JP6787133B2 - Polyamide composition and molded articles made from it - Google Patents

Description

The present invention relates to a polyamide composition and a molded article comprising the polyamide composition.

Polyamide resins are used in a wide range of applications because they have excellent properties. Inorganic reinforcing materials, especially polyamide resins containing glass fibers, have significantly improved rigidity, strength, heat resistance, etc., and are also used in applications that require painting or plating. However, by containing glass fiber or the like, the appearance such as surface roughness and mirror surface gloss of the finished molded product may be deteriorated, and the appearance may be further deteriorated by painting or the like.
For example, Japanese Patent Application Laid-Open No. 61-60861 and Japanese Patent Application Laid-Open No. 2008-95066 propose that a crystalline polyamide resin contains an amorphous resin or a deformed glass fiber as a method for improving the appearance.

Special Publication No. 61-60861 Japanese Unexamined Patent Publication No. 2008-95066

However, there is a demand for an improved appearance having a smaller surface roughness or the like than the appearance such as the surface roughness of the molded product obtained by these methods.

An object of the present invention is to provide a polyamide resin composition having a smaller surface roughness in a molded product and a molded product comprising the polyamide resin composition.

A composition (X) containing an aliphatic polyamide resin (A-1), an aromatic polyamide resin (A-2) and a glass fiber (B), which are melt-kneaded,
It has been found that a polyamide resin composition further added with a polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of the polyamide resin (A-1) has a smaller surface roughness when made into a molded product. It was.

That is, the present invention includes the following aspects.
The first aspect is the above-mentioned polyamide in a composition (X) containing an aliphatic polyamide resin (A-1), an aromatic polyamide resin (A-2) and a glass fiber (B), which are melt-kneaded. This is a polyamide resin composition further added with a polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of the resin (A-1).
The second aspect is a molded product made of the polyamide resin composition.
The third aspect is to obtain the composition (X) by melt-kneading the aliphatic polyamide resin (A-1), the aromatic polyamide resin (A-2) and the glass fiber (B), and the composition (X). ) And a polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of the aliphatic polyamide resin (A-1), and a method for producing a polyamide resin composition containing the mixture.

According to the present invention, it is possible to provide a polyamide resin composition having a smaller surface roughness in a molded product and a molded product made of the same.

In the present specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. To do.

The polyamide resin composition of the present invention contains an aliphatic polyamide resin (A-1), an aromatic polyamide resin (A-2) and a glass fiber (B), and these are melt-kneaded into a composition (X). , Polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of the polyamide resin (A-1) is further added. A molded product produced by using such a polyamide resin composition has a smaller surface roughness and has excellent surface gloss.

[Aliphatic polyamide (A-1)]
The aliphatic polyamide (A-1) has an amide bond (-CONH-) in the main chain and is made from the aliphatic polyamide structural unit lactam, aminocarboxylic acid, or aliphatic diamine and aliphatic dicarboxylic acid. , Melt polymerization, solution polymerization, solid phase polymerization and other known methods to polymerize or copolymerize.
Examples of lactam include caprolactam, enantractum, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like, and examples of aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid and 11 -Aminoundecanoic acid, 12-aminododecanoic acid and the like can be mentioned. These can be used alone or in combination of two or more.

As the aliphatic diamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptandiamine, 1, 8-octane diamine, 1,9-nonan diamine, 1,10-decane diamine, 1,11-undecane diamine, 1,12-dodecane diamine, 1,13-tridecane diamine, 1,14-tetradecane diamine, 1,15 -Pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecandiamine, 1,19-nonadecandiamine, 1,20-eicosandiamine, 2-methyl-1,5- Pentandiamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1, Examples thereof include 6-hexanediamine and 5-methyl-1,9-nonanediamine. These can be used alone or in combination of two or more.

Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. Examples thereof include pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eikosandioic acid. These can be used alone or in combination of two or more.

Examples of the aliphatic polyamide (A-1) include polycaproamide (polyamide 6), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyethylene adipamide (polyamide 26), and polytetramethylene succinamide. (Polyamide 44), Polytetramethylene Glutamide (Polyamide 45), Polytetramethylene adipamide (Polyamide 46), Polytetramethylene sveramide (Polyamide 48), Polytetramethylene azelamide (Polyamide 49), Polytetramethylenese Bacamide (polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamid (polyamide 55), polypentamethylene adipamide (polyamide 56), poly Pentamethylene sveramide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64) , Polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sveramide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 69) 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylenetetradecamide (polyamide 614), polyhexamethylene hexadecamide (polyamide 616), polyhexamethylene octadecamide (polyamide 618), polynonamethylene azi. Pamide (polyamide 96), polynonamethylene sveramide (polyamide 98), polynonamethylene azelamide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydeca Methylene adipamide (polyamide 106), polydecamethylene sveramide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), Polydodecamethylene adipamide (polyamide 126), polydodecamethylene sveramide (polyamide 128), polydodecamethylene azelamide (polyamide 12) 9), homopolymers such as polydodecamethylene sebacamide (polyamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and copolymers using several kinds of raw material monomers forming these can be mentioned.

Among these, from the viewpoints of molding processability, mechanical properties, and heat resistance, polyamide 6, polyamide 12, polyamide 66, and polyamide 6/66 copolymer (polyamide 6 and polyamide 66 copolymer, hereinafter, the copolymer is (Similarly described), Polyamide 6/69 copolymer, Polyamide 6/610 copolymer, Polyamide 6/611 copolymer, Polyamide 6/612 copolymer, Polyamide 6/12 copolymer and Polyamide 6/66 / It is preferably one or more selected from the group consisting of 12 copolymers, and is preferably polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer, polyamide 6/12 copolymer and polyamide 6/66/12. It is more preferably one or more selected from the group consisting of copolymers, and further preferably one or more selected from the group consisting of polyamide 6, polyamide 66 and polyamide 6/66 copolymer, and molding processing. From the viewpoint of properties, polyamide 6 is particularly preferable.

