JP5496762B2 - Glass fiber reinforced polyamide resin composition and molded body - Google Patents

Description

  The present invention relates to a glass fiber reinforced polyamide resin composition and a molded body.

Conventionally, polyamide resins and polyester resins have been used in various industrial fields because they have excellent mechanical properties (mechanical strength, rigidity, impact resistance, etc.).
In particular, polyamide is often used in combination with an inorganic compound filler such as glass fiber, glass flake, alumina fiber or layered inorganic compound for the purpose of enhancing mechanical properties. Among these, when compounding with glass fiber as an inorganic compound, a silane coupling agent or a film forming agent is generally used to modify the interface state when compounded with polyamide.

Furthermore, as a technique for further improving the mechanical properties of the polyamide resin, a technique relating to a glass fiber reinforced polyamide resin composition has attracted attention.
For example, a glass fiber surface-treated with a glass fiber sizing agent containing a maleic anhydride and unsaturated monomer copolymer and a silane coupling agent as main constituents is combined with a polyamide resin. Thereby, the technique of improving antifreeze liquid resistance is disclosed (for example, refer patent document 1). Moreover, the technique which improves the fluidity | liquidity of the glass fiber in molten polyamide resin is disclosed by using the compound which introduce | transduced the allyl group into the terminal of a silane coupling agent (for example, refer patent document 2). Furthermore, a technique for increasing the water resistance between the glass fiber surface and the polyamide resin using a polycarbodiimide resin, a polyurethane resin, or a silane coupling agent is disclosed (for example, see Patent Document 3).

JP-A-6-128479 JP 2000-303359 A JP-A-9-227173

When a polyamide resin composition is used for automobile parts, various electronic parts, etc., mechanical strength, impact resistance and workability are required at a high level.
However, the above-mentioned conventional technique cannot stably obtain a polyamide resin composition reaching such a level. Therefore, the request | requirement with respect to the stable supply of the glass fiber reinforced polyamide resin composition applicable to said components is increasing.

  The problem to be solved by the present invention is to provide a glass fiber reinforced polyamide resin composition which is capable of producing a molded article excellent in mechanical strength and impact resistance and excellent in workability.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a glass fiber reinforced polyamide resin composition containing a polyamide resin and containing predetermined glass fibers. The invention has been completed.
That is, the present invention is as follows.

[1]
A polyamide resin composition comprising (A) a polyamide resin and (B) glass fiber,
The (B) glass fiber is 1 to 200 parts by mass with respect to 100 parts by mass of the (A) polyamide resin,
The (B) glass fibers, see contains a glass fiber (b-1) below glass fibers and the following (b-2),
In the (A) polyamide resin, x representing the ratio of the amino group terminal concentration to the carboxyl group terminal concentration and y representing the component concentration of the following (b-1) with respect to the component concentration of the following (b-2) are: Satisfy the relationship of the expression,
0.28 ≦ x / y ≦ 3.56
Y is 0.18 or more and 2.3 or less,
Polyamide resin composition.
(B-1): A sizing agent containing a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer is contained. Glass fiber to do.
(B-2): Glass fiber containing a sizing agent containing a polycarbodiimide compound.

[2]
In (A) the polyamide resin, x representing the ratio of the amino group terminal concentration to the carboxyl group terminal concentration, and y representing the component concentration of (b-1) to the component concentration of (b-2),
The polyamide resin composition according to [1], which satisfies the following formula (1).
0.5 ≦ x / y ≦ 2.0 (1)

[3]
The polyamide resin composition according to [1] or [2], wherein the ratio of the amino group terminal concentration to the carboxyl group terminal concentration exceeds 0.5 in the (A) polyamide resin.

[4]
The polyamide resin composition according to any one of [1] to [3], wherein the (A) polyamide resin has a carboxyl group terminal concentration of 50 μmol / g or more.

[5]
The (A) polyamide resin is
Polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 6
The polyamide resin composition according to any one of [1] or [4] , wherein the polyamide resin composition is one or more selected from the group consisting of T, polyamide 6I and polyamide 9T, and a copolymerized polyamide containing these as constituent components.
[6]
The polyamide resin composition according to any one of [1] to [5], wherein x representing the ratio of the amino group terminal concentration to the carboxyl group terminal concentration in the (A) polyamide resin is 0.43 ≦ x. object.

[7]
The molded object using the polyamide resin composition as described in any one of said [1] thru | or [6].

