are included. Of these, 5-ethylidene-2-norbornene (ENB) is preferable. The non-conjugated polyene structural unit may be of one type or may be used in combination of two or more types.

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

The ultimate 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. It is particularly preferably 5 to 4.0 dl / g. This ultimate viscosity [η] is a value measured in decalin at a temperature of 135 ° C., and can be obtained by measuring according to ASTM D 1601.

The content of the copolymer rubber (BI) shall be 30 to 80 parts by mass with respect to 100 parts by mass in total of the (BI) component, the (B-II) component and the (B-III) component. Is preferable. 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, so that the impact resistance of the obtained resin composition is sufficiently enhanced. On the other hand, since the content of the ethylene / unsaturated carboxylic acid copolymer (B-II) does not become too large, the moldability, mechanical strength (bending strength, etc.) and heat resistance are not easily impaired. When the content of the copolymer rubber (BI) is 80 parts by mass or less, the content of the ethylene / unsaturated carboxylic acid copolymer (B-II) does not become too small, so that the engineering plastic (A) The compatibility between the copolymer (B) and the thermoplastic elastomer (B) and the effect of improving the impact resistance due to the compatibility are not easily impaired. The content of the copolymer rubber (BI) shall be 35 to 80 parts by mass with respect to 100 parts by mass in total of the (BI) component, the (B-II) component and the (B-III) component. Is more preferable, and 45 to 70 parts by mass is further 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 unsaturated carboxylic acid. Because the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer (B-II) easily interacts with the polar group that the engineering plastic (A) can have (for example, in the case of polyamide, the carboxyl group or the amino group). , The compatibility between the engineering plastic (A) and the thermoplastic elastomer (B) can be enhanced, and the impact resistance can be further enhanced.

The unsaturated carboxylic acid copolymerized with ethylene can be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid monoester, or the like. Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid and the like; examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid and the like; examples of unsaturated dicarboxylic acid monoesters include Includes monomethyl maleate, monoethyl maleate, and monoisobutyl maleate. Among these, acrylic acid or methacrylic acid is preferable, and methacrylic acid is particularly preferable.

The content (acid content) of the structural unit derived from the unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer (B-II) is preferably 5 to 20% by mass, preferably 5 to 15% by mass. % Is more preferable. When the content (acid content) of the structural unit derived from the unsaturated carboxylic acid is above a certain level, the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer (B-II) may be, for example, the engineering plastic (A). Since it easily interacts with a possible polar group or the like, it is easy to improve the compatibility between the engineering plastic (A) and the thermoplastic elastomer (B), and it is easy to improve the impact resistance. On the other hand, when the content (acid content) of the structural unit derived from the unsaturated carboxylic acid is below a certain level, the content of the carboxyl group in the resin composition does not increase too much, so that the engineering plastic (A) and the thermoplastic The elastomer (B) does not interact too much and the fluidity is not easily impaired. 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 polymorphic weight of ethylene, an unsaturated carboxylic acid and another monomer. 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. , Unsaturated carboxylic acid esters such as dimethyl maleate, and the like. However, if too much of these other monomers is contained, the melting point is low and the heat resistance may be impaired. Therefore, the content ratio of the structural unit derived from other monomers may be 20% by weight or less, preferably 10% by weight or less, based on 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 not easily impaired. When the melting point is 120 ° C. or lower, the viscosity of the thermoplastic elastomer (B) at the time of melting is unlikely to be excessively high, and the moldability is not easily 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 an ethylene / unsaturated carboxylic acid copolymer (B-II) measured at 190 ° C. under a 2.16 kg load according to JIS K 7210: 1999 has impaired moldability. Unless otherwise limited, it may 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 with respect to a total of 100 parts by mass of the (BI) component, the (B-II) component and the (B-III) component. It is preferably parts by mass. 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 (BI) and the engineering plastic (A), and eventually the thermoplastic elastomer It is easy to sufficiently enhance the compatibility between (B) and the engineering plastic (A), and it is easy to impart sufficient impact resistance to the obtained resin composition. When the content of the ethylene / unsaturated carboxylic acid copolymer (B-II) is 60 parts by mass or less, the moldability, mechanical strength (bending strength, etc.) and heat resistance of the obtained resin composition are not easily impaired. .. The content of the ethylene / unsaturated carboxylic acid copolymer (B-II) is 15 to 55 with respect to a total of 100 parts by mass of the (BI) component, the (B-II) component and the (B-III) component. It is more preferably parts by mass, and even more preferably 20 to 50 parts by mass.