Examples of the apparatus for producing the aliphatic polyamide (A-1) include a batch type reaction kettle, a single-tank or multi-tank continuous reaction device, a tubular continuous reaction device, a uniaxial kneading extruder, a twin-screw kneading extruder, and the like. Known polyamide production equipment such as a kneading reaction extruder can be mentioned. As a polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure, and pressurizing operations. These polymerization methods can be used alone or in combination as appropriate.

Further, it is desirable that the relative viscosity of the aliphatic polyamide (A) measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. in accordance with JIS K-6920 ensures mechanical properties. From the viewpoint of ensuring moldability, it is preferably 1.5 or more and 5.0 or less, more preferably 1.5 or more and 4.5 or less, and preferably 1.5 or more and 3.0 or less. More preferably, it is more preferably 2.0 or more and 3.0 or less.

In the aliphatic polyamide (A-1), in order to obtain a polyamide having an arbitrary molecular weight, an arbitrary terminal amino group concentration, and an arbitrary carboxy concentration, the polyamide raw material is melt-polymerized in the presence of amines or carboxylic acids. It may be produced by polymerization or copolymerization by a known method such as solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines or carboxylic acids after polymerization. As described above, amines or carboxylic acids can be added at any stage during polymerization, or at any stage during melt-kneading after polymerization, but when surface properties are taken into consideration, they should be added at the stage during polymerization. Is preferable.

Examples of the amines include monoamines, diamines, triamines and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid may be added, if necessary, as long as they do not deviate from the above-mentioned terminal group concentration conditions. These amines and carboxylic acids may be added at the same time or separately. Further, as the amines and carboxylic acids exemplified below, one kind or two or more kinds can be used.

Specific examples of the monoamine to be added include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine and tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecyleneamine, eicosylamine, docosylamine and other aliphatic monoamines; cyclohexylamine, methylcyclohexylamine and other alicyclic monoamines; benzylamine, β- Aromatic monoamines such as phenylmethylamine; N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, N, N-dihexylamine, N, N-dioctyl Symmetrical secondary amines such as amines; N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecyl Examples thereof include mixed secondary amines such as amines, N-ethyl-N-octadecylamines, N-propyl-N-hexadecylamines and N-propyl-N-benzylamines. These can be used alone or in combination of two or more.

Specific examples of the diamine to be added include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptanediamine. , 1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-Pentadecanediamine, 1,16-Hexadecandiamine, 1,17-Heptadecandiamine, 1,18-Octadecanediamine, 2-Methyl-1,5-pentanediamine, 3-Methyl-1,5-pentanediamine , 2-Methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9- Aliper diamines such as nonandiamine; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane , Bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-Amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornan, 2,6-bis (aminomethyl) norbornan , 3,8-Bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane and other alicyclic diamines; and aromatic diamines such as m-xylylene diamine and p-xylylene diamine Can be mentioned. These can be used alone or in combination of two or more.

Specific examples of the triamine to be added include 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, 1,2,4-triaminobutane, 1,2,3,4-. Tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5- Triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetraminobenzene, 1,2,4-triaminonaphthalene, 2,5,7 Examples thereof include 1,4,5,8-tetraminonaphthalene such as −triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene and the like. These can be used alone or in combination of two or more.

The polyamine to be added may be a compound having a plurality of primary amino groups (-NH ₂ ) and / or secondary amino groups (-NH-), for example, polyalkyleneimine, polyalkylene polyamine, polyvinylamine, polyallylamine and the like. Can be mentioned. The amino group with active hydrogen is the reaction site for polyamines.

Polyalkyleneimine is produced by a method of ion-polymerizing an alkyleneimine such as ethyleneimine or propyleneimine, or a method of polymerizing an alkyloxazoline and then partially or completely hydrolyzing the polymer. Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and a reaction product of ethylenediamine and a polyfunctional compound. Polyvinylamine can be obtained, for example, by polymerizing N-vinylformamide to obtain poly (N-vinylformamide), and then partially or completely hydrolyzing the polymer with an acid such as hydrochloric acid. Polyallylamine is generally obtained by polymerizing a hydrochloride salt of an allylamine monomer and then removing hydrochloric acid. These can be used alone or in combination of two or more. Among these, polyalkyleneimine is preferable.

The polyalkyleneimine is one or 2 of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. Examples thereof include homopolymers and copolymers obtained by polymerizing seeds or more by a conventional method. Among these, polyethyleneimine is more preferable. Polyalkyleneimine is obtained by ring-opening polymerization of alkyleneimine as a raw material, and branched polyalkyleneimine containing primary amine, secondary amine, and tertiary amine, or alkyloxazoline as a raw material, which is polymerized. It may be either a linear polyalkyleneimine containing only the primary amine and the secondary amine obtained by the above, or a three-dimensionally crosslinked structure. Further, it may contain ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and the like. Polyalkyleneimines are usually derived from the reactivity of active hydrogen atoms on the contained nitrogen atoms, and in addition to tertiary amino groups, primary amino groups and secondary amino groups (imino) having active hydrogen atoms. Group).

The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 or more and 3,000, more preferably 8 or more and 1,500 or less, and further preferably 11 or more and 500 or less. .. The number average molecular weight of polyalkyleneimine is preferably 100 or more and 20,000 or less, more preferably 200 or more and 10,000 or less, and further preferably 500 or more and 8,000 or less.

On the other hand, as the carboxylic acids to be added, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, Adicyclic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, araquinic acid, behenic acid and erucic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; , Ethylbenzoic acid, aromatic monocarboxylic acids such as phenylacetic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid , Hexadecenedioic acid, octadecanedioic acid, octadecenedioic acid, eicosandioic acid, eicosendioic acid, docosanedioic acid, diglycolic acid, 2,2,4-trimethyladiponic acid, 2,4,4-trimethyladipic acid, etc. Aliphatic dicarboxylic acid; alicyclic dicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, norbornandicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, m-xylylene dicarboxylic acid, p- Aromatic dicarboxylic acids such as xylylene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid; 1,2,4-butanetricarboxylic acid, 1,3,5 Examples thereof include tricarboxylic acids such as -pentanetricarboxylic acid, 1,2,6-hexanetricarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid and trimesic acid. These can be used alone or in combination of two or more.

The amount of amines and carboxylic acids to be added is appropriately determined by a known method in consideration of the terminal amino group concentration, terminal carboxyl group concentration, and relative viscosity of the terminally modified aliphatic polyamide to be produced.