  According to the present invention, a glass fiber reinforced polyamide resin composition having excellent mechanical strength and impact resistance and capable of producing a molded article excellent in workability can be obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is a polyamide resin composition containing (A) a polyamide resin and (B) glass fibers.
The (B) glass fiber contains the following (b-1) and (b-2).
(B-1) Glass fiber sizing agent comprising a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer Containing glass fiber.
(B-2) A glass fiber containing a glass fiber sizing agent containing a polycarbodiimide compound.

  Hereinafter, each component of the polyamide resin composition of the present embodiment will be described in detail.

((A) Polyamide resin)
Polyamide means a polymer compound having a —CO—NH— (amide) bond in the main chain.
Although not limited to the following, for example, polyamide obtained by ring-opening polymerization of lactam, polyamide obtained by self-condensation of ω-aminocarboxylic acid, polyamide obtained by condensing diamine and dicarboxylic acid, and copolymers thereof Is mentioned.
Polyamide may be used alone or as a mixture of two or more.

Hereinafter, the raw material of (A) polyamide resin is demonstrated.
(A) The raw material of the polyamide resin includes lactam and ω-aminocarboxylic acid.
The lactam as a monomer which is a constituent component of polyamide is not limited to the following, and examples thereof include pyrrolidone, caprolactam, undecaractam and dodecaractam.
On the other hand, the ω-aminocarboxylic acid is not limited to the following, and examples thereof include ω-amino fatty acids which are ring-opening compounds of the above lactams with water.
In addition, as lactam or ω-aminocarboxylic acid, two or more monomers may be used together and condensed.

Moreover, diamine and carboxylic acid are mentioned as a raw material of (A) polyamide resin, (A) polyamide resin is obtained by these condensation.
First, the diamine (monomer) is not limited to the following. For example, a linear aliphatic diamine such as hexamethylene diamine or pentamethylene diamine; 2-methylpentane diamine or 2-ethylhexamethylene diamine Branched aliphatic diamines such as: aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine.
Examples of the dicarboxylic acid (monomer) include, but are not limited to, for example, aliphatic dicarboxylic acids such as adipic acid, pimelic acid and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; cyclohexanedicarboxylic acid And alicyclic dicarboxylic acids such as
The diamine and dicarboxylic acid as the above-described monomers may be used alone or in combination of two or more.

The polyamide produced from the raw materials described above will be described below.
Examples of the polyamide include, but are not limited to, polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), and polyamide 46 (polytetraamide). Methylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), and polyamide 6I (polyhexamethylene) Isophthalamide) and copolymerized polyamides containing these as constituents.
Preferably, it is at least one selected from the group consisting of polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 6T, polyamide 6I and polyamide 9T, and a copolymerized polyamide containing these as constituent components.

  Examples of the copolymer polyamide include, but are not limited to, for example, a copolymer of hexamethylene adipamide and hexamethylene terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and hexamethylene terephthalamide. And a copolymer of 2-methylpentanediamine terephthalamide.

As an end group of polyamide, an amino group or a carboxyl group is generally present.
From the viewpoint of improving the mechanical strength, toughness, and processability of the polyamide resin composition, the ratio of these terminal groups is preferably such that the amino group terminal concentration / carboxyl terminal group concentration (= x) exceeds 0.5.

Further, the lower limit of the amino group terminal concentration / carboxyl terminal concentration is more preferably a value exceeding 0.60, and further preferably 0.65 or more.
On the other hand, the upper limit of amino group terminal concentration / carboxyl terminal concentration is preferably 1.0 or less, more preferably 0.90 or less.

The concentration of the carboxyl group at the end of the polyamide is preferably 50 μmol / g or more, more preferably 50 to 150 μmol / g, still more preferably 50 to 100 μmol / g, still more preferably 50 to 80 μmol / g. It is.
When the concentration of the terminal carboxyl group is within the above range, the mechanical strength can be significantly improved.

Here, the concentration of the terminal amino group and the terminal carboxyl group in the present specification can be determined by the integral value of the characteristic signal corresponding to each terminal group measured by ¹ H-NMR.

Further, the end groups of the polyamide may be adjusted separately. As the adjustment method, a known method can be used.
Although it does not restrict | limit to the following, For example, the method of using a terminal regulator is mentioned.
As a specific example, a method of adding one or more selected from the group consisting of a monoamine compound, a diamine compound, a monocarboxylic acid compound and a dicarboxylic acid compound to a solvent so as to have a predetermined terminal concentration at the time of polyamide polymerization can be mentioned.
The timing of addition of these components to the solvent is not particularly limited as long as it functions as a terminal regulator, and for example, the above-described polyamide raw material may be added to the solvent.