The mass ratio ((B-II) / (BI)) of the ethylene / unsaturated carboxylic acid copolymer (B-II) to the copolymer rubber (BI) is 30/70 to 90 /. It is preferably 10, more preferably 40/60 to 80/20, and even more preferably 40/60 to 75/25. When the mass ratio of the ethylene / unsaturated carboxylic acid copolymer (B-II) is above a certain level, the compatibility between the engineering plastic (A), the copolymer rubber (BI), and the thermoplastic elastomer (B) is compatible. It is easy to increase the impact resistance of the obtained resin composition. When the mass ratio of the ethylene / unsaturated carboxylic acid copolymer (B-II) is not more than a certain level, the obtained resin composition has good impact resistance and mechanical strength (bending strength, etc.). Hard to be damaged.

Further, the mass ratio ((B-II) / (A)) of the ethylene / unsaturated carboxylic acid copolymer (B-II) to the engineering plastic (A) further enhances the impact resistance of the obtained resin composition. From the viewpoint of facilitating, it is preferably 5/95 to 15/85 (mass ratio), and from the viewpoint of enhancing the impact resistance of the obtained resin composition, it is 8/92 to 12/88 (mass ratio). Is more preferable.

1-2-3. Phenol resin-based cross-linking agent (B-III)
The phenol resin-based cross-linking agent (B-III) is typically a resolution resin obtained by condensing an alkyl-substituted or unsubstituted phenol with an aldehyde (preferably formaldehyde) in the presence of an alkaline catalyst. .. The alkyl group of the alkyl-substituted phenol is preferably an alkyl group having 1 to 10 carbon atoms. That is, the 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 a compound represented by the following formula (1).

In the formula (1), R is an organic group such as an alkyl group, preferably an organic group having less than 20 carbon atoms, and 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 to 20, preferably an integer of 0 to 15, and more preferably an integer of 0 to 10.

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

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

Examples of commercially available phenolic resin-based cross-linking agents (B-III) include Tacki Roll 201, Tacky Roll 250-I, Tacky Roll 250-III from Taoka Chemical Industry Co., Ltd .; SP1045, SP1055, SP1056 from SI Group; Showa Denko. Showa Denko CRM Co., Ltd .; Tamanol 531 of Arakawa Chemical Industry Co., Ltd.; Sumitomo Bakelite Co., Ltd. Sumilite Resin PR; Gun Ei Chemical Industry Co., Ltd. Is done. These may be used alone or in combination of two or more. Of these, Tackylol 250-III (brominated alkylphenol formaldehyde resin) manufactured by Taoka Chemical Industry Co., Ltd. and SP1055 (brominated alkylphenol formaldehyde resin) manufactured by SI Group are preferable.

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

When the phenolic resin-based cross-linking agent (B-III) is a powder-like cross-linking agent, the average particle size thereof is preferably 0.1 μm to 3 mm, more preferably 1 μm to 1 mm, and particularly preferably 5 μm to 0.5 mm. Is. The flake-shaped curing agent is preferably used after being powdered by a crusher such as a jet mill or a crusher with a crushing blade.

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

1-2-4. Other components The composition for obtaining the thermoplastic elastomer (B) is other than the components (BI), (B-II) and (B-III) as long as the effects of the present invention are not impaired. It may further contain the components of. Examples of other components include cross-linking agents other than the phenolic resin-based cross-linking agent (B-III), cross-linking aids, auxiliary stabilizers (antioxidants), and the like.

The other cross-linking agent may be any cross-linking agent capable of dynamically cross-linking the above-mentioned composition, and examples thereof 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 component (BI) and the component (B-II) is high, so that the organic peroxide does not easily function as a cross-linking agent.

Examples of cross-linking aids include magnesium hydroxide, calcium hydroxide, magnesium oxide, zinc oxide and the like.

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

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

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

Dynamic cross-linking is usually carried out by supplying the above-mentioned composition to a melt-kneading device and heating it to a predetermined temperature for melt-kneading. As the melt-kneading device, for example, a twin-screw extruder, a single-screw extruder, a kneader, a Banbury mixer and the like can be used. Of these, a twin-screw extruder is preferable because it has good shearing force and continuous productivity. The melt-kneading temperature is usually 200 to 320 ° C. The melt-kneading time is usually 0.5 to 30 minutes.

