JP2009035593A - Glass fiber-reinforced polyamide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reinforced polyamide resin composition in which both glass fibers and a swelling laminar silicate are used to improve the mechanical properties, especially tensile strength, of the reinforced polyamide resin composition. <P>SOLUTION: This polyamide resin composition comprises: a swelling laminar silicate (A) prepared by inserting 0.5 to 30 pts.mass of an aliphatic primary amine between the layers based on 100 pts.mass of a swelling laminar silicate; and surface-treated glass fibers (B) surface-treated with a sizing agent including 0.01 to 1 pt.mass of a silane coupling agent based on 100 pts.mass of the glass fibers, wherein 100 pts.mass of a polyamide resin composition (C) prepared by mixing 100 pts.mass of a polyamide monomer, 0.5 to 20 pts.mass of the swelling laminar silicate (A), and 0 to 20 pts.mass of pure water and then polymerizing the polyamide monomer and 5-200 pts.mass of the surface-treated glass fibers (B) are compounded. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a reinforced polyamide resin composition, and further relates to a reinforced polyamide resin composition using glass fibers and a swellable layered silicate in combination.

  Conventionally, for the purpose of improving the strength of a polyamide resin, it has been carried out to obtain a reinforced polyamide resin by blending inorganic fillers including various glass fibers. In order to further increase the strength-increasing effect, a technique of treating the surface of the inorganic filler with a silane coupling agent having a high affinity for both the filler and the polyamide resin is widely used.

  On the other hand, these inorganic fillers generally have a heavier specific gravity than the resin, and the specific gravity has increased with increasing strength. Therefore, a reinforced polyamide resin composition that uses a swellable layered silicate as a starting material, and the size of the inorganic filler present in the resin is changed from the micrometer order to the nanometer order, greatly improving the reinforcement efficiency. A product was developed (Cited document 1). Depending on the application, inorganic fillers of different sizes may be used in combination, but when different types of inorganic fillers are used, such as glass fibers and swellable layered silicates, among the mechanical properties, the orientation direction of the inorganic fillers in particular. However, there is a problem that the reinforcing effect cannot be expected with respect to the tensile strength indicating the force drawn in the parallel direction.

  In contrast, a method of treating the surface of a layered clay mineral using a higher aliphatic amine typified by octadecylamine (Patent Document 2), a higher aliphatic amine as a molding improver at the time of molding of a polyamide resin, etc. A method of obtaining a molded product by mixing and injection molding (Patent Document 3) is disclosed.

However, all are just one of many other organic agents and molding improvers that have been invented to achieve their respective purposes, and when a single reinforcing agent is used against a polyamide resin, Although the effect of improving the strength was recognized, when the glass fiber and the swellable layered silicate were used in combination, the mechanical properties of the obtained reinforced polyamide resin, particularly the effect of improving the tensile strength, was not sufficient. In such a case, when the fracture surface of the sample subjected to the tensile test by the ISO-527 measurement method is observed, the adhesion between the glass and the resin is generally poor, and the synergistic effect of each reinforcing agent cannot be obtained. It was.
JP-A-6-248176 Pamphlet of International Publication No. 1999050340 JP-A-9-012870

  The problem to be solved by the present invention is to improve the mechanical properties of polyamide resin by using glass fiber and swellable layered silicate together, and to strengthen the polyamide resin composition by using glass fiber and swellable layered silicate in combination. An object of the present invention is to provide a reinforced polyamide resin composition having improved mechanical properties, particularly tensile strength.

  As a result of intensive studies to solve such problems, the present inventors have found that a swellable layered silicate (A) in which a cation of an aliphatic primary amine is inserted between layers and an amino group at the end. Alternatively, by using a glass fiber / swellable layered silicate combined reinforced polyamide resin having a unsaturated bond and a glass fiber (B) surface-treated with a silane coupling agent having a silanol group at the other end, The inventors have found that this problem can be solved and have reached the present invention.

That is, the gist of the present invention is that a swellable layered silicate (A) in which 0.5 to 30 parts by weight of an aliphatic primary amine is inserted between layers with respect to 100 parts by weight of a swellable layered silicate, and glass Polyamide resin formed by blending surface-treated glass fiber (B) surface-treated with a sizing agent containing 0.01 to 1% by mass of a silane coupling agent represented by the following formula (1) with respect to 100 parts by mass of fiber. A composition comprising 100 parts by mass of a polyamide monomer, 0.5-20 parts by mass of a swellable layered silicate represented by (A), and 0-20 parts by mass of pure water, and then polymerizing the polyamide monomer. A polyamide resin composition comprising 100 parts by mass of the polyamide resin composition (C) obtained and 5 to 200 parts by mass of the surface-treated glass fiber represented by (B).
R ₁ Si (OR ₂ ) ₃ (1)
(In the formula, R ₁ is an alkyl group having 2 to 10 carbon atoms having an amino group or an epoxy group at the terminal, and R ₂ is a methyl group or an ethyl group)

  A silane having an aliphatic primary amine inserted between layers for a swellable layered silicate and an amino group or an unsaturated bond at the terminal and a silanol group at the other terminal for a glass fiber A polyamide resin composition using a material treated with a coupling agent has improved tensile strength and can be suitably used in the material field requiring high mechanical properties, and has a very high industrial utility value.