[Aromatic polyamide resin (A-2)]
Examples of the aromatic polyamide resin (A-2) include polymethoxylylen adipamide (polyamide MXD6), polymethoxylylence veramide (polyamide MXD8), polymethoxylylene azeramide (polyamide MXD9), and polymethoxylylene sevacamamide. (Polyamide MXD10), Polymethaxylylene dedecamide (Polyamide MXD12), Polymethoxylylene terephthalamide (Polyamide MXDT), Polymethoxylylene isophthalamide (Polyamide MXDI), Polymethoxylylene hexahydroterephthalamide (Polyamide MXDT (H)) )), Polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), polyparaxylylene azelamide (polyamide PXD9), polyparaxili Lensebacamide (polyamide PXD10), polyparaxylylene dedecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydro Telephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA) ), Polymetaphenylene isophthalamide (PMIA), Poly (2,6-naphthalenedimethylene adipamide) (Polyamide 2,6-BAN6), Poly (2,6-naphthalenedimethylene sveramide) (Polyamide 2, 6-BAN8), poly (2,6-naphthalenedimethylene azelamide) (polyamide 2,6-BAN9), poly (2,6-naphthalenedimethylene sebacamide) (polyamide 2,6-BAN10), poly (polyamide 2,6-BAN10) 2,6-naphthalenedimethylene dodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalenedimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalenedimethylene) Isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalenedimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalenedimethylenenaphthal) Lamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedi) Methylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethyleneisophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylenehexahydroterephthalamide) ) (Polyamide 1,3-BACT (H)), Poly (1,3-Cyclohexanedimethylenenaphthalamide) (Polyamide 1,3-BACN), Poly (1,4-Cyclohexanedimethyleneterephthalamide) (Polyamide 1) , 4-BACT), Poly (1,4-Cyclohexanedimethyleneisophthalamide) (Polyamide 1,4-BACI), Poly (1,4-Cyclohexanedimethylenehexahydroterephthalamide) (Polyamide 1,4-BACT) (H)), Poly (1,4-cyclohexanedimethylenenaphthalamide) (Polyamide 1,4-BACN), Poly (4,4'-methylenebiscyclohexylene adipamide) (Polyamide PACM6), Poly (4, 4'-Methylenebiscyclohexylene veramide) (polyamide PACM8), poly (4,5'-methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,4'-methylenebiscyclohexylene sebacamide) ( Polyamide PACM10), poly (4,5'-methylenebiscyclohexylenedodecamide) (polyamide PACM12), poly (4,5'-methylenebiscyclohexylenetetradecamide) (polyamide PACM14), poly (4,4'- Methylenebiscyclohexylene hexadecamide) (polyamide PACM16), poly (4,5'-methylenebiscyclohexylene octadecamide) (polyamide PACM18), poly (4,4'-methylenebiscyclohexylene terephthalamide) (polyamide) PACMT), Poly (4,5'-methylenebiscyclohexylene isophthalamide) (Polyamide PACMI), Poly (4,4'-Methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), Poly (Polyamide PACMT (H)) 4,4'-Methylenebiscyclohexylene naphthalamide) (polyamide PACMN), poly (4,5'-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), poly (4,4'-methylenebis (2) -Methyl-cyclohexylene) sveramide) (polyamide MACM8), poly (4,5'-methylenebis (2-methyl-cyclohexylene) azelamide) (po Riamide MACM9), poly (4,4'-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,54'-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), Poly (4,4'-methylenebis (2-methyl-cyclohexylene) tetradecamide) (polyamide MACM14), poly (4,4'-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4, 4'-Methylenebis (2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,5'-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,5'-methylenebis) (2-Methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,5'-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4) '-Methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide MACMN), poly (4,4'-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4'-propylene biscyclohexylene sve Lamide) (Polyamide PACP8), Poly (4,4'-propylene biscyclohexylene azelamide) (Polyamide PACP9), Poly (4,4'-propylene biscyclohexylene sebacamide) (Polyamide PACP10), Poly (4, 4'-propylene biscyclohexylenedodecamide) (polyamide PACP12), poly (4,4'-propylene biscyclohexylene tetradecamide) (polyamide PACP14), poly (4,5'-propylene biscyclohexylene hexadecamide) (Polyamide PACP16), Poly (4,4'-propylene biscyclohexylene octadecamide) (Polyamide PACP18), Poly (4,4'-propylene biscyclohexylene terephthalamide) (Polyamide PACPT), Poly (4,4) '-Propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4'-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4'-propylene biscyclohex Sirenna phthalamide) (Poly Amid PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorone sveramide (polyamide IPD8), polyisophorone azelamide (polyamide IPD9), polyisophorone sebacamide (polyamide IPD10), polyisophorondodecamide (polyamide IPD12) , Polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophoron naphthalamide (polyamide IPDN), polytetramethylene terephthal. Ramide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylenenaphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 4N) Polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T) ), Polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylenenaphthalamide (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (Polyamide M5T), Poly (2-Methylpentamethyleneisophthalamide) (Polyamide M5I), Poly (2-Methylpentamethylenehexahydroterephthalamide) (Polyamide M5T (H)), Poly (2-Methylpentamethylenenaphthal) Ramide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9T (H)) Polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethyleneisophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) ( Polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polya) Mid TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylenenaphthalamide (polyamide TMHN), polydecamethylene terephthalamide (Polyamide 10T), Polydecamethylene isophthalamide (Polyamide 10I), Polydecamethylene hexahydroterephthalamide (Polyamide 10T (H)), Polydecamethylene naphthalamide (Polyamide 10N), Polyundecamethylene terephthalamide (Polyamide 10N) Polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (Polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), and raw material monomers for these polyamides. Examples thereof include a copolymer using several kinds. These can be used alone or in combination of two or more.

Among these, from the viewpoint of molding processability, one or more selected from the group consisting of polyamide 6T, polyamide 9T, polyamide 10T, polyamide 11T, polyamide 12T, polyamide IPD6, polyamide 6T / 6I and polyamide MXD6 is preferable, and polyamide 6T / 6I is more preferable.