Examples of the monoamine compound as the terminal adjuster include, but are not limited to, for example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dipropylamine. Examples thereof include aliphatic monoamines such as butylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, and arbitrary mixtures thereof.
In particular, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, stability of the sealing end, price, and the like. These may be used alone or in combination of two or more.

As the diamine compound as the terminal adjusting agent, those mentioned as the above-mentioned polyamide materials can be used.
These may be used alone or in combination of two or more.

Examples of the monocarboxylic acid compound as the terminal adjuster include, but are not limited to, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid. Aliphatic monocarboxylic acids such as acid, pivalic acid and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and Aromatic monocarboxylic acids such as phenylacetic acid can be mentioned.
These carboxylic acid compounds may be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound as the terminal adjuster include, but are not limited to, for example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2 Aliphatic dicarboxylic acids such as 1,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; alicyclic rings such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Formula dicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid , Diphenic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4 Examples thereof include units derived from aromatic dicarboxylic acids such as' -dicarboxylic acid and 4,4'-biphenyldicarboxylic acid.
These may be used alone or in combination of two or more.

((B) Glass fiber)
Glass fiber (the component of (B)) includes the following (b-1) and (b-2).
(B-1) A glass fiber sizing agent comprising a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer. Contains glass fiber.
(B-2) A glass fiber containing a glass fiber sizing agent containing a polycarbodiimide compound.
Here, the “glass fiber containing a glass fiber sizing agent” means a glass fiber obtained by surface treatment with a glass fiber sizing agent.

Here, in the (A) polyamide resin, x representing “amino group terminal concentration / carboxyl terminal concentration”, and (B) glass fiber, “component concentration of (b-1) / (b-2)”. Y representing “component concentration of” preferably satisfies the following formula (1).
0.5 ≦ x / y ≦ 2.0 (1)
The above x / y is more preferably 0.65 to 2.0, and further preferably 0.65 to 1.5. When it is within the above range, it is preferable from the viewpoint of reducing the number of foreign matters due to eyes during processing and improving mechanical strength.

<(B-1) Glass fiber>
(B) (b-1) component which comprises glass fiber is demonstrated.
(B-1) is a glass fiber bundle comprising a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer. It is a glass fiber containing an agent.
The “carboxylic anhydride-containing unsaturated vinyl monomer” constituting the copolymer contained in the glass fiber sizing agent is not limited to the following, but for example, maleic anhydride, itaconic anhydride and citraconic anhydride Examples of the acid include maleic anhydride.
The unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer constituting the copolymer contained in the glass fiber sizing agent is the carboxylic acid anhydride-containing unsaturated vinyl monomer. An unsaturated vinyl monomer different from the body is meant. Examples of such unsaturated vinyl monomers include, but are not limited to, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, Examples include cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Of these, styrene and butadiene are preferred.

  Among these combinations, a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof are more preferable.

The copolymer of the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer has a weight average molecular weight of 2,000 or more. It is preferable that
Moreover, from a viewpoint of the fluidity | liquidity improvement of a glass fiber reinforced polyamide resin composition, More preferably, it is 2,000-1,000,000, More preferably, it is 5,000-500,000.
In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC).

<(B-2) Glass fiber>
Next, the (b-2) component which comprises (B) glass fiber is demonstrated.
(B-2) is a glass fiber containing a glass fiber sizing agent containing a polycarbodiimide compound.
The polycarbodiimide compound contained in the glass fiber sizing agent of the glass fiber (b-2) can be obtained by condensing a compound containing one or more carbodiimide groups (—N═C═N—).

  The degree of condensation of the polycarbodiimide compound is preferably 1-20, and more preferably 1-10. When the condensation degree of the polycarbodiimide compound is in the range of 1 to 20, a more uniform aqueous solution or aqueous dispersion can be obtained. Furthermore, when the degree of condensation is in the range of 1 to 10, a more uniform aqueous solution or aqueous dispersion can be obtained.

  Moreover, it is preferable that the said polycarbodiimide compound has a polyol segment partially. By having a polyol segment, the polycarbodiimide compound is easily water-soluble and can be more suitably used as a glass fiber sizing agent.