By this dynamic cross-linking, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI) is cross-linked. That is, the thermoplastic elastomer (B) is a copolymer rubber (BI) crosslinked with a phenol resin-based cross-linking agent (B-III) and an ethylene / unsaturated carboxylic acid copolymer (B-II). Can include. The thermoplastic elastomer (B) is a sea phase (matrix phase) containing an ethylene / unsaturated carboxylic acid copolymer (B-II) and an island phase containing a crosslinked copolymer rubber (BI). It has a sea-island structure with (dispersed phase).

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 the island phase (dispersed phase) containing the copolymer rubber (BI) crosslinked with the engineering plastic (A). Can increase the compatibility of The average particle size of the island phase (dispersed phase) is relatively small and is finely dispersed. Such thermoplastic elastomers (B) may have good flexibility or impact resistance and may have good compatibility with engineering plastics (A). As a result, the obtained resin composition can have good impact resistance without causing delamination or the like.

The content of the thermoplastic elastomer (B) is preferably 5 to 40 parts by mass with respect to 100 parts by mass in total of the engineering plastic (A) and the thermoplastic elastomer (B). When the content of the thermoplastic elastomer (B) is 5 parts by mass or more, the impact resistance of the obtained resin composition is likely to be enhanced, and when it is 40 parts by mass or less, the heat resistance and mechanical properties of the obtained resin composition are increased. The target strength is not easily impaired. The content of the thermoplastic elastomer (B) is more preferably 10 to 30 parts by mass, more preferably 15 to 25 parts by mass, based on 100 parts by mass of the total of the engineering plastic (A) and the thermoplastic elastomer (B). Is even more preferable.

1-3. Other Components The resin composition of the present invention may further contain components other than the engineering plastic (A) and the thermoplastic elastomer (B). Examples of other components include the compatibilizer (C).

(Compatible agent (C))
The compatibilizer (C) is not particularly limited, but in order to make the engineering plastic (A) and the thermoplastic elastomer (B) better compatible, a polar group-containing compound such as a hydroxyl group, a carbonyl group, or an epoxy is used. Polarity having a group, acid hydride, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanic acid ester, amino group, imide group, oxazoline group, thiol group, etc. as polar groups It can be a polymer or copolymer of a group-containing compound.

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

Examples of maleic acid-modified styrene-based copolymers include maleic anhydride-modified SEBS. Examples of the maleic acid-modified olefin resin 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-based copolymer is preferably 0.1 to 20% by mass, for example.

Examples of commercially available compatible agents (C) include Bond First 2C, E, 2B, 7B, 7L, 7M, VC40 (manufactured by Sumitomo Chemical Co., Ltd.), Clayton FG1901, FG1924 (Clayton Polymer Japan Co., Ltd.). ), Tough Tech M1911, M1913, M1943, MP10 (manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like.

When the resin composition of the present invention contains the compatibilizer (C), the content of the compatibilizer (C) is 100 parts by mass in total of the component (A), the component (B) and the component (C). On the other hand, it is preferably 0.1 to 20% by mass, and more preferably 1 to 15% by mass. When the content of the compatibility agent (C) is 0.1% by mass or more, the compatibility between the engineering plastic (A) and the thermoplastic elastomer (B) can be further enhanced without impairing the moldability. When the content of the compatibilizer (C) is 20% by mass or less, the heat-resistant deformability is not easily impaired.

The resin composition of the present invention is, 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 object of the present invention is not impaired. (Eg stearic acid, silicone oil, etc.), lubricants (polyethylene wax, etc.), colorants, pigments, inorganic fillers (eg alumina, talc, calcium carbonate, mica, valastenite, clay), flame retardants (eg magnesium hydroxide, etc.) (Aluminum hydroxide), a foaming agent (for example, organic or inorganic) may be further contained.

2. 2. Method for Producing Resin Composition The resin composition of the present invention can be produced by any method, for example, a step of obtaining a thermoplastic elastomer (B) by the above-mentioned method, and the obtained thermoplastic elastomer (B). It can be manufactured through a step of mixing the engineering plastic (A) with a known method. After the above mixing, the mixture may be further melt-kneaded using an extruder.

The optional cross-linking aid or compatibilizer (C) may be mixed with any of the components in advance, or the copolymer rubber (BI) and the ethylene / unsaturated carboxylic acid copolymer ( It may be added when dynamically cross-linking B-II) or when mixing the thermoplastic elastomer (B) and the engineering plastic (A).