According to ISO1133, when measured at a temperature of 275 ° C. and a weight of 5 kg, the MVR of the aromatic polyamide resin (A-2) is 10 ml / from the viewpoint of making the surface roughness of the molded product smaller. 10 minutes or more is preferable, 20 ml / 10 minutes or more is more preferable, 50 ml / 10 minutes or more is further preferable, and 90 ml / 10 minutes or more is particularly preferable.

[Glass fiber (B)]
The glass fiber is not particularly limited, but one that has been converged with a converging agent is preferable from the viewpoint of improving the compatibility between the glass fiber and the polyamide resin. From the viewpoint of compatibility, the converging agent preferably contains urethane-based or acrylic-based, and these may be used in combination.

The glass fiber is preferably surface-treated with a surface treatment agent from the viewpoint of enhancing the dispersibility and adhesion in the polyamide resin. Examples of the surface treatment agent include a silane compound, a chromium compound, a titanium compound and the like, and a silane compound and / or a titanium compound surface treatment agent is preferable.

As the surface treatment agent for the silane compound, an aminosilane-based coupling agent having excellent adhesion to the converging agent is preferable, and for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ. -Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminodithiopropyltrihydroxysilane, γ- (Polyethyleneamino) propyltrimethoxysilane, N-β- (aminopropyl) -γ-aminopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) -ethylenediamine, γ-dibutylaminopropyltrimethoxysilane, etc. Be done. These can be used alone or in combination of two or more.

Surface treatment agents for titanium compounds include isopropyltriisostearoyl titanate, isopropyltri (N-aminoethyl) titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraisopropyltitanate, and tetra. Butyl titanate, tetraoctylbis (ditridecylphosphite) titanate, isopropyltrioctanoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltri (dioctylphosphate) titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyldimethacrylic isostearoyl titanate , Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, isopropyltricylphenyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, isopropylisostearoyl diacrylic titanate and the like. .. These can be used alone or in combination of two or more.

Among these, at least selected from the group consisting of N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane and γ-aminopropyltriethoxysilane. One type is preferable.

The glass fiber is a glass fiber having a circular cross section perpendicular to the length direction and / or a glass fiber having a non-circular cross section having a cross section perpendicular to the length direction. The weight average fiber length of the glass fiber having a circular cross section perpendicular to the length direction is preferably 200 μm or more and 600 μm or less, preferably 200 μm or more and 550 μm or less, from the viewpoint of moldability of the composition and dimensional stability of the obtained molded product. More preferably, it is 300 μm or more and 500 μm or less.

The average fiber length of the glass fiber having a circular cross section is a polyamide resin composition or a solvent such as an acid or an alkali that does not dissolve the glass fiber in the molded product obtained by using the polyamide resin composition but dissolves the resin. It can be measured by dissolving it, removing it, and using image analysis software.

The image analysis software can be used without any particular limitation as long as it can measure the fiber length. One example is Mr. A, an image analysis software manufactured by Asahi Kasei Engineering Co., Ltd.

The average fiber diameter of the glass fiber having a circular cross section is not particularly limited, but is preferably 5 μm or more and 25 μm or less, more preferably 5 μm or more and 24 μm or less, and 6 μm or more and 23 μm from the viewpoint of dimensional stability and mechanical properties of the obtained molded product. The following is more preferable.

The average fiber diameter of glass fibers can be measured by JIS R3420.

The glass fiber having a circular cross section is preferably surface-treated with a surface treatment agent from the viewpoint of enhancing dispersibility and adhesion in the polyamide resin. Examples of the surface treatment agent include a silane compound, a chromium compound, a titanium compound and the like, and a silane compound and / or a titanium compound surface treatment agent is preferable.

For glass fibers having a non-circular cross section perpendicular to the length direction, the ratio of the major axis to the minor axis in the cross section perpendicular to the length direction is preferably 1.2 or more and 10 or less from the viewpoint of low warpage and mechanical properties. , 1.5 or more and 6 or less is more preferable, and 1.7 or more and 4.5 or less is further preferable. Here, the major axis is the distance when the straight line distance between any two points on the cross-sectional figure is maximized, and the minor axis intersects the cross-sectional figure among the straight lines orthogonal to the major axis. Take the one with the smallest distance between two points.

The major axis of the glass fiber having a non-circular cross section is preferably 2 μm or more and 100 μm or less, and the minor axis is preferably 1 μm or more and 20 μm or less.

The cross-sectional shape of the non-circular cross-sectional glass fiber is not particularly limited as long as it has a predetermined major axis to minor axis ratio, but is usually eyebrows, oval, semicircular, arcuate, rectangular, parallelogram. A quadrilateral or similar form thereof is used. In practical use, eyebrows, oval shapes, and rectangles are preferable from the viewpoints of fluidity, mechanical properties, and low warpage.

The preferred average fiber length in the polyamide resin composition of the non-circular cross-section glass fiber and the molded body and the measuring method thereof are the same as those of the circular cross-section glass fiber.

From the viewpoint of mechanical properties and moldability, glass fibers have a circular cross-section glass fiber having an average fiber diameter of 5 μm or more and 25 μm or less, and / or a ratio of major axis to minor axis in a cross section perpendicular to the length direction is 1.2. Glass fibers having a non-circular cross section of 10 or more are preferable.

[Composition (X)]
The composition (X) contains an aliphatic polyamide resin (A-1), an aromatic polyamide resin (A-2) and a glass fiber (B), and is a melt-kneaded product obtained by melt-kneading these. From the viewpoint of making the mixing with the polyamide resin (A-3) more uniform, the composition (X) is preferably in the form of powder such as powder or pellets.

The method of melt-kneading is not particularly limited, and is a usual method using a mixer such as a cylindrical mixer, a twin-screw extruder, a single-screw extruder, a multi-screw extruder, a bumper mixer, and a roll mixer. , A method using an extruder such as a kneader, a method of combining a mixer and an extruder, and the like. From the viewpoint of making the mixture of the aliphatic polyamide resin (A-1), the aromatic polyamide resin (A-2) and the glass fiber (B) more uniform, it is preferable to use a twin-screw extruder.