The carbodiimide compound can be obtained by decarboxylation of a diisocyanate compound in the presence of a known carbodiimidization catalyst such as 3-methyl-1-phenyl-3-phospholene-1-oxide.
As the diisocyanate compound, aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates, and mixtures thereof can be used. Although not limited to the following, for example, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate , Dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl Isocyanate and 1,3,5-triisopropylbenzene 2,4-diisocyanate, and the like.
And the polycarbodiimide compound which has two isocyanate groups at the terminal is obtained by carbodiimidizing these diisocyanate compounds.
Of these, dicyclohexylmethane carbodiimide can be suitably used from the viewpoint of improving reactivity.

For a polycarbodiimide compound having two isocyanate groups at the terminal, a method of further converting the monoisocyanate compound to an equimolar amount carbodiimide, or a method of reacting an equimolar amount with a polyalkylene glycol monoalkyl ether to generate a urethane bond, etc. A polycarbodiimide compound having one isocyanate group at the terminal is obtained.
Examples of the monoisocyanate compound include, but are not limited to, hexyl isocyanate, phenyl isocyanate, cyclohexyl isocyanate, and the like.
Examples of the polyalkylene glycol monoalkyl ether include, but are not limited to, polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.

<Other glass fiber sizing agent components>
Examples of the glass fiber sizing agent contained in each of the above-mentioned (b-1) glass fiber and (b-2) glass fiber include, for example, polyurethane resin, acrylic acid homopolymer, acrylic acid and other copolymerizable monomers. Copolymers with these, and salts with these primary, secondary and tertiary amines may also be used. These may be used individually by 1 type, or may use 2 or more types together.

  The polyurethane resin as the <other glass fiber sizing agent component> is not particularly limited as long as it is generally used as a glass fiber sizing agent. For example, m-xylylene diisocyanate (XDI), 4 , 4'-methylenebis (cyclohexyl isocyanate) (HMDI), isophorone diisocyanate (IPDI), and other isocyanates and polyester or polyether diols can be suitably used.

  As the homopolymer of acrylic acid, those having a weight average molecular weight of 1,000 to 90,000 are preferable, and those having a weight average molecular weight of 1,000 to 25,000 are preferable.

  The monomer that forms a copolymer with the acrylic acid constituting a copolymer of acrylic acid and other copolymerizable monomer is not limited to the following, but, for example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid , Maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, including at least one type (except for acrylic acid only) .) Of the above monomers, it is preferable to have one or more ester monomers.

  The salts of acrylic acid homopolymers and / or copolymers with primary, secondary and tertiary amines are not limited to the following, but specific examples include triethylamine, triethanolamine and glycine. The degree of neutralization is preferably 20 to 90%, and preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

  The weight average molecular weight of the acrylic acid polymer forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more are preferable from the viewpoint of improving the converging property of the glass fiber, and 50,000 or less are preferable from the viewpoint of improving the mechanical properties when the polyamide resin composition is obtained.

The glass fiber sizing agent solution may further contain a silane coupling agent as a glass fiber surface treatment agent.
Although it does not restrict | limit especially as said silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane. And the like; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes.
Especially, it is preferable that it is 1 or more types selected from said enumeration component, and aminosilanes are more preferable.

<Preparation of glass fiber sizing agent>
The glass fiber sizing agent contained in the glass fibers of (b-1) and (b-1) described above is added to each of the above-described essential components with a polyurethane resin, a silane coupling agent, and a lubricant as necessary. It is obtained by diluting with water.
As the lubricant, any ordinary liquid or solid lubricant material suitable for the purpose can be used.
For example, animal and plant or mineral waxes such as carnauba wax and lanolin wax, or surfactants such as fatty acid amides, fatty acid esters or fatty acid ethers, or aromatic esters or aromatic ethers can be used.

  The glass fiber sizing agent contained in the glass fiber of (b-1) is a solid content other than the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer. 1 to 5% by weight of copolymer with unsaturated vinyl monomer, 1 to 5% by weight of polyurethane resin, 0.1 to 1% by weight of silane coupling agent, and 0.01 to 0.5% by weight of lubricant Is preferably prepared by diluting with water and adjusting the total mass to 100% by mass.

  The glass fiber sizing agent contained in the glass fiber of (b-2) has a solid content of 1 to 5% by mass of a polycarbodiimide compound, 1 to 5% by mass of a polyurethane resin, and 0.1 to 0.1% of a silane coupling agent. It is preferable to prepare by diluting 1% by mass and 0.01 to 0.5% by mass of the lubricant with water and adjusting the total mass to 100% by mass.