3. 3. Molded bodies and their uses The molded bodies obtained by molding the resin composition of the present invention can be used for various purposes, such as automobile parts, building material parts, sports goods, medical equipment parts, industrial parts, and the like. It is useful as a molded product of.

Among them, the molded body obtained from the resin composition of the present invention has good moldability and impact resistance, and therefore, a hollow molded body (industrial tube), a specific molding method (blow molding, two-color molding, etc.), etc. ) Is suitable for the molded product.

<Hollow molded body (industrial tube)>
Industrial tubes include at least a layer containing the resin composition described above. Industrial tube means a tube used especially for industrial equipment. Examples of industrial tubes include tubes through which fluids (fuel, solvent, chemicals, gas, etc.) required for industrial equipment such as vehicles (eg automobiles), pneumatic / hydraulic equipment, painting equipment, medical equipment, etc. are passed. In particular, it is very useful in applications such as vehicle piping tubes (for example, fuel system tubes, intake system tubes, cooling system tubes), pneumatic tubes, hydraulic tubes, paint spray tubes, medical tubes (for example, catheters) and the like.

<Molded product obtained by injection molding, blow molding or two-color molding>
The molded product obtained by injection molding, blow molding or two-color molding can be widely used in various applications (for example, automobiles and electric products) in which such physical characteristics are required. Examples of molded bodies obtained by injection molding, blow molding or two-color molding include constant velocity joint boots, boot parts such as dust covers, oil seals, gaskets, packings, dust covers, valves, stoppers, precision seal rubber, weather strips. And so on. Of these, constant velocity joint boots for automobiles are preferable. As a method for manufacturing constant velocity joint boots for automobiles, known methods such as an injection molding method and a blow molding method (injection blow molding method, press blow molding method) can be adopted.

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

Hereinafter, the present invention will be described in more detail with reference to examples. These examples do not limit the scope of the invention to be construed.

1. 1. Material of resin composition <Engineering plastic (A)>
A-1: Aliphatic polyamide (nylon 6, manufactured by Toray Industries, Inc., Alamine CM1017, melting point: 225 ° C., MFR: 127 g / 10 minutes)

<Thermoplastic elastomer (B)>
The following thermoplastic elastomers (B-1) to (B-3) were prepared as the thermoplastic elastomer (B).

(Preparation of Thermoplastic Elastomer (B-1))
As ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI), ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (ethylene content 65% by mass, diene content 4.6% by mass, [ η] = 2.4 dl / g) in 55% by mass, as an ethylene / unsaturated carboxylic acid copolymer (B-II), an ethylene / methacrylic acid copolymer (trade name: Nuclel N035C (trade name), Mitsui / Duponpoly). Made by Chemicals, Density (JIS K 7112: 1999): 940 kg / m ³ , Melting point: 86 ° C., Acid content: 10% by mass, MFR (JIS K 7210: 1999 (190 ° C., 2.16 kg load) 35 g / 10 , 40% by mass, and flake-shaped brominated alkylphenol formaldehyde resin (manufactured by Taoka Chemical Industry Co., Ltd., trade name: Tuckyrol 250-III) as a phenol resin-based cross-linking agent (B-III) is stirred with a Henshell mixer for 10 seconds. Premixed 5% by mass of the powdered polymer and a small amount of zinc oxide 2 types (manufactured by Hakusui Tech Co., Ltd.) as a cross-linking aid, and this is used as a twin-screw extruder (manufactured by Nippon Steel Works Co., Ltd., TEX-30). ) Was melt-kneaded at a cylinder temperature of 200 ° C. and a screw rotation speed of 300 rpm. Strands extruded from this twin-screw extruder were cut to obtain pellets of a thermoplastic elastomer (B-1).

(Preparation of Thermoplastic Elastomers (B-2) and (B-3))
Thermoplastic except that the mass ratio of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI) and the ethylene / unsaturated carboxylic acid copolymer (B-II) was changed as shown in Table 1. Thermoplastic elastomers (B-2) and (B-3) were obtained in the same manner as the elastomer (B-1).

<Comparative resin (b)>
The following comparative resins (b-1) to (b-3) were prepared as the comparative resin (b).