From the viewpoint of moldability, the content of the aromatic polyamide resin (A-2) is relative to the total of the composition (X) of the aliphatic polyamide resin (A-1) and the aromatic polyamide resin (A-2). However, it is preferably 5% by weight or more and 30% by weight or less, and more preferably 10% by weight or more and 20% by weight or less.
From the viewpoint of moldability, the total amount of the composition (X) preferably contains 20% by weight or more and 65% by weight or less of the aliphatic polyamide resin (A-1), and 23% by weight or more and 50% by weight or less. It is more preferable that the content is 25% by weight or more and 45% by weight or less.
From the viewpoint of molding processability and good appearance, the total amount of the composition (X) preferably contains 2% by weight or more and 20% by weight or less of the aromatic polyamide resin (A-2), and 3% by weight or more and 15% by weight or less. It is more preferable that it is contained in an amount of 4% by weight or more and 10% by weight or less.
The content ratio (A-2 / A-1) (% by weight) of the aromatic polyamide resin (A-2) to the aliphatic polyamide resin (A-1) in the composition (X) is 5 from the viewpoint of surface appearance. By weight% or more and 30% by weight or less is preferable, and 10% by weight or more and 20% by weight or less is more preferable.

In the total amount of the composition (X), from the viewpoint of mechanical properties, the glass fiber (B) is preferably 30% by weight or more and 70% by weight or less, more preferably 40% by weight or more and 70% by weight or less, and 45% by weight or more and 70% by weight or less. % Or less is more preferable.

From the viewpoint of material rigidity, 80% by weight or more and 100% by weight or less of the aliphatic polyamide resin (A-1), the aromatic polyamide resin (A-2) and the glass fiber (B) are contained in the total amount of the composition (X). Is more preferable, 90% by weight is 100% by weight or less, and 95% by weight or more and 100% by weight or less is further preferable.

The composition (X) contains various additives, modifiers, and reinforcing materials that are usually blended, for example, a heat stabilizer, an antioxidant, and an ultraviolet absorber, as long as the characteristics of the composition of the present invention are not impaired. , Weatherproofing agents, fillers, plasticizers, foaming agents, blocking inhibitors, tackifiers, sealing improvers, cloudproofing agents, mold release agents, cross-linking agents, foaming agents, flame retardants, colorants (pigments, dyes, etc.) ), Coupling agent, fluidity improver, talc and other inorganic compounds other than glass can be contained.

The composition (X) may contain a thermoplastic resin other than the polyamide resin as long as the characteristics of the polyamide resin composition are not impaired.

Examples of thermoplastic resins other than polyamide resins include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), and polypropylene. (PP), polybutene (PB), polymethylpentene (TPX), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic Acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer Polyolefin resins such as coalesced (EEA); polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), styrene / Butadiene copolymer (SBR), styrene / isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer Polystyrene resins such as coalescence (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS); carboxyl groups and salts thereof, acid anhydride groups, epoxys The above-mentioned polyolefin-based resin and polystyrene-based resin containing functional groups such as groups; polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene isophthalate) copolymer. (PET / PEI), Polytrimethylene terephthalate (PTT), Polycyclohexanedimethylene terephthalate (PCT), Polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN), Polyarylate (PAR), Liquid crystal polyester (LCP), Polyester resins such as polylactic acid (PLA) and polyglycolic acid (PGA); polyether resins such as polyacetal (POM) and polyphenylene ether (PPO); polysulfone (PSU), polyether sulfone (PESU), polyphenylsal Polysalphone such as phone (PPSU) Co-resins: Polythioether-based resins such as polyphenylene sulfide (PPS) and polythioethersalphon (PTES); polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK) , Polyetheretheretherketone (PEEEK), Polyetheretherketoneketone (PEEKK), Polyetherketoneketoneketone (PEKKK), Polyetherketoneetherketoneketone (PEKEKK) and other polyketone resins; Polyacrylonitrile (PAN), Poly Polynitrile resins such as methacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylnitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR), Polymethacrylate resins such as polymethyl methacrylate (PMMA) and ethyl polymethacrylate (PEMA); polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer , Polyvinyl resin such as vinylidene chloride / methyl acrylate copolymer; Cellulosic resin such as cellulose acetate and cellulose butyrate; Polyfluorovinylidene (PVDF), Polyfluorovinyl (PVF), Polytetrafluoroethylene (PTFE), Poly Chlorfluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / Hexafluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer ( Fluorine resins such as PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT); Polycarbonate resin such as PC); thermoplastic polyimide (TPI), polyether imitation De, Polyesterimide, Polyamideimide (PAI), Polyamide-imide and other polyimide resins; Thermoplastic polyurethane-based resins, polyamide elastomers, polyurethane elastomers, polyester elastomers and the like can be mentioned. These can be used alone or in combination of two or more.

Examples of the flow improving material include dicarboxylic acids and polyhydric alcohols, and polyhydric alcohols are preferable from the viewpoint of reactivity with the polyamide resin.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acid and aromatic dicarboxylic acid, and specific examples thereof include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, and terephthalic acid. ..

The polyhydric alcohol includes not only the polyhydric alcohol itself, but also a partial ester compound of the polyhydric alcohol and the fatty acid, and a partial ester compound of the alkylene oxide adduct of the polyhydric alcohol and the fatty acid. Specifically, ethylene glycol, propylene glycol, 1,3- / 1,4-butanediol, 2-methyl-1,3-propanediol, 1,2- / 1,3- / 1,4- / 1 , 5-Pentanediol, Neopentyl glycol, 1,6-Hexanediol, 2-Ethyl-2-methyl-1,3-Propanediol, 1,7-Heptanediol, 2-Methyl-2-propyl-1,3 -Propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecane Diol, Glycerin, Diglycerin, Triglycerin, Tetraglycerin, Polyglycerin, Trimethylol ethane, Trimethylol propane, Ditrimethylol propane, Tri- (Trimethylol propane), Trimethylol butane, Erythritol, Pentaerythritol, Dipentaerythritol, Tri Pentaerythritol, polypentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butantetrol, sorbitan, isosorbide, Examples thereof include sorbitol, adonitol, arabitol, xylitol, mannitol, xylose, arabinose, ribose, ramnorth, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose and meregitos.