  The glass fiber sizing agent contained in the glass fibers of (b-1) and (b-2) is preferably a homopolymer of acrylic acid or a copolymer of acrylic acid and other monomer components, if desired. 1 to 10% by mass, more preferably 2 to 5% by mass, and a reactive polyurethane resin having an active amino group in the main chain skeleton, preferably 1 to 5% by mass, more preferably 2 to 4% by mass, and carboxylic acid You may prepare so that the copolymer of an anhydride containing unsaturated vinyl monomer and other unsaturated vinyl monomers may be included preferably 1-5 mass%, More preferably, 2-4 mass%.

  In addition, in the glass fiber sizing agent contained in the glass fibers of the above (b-1) and (b-2), if desired, a homopolymer of acrylic acid monomer or a copolymer of acrylic acid and other copolymerizable monomer may be added. Preferably 1 to 10% by mass (more preferably 2 to 5% by mass) and / or reactive polyurethane resin having an active amino group in the main chain skeleton is preferably 1 to 5% by mass, more preferably 2 to 4% by mass. %, May further be included.

In the glass fiber sizing agent contained in the glass fiber of (b-1) above, an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride is used. The blending amount of the copolymer with the monomer is preferably 1% by mass or more from the viewpoint of improving the mechanical strength of the glass fiber reinforced polyamide resin composition, and 5% by mass or less from the viewpoint of improving the converging property of the glass fiber. It is preferable that
In the glass fiber sizing agent contained in the glass fiber of (b-2) above, the blending amount of the polycarbodiimide compound is 1% by mass or more from the viewpoint of improving the mechanical strength of the glass fiber reinforced polyamide resin composition. Is preferable, and it is preferable that it is 5 mass% or less from a viewpoint of the convergence property of glass fiber.
In the glass fiber sizing agent contained in the glass fibers (b-1) and (b-2), the blending amount of the polyurethane resin is 1% by mass or more from the viewpoint of improving the sizing property of the glass fibers. Preferably, it is preferably 5% by mass or less from the viewpoint of improving the mechanical strength of the glass fiber reinforced polyamide resin composition.

  In the glass fiber sizing agent contained in the glass fibers of the above (b-1) and (b-2), a homopolymer of acrylic acid, a copolymer of acrylic acid and other monomer components, and their primary grades The blending amount of one or more polymers selected from secondary and tertiary amine salts is improved in the mechanical strength of the glass fiber reinforced polyamide resin composition at the time of water absorption in a field requiring water resistance strength. From the viewpoint of the above, 1% by mass or more is preferable, and from the viewpoint of improving the converging property of the glass fiber, the color tone, appearance and surface smoothness of the composition, it is preferably 10% by mass or less.

The blending amount of the silane coupling agent in the glass fiber sizing agent of the above (b-1) and (b-2) is the viewpoint of improving the glass fiber sizing property and improving the mechanical strength of the glass fiber reinforced polyamide resin composition. From 0.1 to 1% by mass is preferable.
Further, the blending amount of the lubricant in the glass fiber sizing agent contained in the glass fibers (b-1) and (b-2) is 0.01% by mass or more from the viewpoint of providing sufficient lubricity. It is preferable that it is 0.5 mass% or less from a viewpoint of the mechanical strength improvement of a glass fiber reinforced polyamide resin composition.

<The manufacturing method of the glass fiber of (b-1) and (b-2)>
The glass fibers of (b-1) and (b-2) can be continuously produced by drying glass fiber strands produced by imparting to the glass fibers using a known method such as a roller type applicator.
The glass fiber strand may be used as a roving as it is, or may be used as a chopped glass strand after further obtaining a cutting step.
The glass fiber sizing agent preferably imparts (adds) 0.2 to 3% by mass or more, more preferably 0.3 to 2% by mass (addition) as a solid content with respect to 100% by mass of glass fiber. To do. From the standpoint of maintaining the glass fiber bundling, the addition amount of the glass fiber bundling agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber.
On the other hand, it is preferably 3% by mass or less from the viewpoint of improving the thermal stability of the glass fiber reinforced polyamide resin composition. Moreover, drying of a strand may be performed after a cutting process, and you may cut | disconnect, after drying a strand.

(Other components of polyamide resin composition)
In addition to the above-described components, other components may be added as necessary within a range not impairing the effects of the present embodiment.
For example, inorganic fillers other than glass fibers, antioxidants, UV absorbers, heat stabilizers, photodegradation inhibitors, plasticizers, lubricants, mold release agents, nucleating agents, flame retardants, colorants, dyeing agents, pigments, etc. May be added, or other thermoplastic resin may be mixed.
Here, since the above-mentioned other components are greatly different in properties, there are various suitable contents for each component that hardly impair the effects of the present embodiment. A person skilled in the art can easily set a suitable content for each of the other components described above.