(Preparation of comparative resin (b-1))
In a glass flask fully substituted with nitrogen, 0.63 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was placed, and 1.57 ml of a toluene solution of methylaminoxane (Al; 0.13 mmol / liter) was added. , And 2.43 ml of toluene were added to obtain a catalytic solution.
Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a stainless steel autoclave having an internal volume of 2 liters sufficiently substituted with nitrogen, and the temperature in the system was raised to 80 ° C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml (0.0005 mmol as Zr) of the catalyst solution prepared above were press-fitted into the system with ethylene to initiate a polymerization reaction. The total pressure was maintained at 8.0 kg / cm ² -G by continuously supplying ethylene, and the mixture was polymerized at 80 ° C. for 30 minutes.
After introducing a small amount of ethanol into the system to terminate the polymerization of the polymer, unreacted ethylene was purged. The obtained solution was poured into a large excess of methanol to precipitate a white solid. This white solid was recovered by filtration and dried under reduced pressure overnight to obtain a white solid (ethylene 1-butene copolymer). The density of the obtained ethylene / 1-butene copolymer is 0.865 g / cm3, the MFR (ASTMD1238 standard, 190 ° C.: 2160 g load) is 0.5 g / 10 minutes, and the 1-butene structural unit content is 4 mol%. was.
To 100 parts by mass of the obtained ethylene / 1-butene copolymer, 1.0 part by mass of maleic anhydride and 0.04 part by mass of peroxide (perhexin 25B, manufactured by Nippon Oil & Fats Co., Ltd.) were mixed. .. The obtained mixture was melt-grafted and modified with a uniaxial extruder set at 230 ° C. to obtain a modified ethylene / 1-butene copolymer (b-1).
The amount of maleic anhydride graft modification of the obtained modified ethylene / 1-butene copolymer (b-1) was 0.98% by mass. The ultimate viscosity [η] measured in a 135 ° C. decalin solution was 1.90 dl / g.

(Preparation of modified ethylene / 1-butene copolymer (b-2))
Modified ethylene / 1-butene copolymer (b-) in the same manner as the modified ethylene / 1-butene copolymer (b-1) except that 1.0 part by mass of maleic anhydride was changed to 0.5 parts by mass. 2) was obtained.
The amount of maleic anhydride graft modification of the obtained modified ethylene / 1-butene copolymer (b-2) was 0.47% by mass, and the ultimate viscosity [η] measured in a decalin solution at 135 ° C. was 1.80 dl. It was / g.

(Preparation of mixture (b-3))
Ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI) and ethylene / unsaturated carboxylic acid copolymer (B-) without adding a phenol resin-based cross-linking agent (B-III) and a cross-linking aid. The mixture (b-3) is obtained in the same manner as the thermoplastic elastomer (B-1) except that the mass ratio of II) is (BI) :( B-II) = 11: 9. rice field.

2. 2. Preparation of resin composition <Examples 1 to 3>
The above-mentioned aliphatic polyamide (A-1) as the engineering plastic (A) and the thermoplastic elastomer shown in Table 2 as the thermoplastic elastomer (B) are premixed at the composition ratio shown in Table 2, and the two are mixed. It was supplied to a shaft extruder (manufactured by Japan Steel Works, Ltd., TEX-30) and melt-kneaded at a cylinder temperature of 280 ° C. and a screw rotation speed of 300 rpm. Strands extruded from this twin-screw extruder were cut to obtain pellets of the resin composition.

<Comparative Examples 1 to 3>
Pellets of the resin composition were obtained in the same manner as in Example 1 except that the comparative resin shown in Table 2 was used instead of the thermoplastic elastomer (B).

In Examples 1 to 3 and Comparative Examples 1 to 3, the bending characteristics (bending strength / flexural modulus), deflection temperature under load, impact strength and injection flow length of the resin composition were evaluated by the following methods.

(Bending strength / flexural modulus)
The obtained resin composition was injection-molded under the following molding conditions to prepare a test piece having a length of 127 mm, a width of 12.7 mm and a thickness of 3.2 mm.
Molding machine: SG50M3 manufactured by Sumitomo Heavy Industries, Ltd.
Molding machine cylinder temperature: Melting point (Tm) of aliphatic polyamide (A-1) + 15 ° C.
Mold temperature: 50 ° C
The obtained test piece was left at a temperature of 23 ° C. in a nitrogen atmosphere for 24 hours. Next, a bending test was performed at a bending tester AB5 manufactured by NTESCO, a span of 51 mm, and a bending speed of 12.7 mm / min in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. Was measured.