Among these, from the viewpoint of improving fluidity, at least one selected from the group consisting of pentaerythritol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, dipentaerythritol, sorbitan and sorbitol is preferable, and pentaerythritol, At least one selected from the group consisting of polyglycerin, trimethylolethane, trimethylolpropane and dipentaerythritol is more preferable, and from the viewpoint of reduction of scattering and dispersibility during kneading and molding, pentaerythritol, polyglycerin and trimethylolerythritol are used. And at least one selected from the group consisting of dipentaerythritol is more preferred.

[Polyamide resin (A-3)]
The polyamide resin (A-3) used in the polyamide resin composition may be either an aliphatic polyamide resin or an aromatic polyamide resin, but in accordance with JIS K-6920, 96% sulfuric acid, polymer concentration 1%, 25 ° C. The relative viscosity of the polyamide resin (A-3) measured under the above conditions is smaller than the relative viscosity of the aliphatic polyamide resin (A-1). Otherwise, the polyamide resin composition of the present invention will not be effective. The difference in the relative viscosities of the aliphatic polyamide resin (A-1) and the polyamide resin (A-3) is the relative viscosity of (A-3) from the viewpoint of making the surface roughness of the molded product smaller. The value divided by the relative viscosity of A-1) is preferably 0.3 to 0.95, more preferably 0.3 to 0.9, and even more preferably 0.3 to 0.8. When it is 0.3 or more, the mechanical properties of the material tend to be further improved. When it is 0.95 or less, the fluidity tends to be good and the surface appearance tends to be further improved.
The form of the polyamide resin (A-3) is not particularly limited, and the polyamide resin (A-3) is preferably in the form of powder such as powder or pellets from the viewpoint of making the mixing with the composition (X) more uniform. ..

As the polyamide resin (A-3), an aliphatic polyamide resin is preferable from the viewpoint of molding processability, mechanical properties and heat resistance.

Among the aliphatic polyamide resins, the polyamide resin (A-3) is a polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymer (polyamide 6 and polyamide 66 copolymer,) from the viewpoint of molding processability. The copolymers are described in the same manner below), polyamide 6/69 copolymer, polyamide 6/610 copolymer, polyamide 6/611 copolymer, polyamide 6/612 copolymer, polyamide 6/12 copolymer. And more than one selected from the group consisting of polyamide 6/66/12 copolymers, polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 copolymers, polyamide 6/12 copolymers and It is more preferably one or more selected from the group consisting of the polyamide 6/66/12 copolymer, and more preferably one or more selected from the group consisting of the polyamide 6, polyamide 66 and the polyamide 6/66 copolymer. Is more preferable, and polyamide 6 and / or polyamide 66 is particularly preferable from the viewpoint of moldability.

[Polyamide resin composition]
The polyamide resin composition is formed by adding a polyamide resin (A-3) having a viscosity smaller than the relative viscosity of the aliphatic polyamide resin (A-1) to the composition (X). As the production method, a method of uniformly dry-blending the pellets to the above-mentioned mixing ratio using a tumbler or a mixer, and a melt-kneader of the dry-blended mixture described in the section of composition (X). A method of melt-kneading can be mentioned. From the viewpoint of more exerting the effect of the present invention, the dry blending method is preferable. That is, the polyamide resin composition is preferably a dry blend of the composition (X) which is a melt-kneaded product and the polyamide resin (A-3).

That is, the polyamide resin composition is obtained by melt-kneading the aliphatic polyamide resin (A-1), the aromatic polyamide resin (A-2) and the glass fiber (B) to obtain the composition (X). It is preferably produced by a production method including mixing (X) with a polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of the aliphatic polyamide resin (A-1). The composition (X) is obtained by melt-kneading the group polyamide resin (A-1), the aromatic polyamide resin (A-2) and the glass fiber (B), and the composition (X) and the aliphatic polyamide resin are obtained. More preferably, it is produced by a production method including dry blending with a polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of (A-1).

Since the polyamide resin composition is excellent in surface properties after molding, it can be suitably used for applications such as applying a thin film to the surface. Specific examples include painting and film printing. It is preferably used for painting. That is, the present invention contains a composition (X) containing an aliphatic polyamide resin (A-1), an aromatic polyamide resin (A-2) and a glass fiber (B), which are melt-kneaded, and the polyamide. This includes the use of a polyamide resin composition containing a polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of the resin (A-1) as a coating application.

From the viewpoint of reducing the surface roughness when formed into a molded product, the polyamide resin composition preferably contains 40% by weight or more and 98% by weight or less of the composition (X) with respect to the total amount of the polyamide resin composition. It is more preferable to contain 40% by weight or more and 80% by weight or less, and further preferably 40% by weight or more and 70% by weight or less.

From the viewpoint of reducing the surface roughness of the molded product, the polyamide resin composition may be contained in an amount of 2% by weight or more and 60% by weight or less of the polyamide resin (A-3) with respect to the total amount of the polyamide resin composition. It is more preferable to contain 10% by weight or more and 60% by weight or less, and further preferably 30% by weight or more and 60% by weight or less.

In the polyamide resin composition, the content ratio (A-3 / A-1) of the polyamide resin (A-3) to the aliphatic polyamide resin (A-1) is preferably 0.1 or more and 6.0 or less, and 0. More preferably, it is 6 or more and 5.5 or less. In the polyamide resin composition, the content ratio (A-3 / A-2) of the polyamide resin (A-3) to the aromatic polyamide resin (A-2) is preferably 0.5 or more and 45 or less, preferably 1.0 or more. 30 or less is more preferable. In the polyamide resin composition, the content ratio (A-3 / B) of the polyamide resin (A-3) to the glass fiber (B) is preferably 0.05 or more and 2.0 or less, and 0.1 or more and 2.0 or less. Is more preferable.