[Production method of polyamide resin composition]
The polyamide resin composition is kneaded with (A) a polyamide resin, (B) glass fiber, and predetermined other components in a state where (A) the polyamide resin is melted, using a predetermined extruder. Can be manufactured.
(B) When using chopped strands as glass fibers, a twin-screw extruder provided with an upstream supply port and a downstream supply port was used, and (A) polyamide resin was supplied from the upstream supply port and melted. Thereafter, it is preferable to use a method in which chopped strands are supplied from the downstream supply port and melt kneaded. Moreover, also when using glass fiber roving, it can compound by a well-known method.
Here, with respect to 100 parts by mass of the component (A) (polyamide resin), the content of the component (B) (predetermined glass resin) is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts. It is a mass part, More preferably, it is 15-100 mass parts. In the above-mentioned range, both the fluidity and appearance of the glass fiber reinforced polyamide resin composition are further improved.

[Molded body using polyamide resin composition]
The polyamide resin composition of the present embodiment is not particularly limited, and can be used as a molded body of various parts by, for example, injection molding.

[Use of molded body using polyamide resin composition]
The molded article of the polyamide resin composition of the present embodiment can be suitably used, for example, as various parts for automobiles, machine industries, electrical / electronics, industrial materials, industrial materials, daily use / household goods.

Hereinafter, although an example and a comparative example of the present invention are given and explained concretely, the present invention is not limited to the following examples.
The preparation, measurement method and production method of raw materials used in Examples and Comparative Examples are shown below.

[Preparation of raw materials]
<1. Polyamide resin>
(1) Polyamide 66 (hereinafter abbreviated as “PA-1”)
1600 kg of equimolar salt of hexamethylene diamine (manufactured by Asahi Kasei Chemicals) and adipic acid (manufactured by Asahi Kasei Chemicals) as a polyamide raw material was added to distilled water to obtain a 50% by mass aqueous solution as a polyamide resin raw material. The obtained aqueous solution was charged into an autoclave of about 4,000 liters having a discharge nozzle at the bottom, and replaced with nitrogen while mixing at 50 ° C.

Subsequently, the temperature was raised from 50 ° C. to about 150 ° C. over about 1 hour.
At that time, in order to keep the pressure in the autoclave at about 0.15 MPa (gauge pressure), heating was continued while removing water out of the system.
Thereafter, the autoclave was sealed, and the temperature was raised from 150 ° C. to about 220 ° C. over about 1 hour to raise the pressure to about 1.77 MPa (gauge pressure).

Subsequently, the temperature was raised from about 220 ° C. to about 280 ° C. over about 1 hour, while maintaining the pressure at about 1.77 MPa, heating was performed by removing water from the system.
Thereafter, the pressure was reduced to atmospheric pressure over about 1 hour, and after reaching atmospheric pressure, the pellets were discharged in a strand form from the lower nozzle, water-cooled and cut to obtain PA-1 pellets. The obtained pellets were dried in a nitrogen stream at 90 ° C. for 4 hours.

Here, the 98% sulfuric acid relative viscosity [ηr: 25 ° C., 1 g / 100 ml] of PA-1 was 2.79.
The amino group terminal was 46 μmol / g, the carboxyl group terminal was 72 μmol / g, and the amino group terminal concentration / carboxyl group terminal concentration was 0.639.
In addition, JIS K 6920 was adopted as a method for measuring sulfuric acid relative viscosity in the present specification.

(2) Polyamide 66 (hereinafter abbreviated as “PA-2”)
Hexamethylenediamine was added as a terminal modifier.
Other conditions were the same as in the case of PA-1 above to obtain PA-2.
Here, the 98% sulfuric acid relative viscosity ηr was 2.78, the amino group terminal was 53 μmol / g, the carboxyl group terminal was 67 μmol / g, and the amino group terminal concentration / carboxyl group terminal concentration was 0.791.

(3) Polyamide 66 (hereinafter abbreviated as “PA-3”)
Adipic acid was added as a terminal adjuster.
Other conditions were the same as in the case of PA-1 to obtain PA-3.
Here, the 98% sulfuric acid relative viscosity ηr was 2.78, the amino group terminal was 38 μmol / g, the carboxyl group terminal was 89 μmol / g, and the amino group terminal concentration / carboxyl terminal concentration was 0.427.