(Deflection temperature under load)
The obtained resin composition was injection-molded under the following molding conditions to prepare a test piece having a thickness of 3.2 mm.
Molding machine: Sodick Plastic Co., Ltd., Tupearl TR40S3A
Molding machine cylinder temperature: Melting point (Tm) of aliphatic polyamide (A-1) + 15 ° C.
Mold temperature: Glass transition temperature (Tg) of aliphatic polyamide (A-1) + 20 ° C.
The obtained test piece was fixed at a span of 100 mm and a pressure of 0.45 MPa was applied from 35 ° C. at a heating rate of 120 ° C./hr. Then, the temperature when the amount of deflection became 0.254 mm was defined as the deflection temperature under load.

(IZOD impact strength)
The obtained resin composition was injection-molded under the following molding conditions to prepare a test piece with a notch having a thickness of 3.2 mm.
Molding machine: SG50M3 manufactured by Sumitomo Heavy Industries, Ltd.
Molding machine cylinder temperature: Melting point (Tm) of aliphatic polyamide (A-1) + 15 ° C.
Mold temperature: 50 ° C
The IZOD impact strength of the obtained test piece was measured in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% in accordance with ASTMD256.

(Injection flow length)
The resin compositions of Examples and Comparative Examples were injected using a bar flow mold having a width of 10 mm and a thickness of 0.5 mm under the following conditions, and the flow length (mm) of the resin composition in the mold was measured. .. The longer the flow length, the better the injection fluidity.
Molding machine: Sodick plastic, Tupearl TR40S3A
Injection set pressure: 2000kg / cm ²
Molding machine cylinder temperature: Melting point (Tm) of aliphatic polyamide (A-1) + 15 ° C.
Mold temperature: 50 ° C

The evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3 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) is used. The resin compositions of Examples 1 to 3 containing the modified olefin polymer (b-1) or (b-2), the copolymer rubber (BI) and the ethylene / unsaturated carboxylic acid copolymer (B) are included. It can be seen that it has a higher impact strength than the resin compositions of Comparative Examples 1 to 3 containing the mixture of -II).

According to the present invention, it is possible to provide a resin composition and a molded product that can impart a molded product having particularly excellent impact resistance, and a method for producing the resin composition.

Claims (6)

60 to 95 parts by mass of the aliphatic polyamide (A) having a melting point (Tm) of 150 to 290 ° C. measured by a differential scanning calorimeter (DSC).
It contains 5 to 40 parts by mass of the thermoplastic elastomer (B) (however, the total of (A) and (B) 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 one or more carbon-carbon double bonds in one molecule. Containing ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI),
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,
It is a cross-linked product of a composition containing a phenol resin-based cross-linking agent (B-III).
The content of the structural unit 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. The aliphatic polyamide (A) is
(I) A structural unit derived from a dicarboxylic acid and a structural unit derived from a diamine are included, and the structural unit derived from the dicarboxylic acid is 80 with respect to a total of 100 mol% of the structural unit derived from the dicarboxylic acid. It contains a structural unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms of mol% or more.
The structural unit derived from the diamine is an aliphatic polyamide containing a structural unit derived from an aliphatic diamine having 80 mol% or more of carbon atoms 4 to 12 with respect to a total of 100 mol% of the structural units derived from the diamine. An aliphatic polyamide which is present or contains (ii) a structural unit derived from lactam or aminocarboxylic acid having 6 to 12 carbon atoms.
The resin composition according to claim 1 or 2. The thermoplastic elastomer (B) is the ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI), the ethylene / unsaturated carboxylic acid copolymer (B-II), and the phenol resin system. 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)
The ethylene / unsaturated carboxylic acid copolymer (B-II) was added to 15 to 60 parts by mass.
The phenol resin-based cross-linking agent (B-III) is contained in an amount of 1 to 10 parts by mass.
The resin composition according to any one of claims 1 to 3. A molded product obtained from the resin composition according to any one of claims 1 to 4. 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. Containing ethylene / α-olefin / non-conjugated polyene copolymer rubber (BI),
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 phenol resin-based cross-linking agent (B-III) to obtain a thermoplastic elastomer (B),
A step of mixing the thermoplastic elastomer (B) with 60 to 95 parts by mass of the aliphatic polyamide (A) having a melting point (Tm) of 150 to 290 ° C. measured by a differential scanning calorimeter (DSC) (however). , (A) and (B) are 100 parts by mass)
including,
A method for producing a resin composition.