The polyamide resin composition contains various additives, modifiers, and reinforcing materials that are usually blended, for example, heat stabilizers, antioxidants, ultraviolet absorbers, weather resistant agents, fillers, and plasticizers, as long as their properties are not impaired. Agents, foaming agents, blocking inhibitors, tackifiers, sealing improvers, cloudproofing agents, mold release agents, cross-linking agents, foaming agents, flame retardants, colorants (pigments, dyes, etc.), coupling agents, fluidization It can contain an inorganic compound other than glass, such as a sex improver and talc. Additives may be included as pellets, so-called master batches, in which various additives are previously contained in a thermoplastic resin or the like, from the viewpoint of dispersibility in the obtained molded product and the characteristics exhibited in the obtained molded product. preferable.

[Molding]
The molded product is produced using a polyamide resin composition. A molded product made of a polyamide resin composition is molded by injection molding, extrusion molding, hollow molding, press molding, roll molding, foam molding, vacuum / pressure molding, stretch molding, etc., and a product having a good surface appearance is obtained. Injection molding is preferred from the viewpoint of ease of molding. That is, the present invention contains a composition (X) containing an aliphatic polyamide resin (A-1), an aromatic polyamide resin (A-2) and a glass fiber (B), which are melt-kneaded, and the polyamide. It includes the use in injection molding of a polyamide resin composition containing a polyamide resin (A-3) having a relative viscosity smaller than the relative viscosity of the resin (A-1).

Since the molded product made of the polyamide resin composition has excellent surface properties, it can be suitably used for applications such as applying a thin film to the surface. Specific examples include painting and film printing. It is preferably used for painting.

Specific examples of the molded product made of the polyamide resin composition include parts to be painted and the like among injection molded products, and from the viewpoint of design and material rigidity, interior and exterior parts of automobiles and two-wheeled vehicles. Exterior parts, frame parts for home appliances, housings for personal computers and cameras, etc. are preferable.

Examples and comparative examples are shown below, and the present invention will be specifically described, but the present invention is not limited thereto.

[Relative viscosity]
According to JIS K-6920, the measurement was carried out under the conditions of 96% sulfuric acid, a polymer concentration of 1%, and a temperature of 25 ° C.

[Molding]
In Examples and Comparative Examples, the obtained polyamide resin composition was subjected to 125 mm × 75 mm × 3 mm under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a resin flow rate of 200 mm / sec and 50 mm / sec in the mold. It was molded on a flat plate with an injection molding machine.
The obtained molded product (flat plate) was used for measuring surface roughness and gloss gloss.

[Surface roughness]
Using Handy Surf E-35B, a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd., the average roughness of the center line of the molded product under the condition of cutoff 0.8 mm and measurement length 4.0 mm in accordance with JIS B0601 standard. (Ra) was measured and evaluated as surface roughness.

[Gloss gloss]
Connect the digital variable angle gloss meter UGV-5K to the SM color computer SM-5 IS-2B manufactured by Suga Test Instruments Co., Ltd., and measure the gloss gloss at 60 ° according to JIS Z8741. It was measured.

[Materials used in Examples and Comparative Examples]
Aliphatic polyamide (A-1)
-Polyamide 6 (A-1-1) (hereinafter, may be referred to as A-1-1).
Add 0.5 kg of water to 20 kg of ε-caprolactam as a polymerization monomer in a 70 liter autoclave, replace the inside of the tank with nitrogen, heat to 100 ° C, and stir for 3 hours so that the pressure inside the tank becomes uniform at 1.0 MPa. did. Next, after releasing the pressure in the tank, polymerization was carried out at 260 ° C. for 3 hours to obtain a polyamide 6. The relative viscosity of the obtained A-1-1 was 1.95.

Polyamide 6 (A-1-2) (hereinafter, may be referred to as A-1-2).
Add 0.5 kg of water to 20 kg of ε-caprolactam as a polymerization monomer in a 70 liter autoclave, replace the inside of the tank with nitrogen, heat to 100 ° C, and stir for 3 hours so that the pressure inside the tank becomes uniform at 1.0 MPa. did. Next, after releasing the pressure in the tank, polymerization was carried out at 260 ° C. for 4 hours to obtain a polyamide 6. The relative viscosity of the obtained A-1-2 was 2.20.

-Polyamide 6 (A-1-3) (hereinafter, may be referred to as A-1-3)
Add 0.5 kg of water to 20 kg of ε-caprolactam as a polymerization monomer in a 70 liter autoclave, replace the inside of the tank with nitrogen, heat to 100 ° C, and stir for 3 hours so that the pressure inside the tank becomes uniform at 1.0 MPa. did. Next, after releasing the pressure in the tank, polymerization was carried out at 260 ° C. for 5 hours to obtain a polyamide 6. The relative viscosity of the obtained A-1-3 was 2.47.

Polyamide 6 (A-1-4) (hereinafter, may be referred to as A-1-4)
Add 0.5 kg of water to 20 kg of ε-caprolactam as a polymerization monomer in a 70 liter autoclave, replace the inside of the tank with nitrogen, heat to 100 ° C, and stir for 3 hours so that the pressure inside the tank becomes uniform at 1.0 MPa. did. Next, after releasing the pressure in the tank, polymerization was carried out at 260 ° C. for 6 hours to obtain a polyamide 6. The relative viscosity of the obtained A-1--4 was 2.64.

-Polyamide 6 (A-1-5) (hereinafter, may be referred to as A-1-5)
Add 0.5 kg of water to 20 kg of ε-caprolactam as a polymerization monomer in a 70 liter autoclave, replace the inside of the tank with nitrogen, heat to 100 ° C, and stir for 3 hours so that the pressure inside the tank becomes uniform at 1.0 MPa. did. Next, after releasing the pressure in the tank, polymerization was carried out at 260 ° C. for 8 hours to obtain a polyamide 6. The relative viscosity of the obtained A-1-5 was 3.35.

Aromatic polyamide resin (A-2)
-Polyamide 6T6I (A-2-1) (hereinafter, may be referred to as A-2-1).
As A-2-1, Grivory G16 of Ems-Chemie Japan Co., Ltd. was used. The MVR of A-2-1 was 100 ml / 10 minutes when measured under the conditions of a temperature of 275 ° C. and a load of 5 kg in accordance with ISO1133.

-Polyamide 6T6I (A-2-2) (hereinafter, may be referred to as A-2-2)
As A-2-2, Grivory G21 of Ems-Chemie Japan Co., Ltd. was used. The MVR of A-2-2 was 20 ml / 10 minutes when measured under the conditions of a temperature of 275 ° C. and a load of 5 kg in accordance with ISO1133.