<2. Carbodiimide compound>
As a carbodiimide compound, Nisshinbo Co., Ltd. product name: Carbodilite (registered trademark) V-02 (an aqueous solution having a solid content of 40% by mass) was used.

<3. Polyurethane resin emulsion>
As the polyurethane resin emulsion, trade name: Bondic (registered trademark) 1050: (aqueous solution having a solid content of 50% by mass) manufactured by Dainippon Ink Co., Ltd. was used.

<4. Maleic anhydride copolymer>
As a maleic anhydride-butadiene copolymer aqueous solution, trade name: Acro Binder (registered trademark) BG-7 (an aqueous solution having a solid content of 25% by mass) manufactured by Sanyo Chemical Industries, Ltd. was used.

<5. Aminosilane coupling agent>
γ-aminopropyltriethoxysilane (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

<6. Lubricant>
Product name: Carnauba wax (manufactured by Hiroyuki Kato) was used.

<7. Glass fiber>
(1) GF-1
First, the solid content is 2% by mass of polyurethane resin, 4% by mass of maleic anhydride-butadiene copolymer, 0.6% by mass of γ-aminopropyltriethoxysilane, and 0.1% by mass of carnauba wax. Dilution with water gave a glass fiber sizing agent.
The obtained glass fiber sizing agent was adhered to the glass fiber by an applicator provided in the middle of being wound around the rotating drum with respect to the melt-proofed glass fiber having an average diameter of 10 μm.
And the roving of the glass fiber bundle surface-treated with the said glass fiber sizing agent was obtained by drying after that.
At that time, the glass fiber was made to be a bundle of 1,000 pieces. The adhesion amount of the glass fiber sizing agent was 0.6% by mass. This was cut into a length of 3 mm to obtain a chopped strand (hereinafter abbreviated as “GF-1”).

(2) GF-2
Diluted with water so that the solid content is 4% by mass of carbodiimide compound, 2% by mass of polyurethane resin, 0.6% by mass of γ-aminopropyltriethoxysilane, and 0.1% by mass of carnauba wax, and glass fiber focusing An agent was obtained.
The obtained glass fiber sizing agent was adhered to the glass fiber by an applicator provided in the middle of being wound around the rotating drum with respect to the melt-proofed glass fiber having an average diameter of 10 μm. And the roving of the glass fiber bundle surface-treated with the said glass fiber sizing agent was obtained by drying after that.
At that time, the glass fiber was made to be a bundle of 1,000 pieces. The adhesion amount of the glass fiber sizing agent was 0.6% by mass. This was cut into a length of 3 mm to obtain a chopped strand (hereinafter abbreviated as “GF-2”).

〔Evaluation method〕
Hereinafter, evaluation methods performed in Examples and Comparative Examples will be described.
<Adhesion amount of glass fiber sizing agent>
After weighing 10 g of the glass fiber surface-treated with the glass fiber sizing agent, it was heated in an electric furnace at 650 ° C. for 1 hour. The amount of mass decrease during this period was defined as the amount of glass fiber sizing agent attached.

<Charpy impact strength>
Using the injection molding machine (PS-40E: made by Nissei Resin Co., Ltd.), the pellets of the polyamide resin compositions obtained in the examples and comparative examples were formed into multi-purpose test pieces A-type molded pieces in accordance with ISO 3167. Molded.
At that time, the injection and pressure holding time were set to 25 seconds, the cooling time was set to 15 seconds, the mold temperature was 80 ° C., and the molten resin temperature was 290 ° C. The obtained molded piece was cut and used, and a Charpy impact strength with a notch was measured according to ISO 179 / 1eA using a test piece having a thickness of 80 mm, a width of 10 mm, and a length of 4 mm.

<Tensile strength>
Using the multi-purpose test piece (A type), a tensile test was performed in accordance with ISO 527 at a tensile speed of 5 mm / min, and the tensile strength was measured.

<Processability (Amount of adhesion to eyes)>
5 kg of the polyamide resin composition pellets obtained in the examples and comparative examples were spread on a metal bat, and the number of foreign matters caused by the eyes (hereinafter referred to as “the number of foreign matters caused by the eyes”) was visually measured.

[Examples 1 to 8] [Comparative Examples 1 and 2]
L / D (extruder cylinder length / extruder cylinder diameter) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the ninth barrel = 48 (number of barrels: 12) twin screw extruder (ZSK-26MC: manufactured by Coperion (Germany)) was used.
In the twin-screw extruder, the distance from the upstream supply port to the die was set to 290 ° C., screw rotation speed 200 rpm, and discharge rate 20 kg / hour. Under such conditions, the polyamide resin (PA-1 to PA-3) is supplied from the upstream supply port so as to have the ratio described in the upper part of Table 1 below, and the glass fiber chopped strand ( GF-1 to GF-2) were supplied.
And the pellet of the polyamide resin composition was manufactured by melt-kneading these.
The obtained polyamide resin composition was molded at a resin temperature of 290 ° C. and a mold temperature of 80 ° C., and Charpy impact strength and tensile strength were evaluated.
At the same time, the number of foreign matters caused by eyes was measured. The evaluation (measurement) results are shown in Table 1 below.

  From Table 1, when Examples 1, 2, 4 to 8 and Comparative Examples 1 and 2 are compared, the glass fiber (B) includes both the glass fibers (b-1) and (b-2). In some cases, the Charpy impact strength and the tensile strength were significantly higher than the case where only one of them was included, and it was confirmed that the number of foreign substances due to eyes was remarkably small.

[Examples 9 and 10] [Comparative Examples 3 to 6]
Polyamide resin (PA-2) and glass fiber chopped strands (GF-1 to GF-2) were melt-kneaded so that the ratio described in the upper part of Table 2 below was obtained.
Other conditions were the same as in Example 1 to produce polyamide resin composition pellets.
These evaluation (measurement) results are shown in Table 2 below.

  From Table 2 above, when Example 9 and Comparative Examples 3 to 4 are compared, and Example 10 and Comparative Examples 5 to 6 are compared, the glass fiber (B) is the same as the comparison result in Table 1 above. When both of the glass fibers of (b-1) and (b-2) are included, the Charpy impact strength and tensile strength are significantly higher compared to the case where only one of them is included. It was confirmed that the number of foreign matters was remarkably small.

  From the above, the polyamide resin composition of the present embodiment has significantly improved mechanical strength, impact resistance and workability compared to conventional ones, and is also used for automobile parts and various electronic parts. It was found that it can be applied sufficiently.

  The polyamide resin composition of the present invention has industrial applicability as a molded product that requires light weight, high mechanical strength, etc., such as automobile parts and electronic parts (connectors, switches).

Claims (7)

A polyamide resin composition comprising (A) a polyamide resin and (B) glass fiber,
The (B) glass fiber is 1 to 200 parts by mass with respect to 100 parts by mass of the (A) polyamide resin,
The (B) glass fibers, see contains a glass fiber (b-1) below glass fibers and the following (b-2),
In the (A) polyamide resin, x representing the ratio of the amino group terminal concentration to the carboxyl group terminal concentration and y representing the component concentration of the following (b-1) with respect to the component concentration of the following (b-2) are: Satisfy the relationship of the expression,
0.28 ≦ x / y ≦ 3.56
Y is 0.18 or more and 2.3 or less,
Polyamide resin composition.
(B-1): A sizing agent containing a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer other than the carboxylic acid anhydride-containing unsaturated vinyl monomer is contained. Glass fiber to do.
(B-2): Glass fiber containing a sizing agent containing a polycarbodiimide compound. In (A) the polyamide resin, x representing the ratio of the amino group terminal concentration to the carboxyl group terminal concentration, and y representing the component concentration of (b-1) to the component concentration of (b-2),
The polyamide resin composition of Claim 1 which satisfy | fills following formula (1).
0.5 ≦ x / y ≦ 2.0 (1)   The polyamide resin composition according to claim 1 or 2, wherein the ratio of the amino group terminal concentration to the carboxyl group terminal concentration exceeds 0.5 in the (A) polyamide resin. The polyamide resin composition according to any one of claims 1 to 3, wherein the (A) polyamide resin has a carboxyl group terminal concentration of 50 µmol / g or more. The (A) polyamide resin is
Polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 6
The polyamide resin composition according to any one of claims 1 to 4 , wherein the polyamide resin composition is at least one selected from the group consisting of T, polyamide 6I, polyamide 9T, and a copolymerized polyamide containing these as constituent components. 6. The polyamide resin composition according to claim 1, wherein x representing the ratio of the amino group terminal concentration to the carboxyl group terminal concentration in the (A) polyamide resin is 0.43 ≦ x.   The molded object using the polyamide resin composition as described in any one of Claims 1 thru | or 6.