Polyamide resin (A-3)
-Polyamide 6 (A-3-1) (hereinafter, may be referred to as A-3-1)
A-1-1 was used as A-3-1.
-Polyamide 6 (A-3-2) (hereinafter, may be referred to as A-3-2)
As A-3-2, A-1-2 was used.
-Polyamide 6 (A-3-3) (hereinafter, may be referred to as A-3-3)
As A-3-3, A-1--3 was used.
-Polyamide 6 (A-3-4) (hereinafter, may be referred to as A-3-4)
As A-3-4, A-1--4 was used.
-Polyamide 6 (A-3-5) (hereinafter, may be referred to as A-3-5)
A-1-5 was used as A-3-5.
All of the polyamide resins (A-3) were pelletized with a pelletizer and used.

Glass fiber (B)
-Glass fiber (B-1) (hereinafter sometimes referred to as B-1)
As B-1, ECS 03T-249 having a diameter of 13 μm, which is a glass fiber having a circular cross section perpendicular to the length direction of Nippon Electric Glass Co., Ltd., was used.

-Glass fiber (B-2) (hereinafter sometimes referred to as B-2)
As B-2, ECS 03T-747N having a diameter of 13 μm, which is a glass fiber having a circular cross section perpendicular to the length direction of Nippon Electric Glass Co., Ltd., was used.

-Glass fiber (B-3) (hereinafter sometimes referred to as B-3)
As B-3, CGS 3PA-820S, which is a glass fiber having a major axis and a minor axis of 28 μm and 7 μm in a cross section perpendicular to the length direction of Nitto Boseki Co., Ltd., a ratio of 4.0, and a deformed cross section, was used. ..

Composition (X)
-Composition (X-1) (hereinafter, may be referred to as X-1)
A-1-3 is 35% by weight, A-2-1 is 5% by weight, and B-1 is 60% by weight using a twin-screw extruder, melt-kneaded, and pelletized X-1 with a pelletizer. Got

-Composition (X-2) (hereinafter, may be referred to as X-2)
A-1-3 was melt-kneaded at a ratio of 25.5% by weight, A-2-2 at 4.5% by weight, and B-2 at a ratio of 70% by weight using a twin-screw extruder, and X was used in a pelletizer. -2 pellets were obtained.

-Composition (X-3) (hereinafter, may be referred to as X-3)
A-1-3 is 35% by weight, A-2-1 is 5% by weight, and B-3 is 60% by weight using a twin-screw extruder, melt-kneaded, and pelletized X-3 with a pelletizer. Got

-Composition (X-4) (hereinafter, may be referred to as X-4)
A-1-3 is 42% by weight, A-2-1 is 8% by weight, and B-3 is 50% by weight by melt-kneading using a twin-screw extruder and pelletizing X-4 with a pelletizer. Got

-Composition (X-5) (hereinafter, may be referred to as X-5)
A-1-4 was melt-kneaded at a ratio of 70% by weight and B-1 at a ratio of 30% by weight using a twin-screw extruder, and pellets of X-5 were obtained by a pelletizer.

-Composition (X-6) (hereinafter, may be referred to as X-6)
A-1--4 was melt-kneaded at a ratio of 55% by weight and B-1 at a ratio of 45% by weight using a twin-screw extruder, and pellets of X-6 were obtained by a pelletizer.

-Composition (X-7) (hereinafter, may be referred to as X-7)
A-1-3 was melt-kneaded at a ratio of 55% by weight and B-3 at a ratio of 45% by weight using a twin-screw extruder, and pellets of X-7 were obtained by a pelletizer.

-Composition (X-8) (hereinafter, may be referred to as X-8)
A-1--4 is 35% by weight, A-2-1 is 5% by weight, and B-2 is 60% by weight using a twin-screw extruder, melt-kneaded, and pelletized X-8 with a pelletizer. Got

-Composition (X-9) (hereinafter, may be referred to as X-9)
A-1-3 was melt-kneaded at a ratio of 40% by weight and B-2 at a ratio of 60% by weight using a twin-screw extruder, and pellets of X-9 were obtained by a pelletizer.

The compositions of compositions X-1 to X-9 are shown in Table 1.

Examples 1-9, Comparative Examples 1-10
The composition (X) and the polyamide resin (A-3) shown in Table 1 are mixed (dry blended) at 60 rpm for 10 minutes using a tumbler to obtain a polyamide resin composition. Tumbler. A molded product was prepared by the above method, and the surface roughness and gloss glossiness of the prepared molded product were measured. The results are shown in Table 2. The blanks in Table 2 indicate that no additives have been added. The composition of the polyamide resin composition is shown in Table 3.

The entire disclosure of Japanese Patent Application No. 2014-218092 (Filing Date: October 27, 2014) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (6)

In the composition (X) containing PA6 (A-1), PA6T / 6I (A-2) and glass fiber (B), which are melt-kneaded,
A polyamide resin composition further added with PA6 (A-3) having a relative viscosity smaller than the relative viscosity of PA6 (A-1). The glass fiber (B) has a circular cross-sectional glass fiber having an average fiber diameter of 5 μm or more and 25 μm or less, and / or a non-major axis to minor axis ratio in a cross section perpendicular to the length direction of 1.2 or more and 10 or less. The polyamide resin composition according to claim 1, which is a glass fiber having a circular cross section. The polyamide resin composition according to claim 1 or 2, wherein the relative viscosity of PA6 (A-1) is 1.5 or more and 5.0 or less. The invention according to any one of claims 1 to 3 , wherein the MVR of PA6T / 6I (A-2) is 10 ml / 10 minutes or more when measured under the conditions of a temperature of 275 ° C. and a weight of 5 kg in accordance with ISO1133 . Polyamide resin composition. A molded product comprising the polyamide resin composition according to any one of claims 1 to 4. PA6 (A-1), PA6T / 6I (A-2) and glass fiber (B) are melt-kneaded to obtain the composition (X).
Mixing the composition (X) with PA6 (A-3) having a relative viscosity smaller than that of PA6 (A-1), and
A method for producing a polyamide resin composition containing.