  Hereinafter, the present invention will be described in detail.

  The swellable layered silicate used in the present invention has a structure composed of a negatively charged crystal layer mainly composed of silicate and a cation having ion exchange ability interposed between the layers. It is desirable that the obtained cation exchange capacity is 50 meq / 100 g or more. When the cation exchange capacity is less than 50 meq / 100 g, the swelling ability is low, so that the polyamide composite material remains substantially in an uncleavage state, and no performance improvement is observed. In the present invention, the upper limit of the value of the cation exchange capacity is not particularly limited, and an appropriate one may be selected from swellable layered silicates that can be actually prepared.

  Such swellable layered silicates may be naturally occurring, artificially synthesized or modified, such as smectites (montmorillonite, beidellite, hectorite, soconite, etc.), vermiculites (vermiculite, etc.), mica Family (fluorine mica, muscovite, paragonite, phlogopite, lepidrite, etc.), brittle mica family (margarite, clintonite, anandite, etc.), chlorite family (donbasite, sudoite, kukeite, clinochlore, chamonite, nimite, etc.) In the present invention, Na-type or Li-type swellable fluorinated mica or montmorillonite is particularly preferably used.

  The swellable fluorine mica preferably used in the present invention generally has a structural formula represented by the following formula (2).

M _α (Mg _X Li _β ) Si ₄ O _Y F _Z (2)
(In the formula, M represents an ion-exchangeable cation, specifically sodium or lithium. Α, β, X, Y, and Z each represents a coefficient, and 0 ≦ α ≦ 1.0. 0 ≦ β ≦ 1.0, 2.5 ≦ X ≦ 4, 10 ≦ Y ≦ 15, 1.0 ≦ Z ≦ 2.0)
As a method for producing such a swellable fluorine mica, for example, silicon oxide, magnesium oxide and various fluorides are mixed, and the mixture is completely melted in a temperature range of 1400 to 1500 ° C. in an electric furnace or a gas furnace. A melting method in which a crystal of swellable fluorinated mica grows in the reaction vessel during the cooling process.

On the other hand, there is also a method of using talc [Mg ₃ Si ₄ O ₁₀ (OH) ₂ ] as a starting material and intercalating alkali metal ions to impart swellability to obtain a swellable fluorine mica (Japanese Patent Laid-Open No. Hei. No. 2-149415). In this method, swellable fluoromica can be obtained by heat-treating talc and alkali silicofluoride mixed at a predetermined blending ratio in a magnetic crucible at a temperature of 700 to 1200 ° C. for a short time.

  At this time, the amount of alkali silicofluoride mixed with talc is preferably in the range of 10 to 35 mass% of the entire mixture. If it is out of this range, the yield of swellable fluorinated mica tends to decrease.

  The montmorillonite used in the present invention is represented by the following formula (3), and can be obtained by refining a naturally produced product using a water treatment or the like.

M _a Si (Al _2-a Mg) O ₁₀ (OH) ₂ .nH ₂ O (3)
(In the formula, M represents a cation such as sodium, and 0.25 ≦ a ≦ 0.7. The number of water molecules bonded to the interlayer ion-exchangeable cation depends on conditions such as cation species and humidity. (It is expressed as nH ₂ O in the formula)
In addition, montmorillonite is known to have isomorphic ion substitution products such as magnesia montmorillonite, iron montmorillonite, iron magnesia montmorillonite, and these may be used.

  In the present invention, there is no particular limitation on the initial particle size of the above-described swellable layered silicate. Here, the initial particle size is the particle size of the swellable layered silicate as a raw material used in producing the polyamide resin composition used in the present invention, and is different from the size of the silicate layer in the composite material. However, this particle size also has a considerable influence on the physical properties of the obtained polyamide composite material, in particular the rigidity and heat resistance. Therefore, it is desirable to take this point into consideration when selecting the mixing ratio of the above-mentioned swellable layered silicate, and it is preferable to control the particle size by pulverizing with a jet mill or the like as necessary.

  Here, when the swellable fluoromica mineral is synthesized by the intercalation method, the initial particle size can be changed by appropriately selecting the particle size of talc as a raw material. This is a preferable method in that the initial particle diameter can be adjusted in a wider range by using in combination with pulverization.

  The aliphatic primary amine inserted between the layers of the swellable layered silicate used in the present invention is specifically octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecyl. Examples include amine, stearylamine, oleylamine and the like. By dissolving the halogenated salt or metal salt of these amines in pure water, mixing a predetermined amount of swellable layered silicate into the solution, stirring at room temperature, filtering and drying, A swellable layered silicate having these amine cations inserted between the layers can be obtained. This was baked at 600 ° C. in the air to remove organic substances, and then the residual mass was measured to calculate the amount of stearylamine.

  The aliphatic primary amine is preferably 0.5 to 30 parts by mass with respect to the swellable layered silicate. When the amount is less than 0.5 parts by mass, the effect of improving the tensile strength of the obtained glass-reinforced resin composition is small, and it is not realistic to obtain an aliphatic primary amine of 30 parts by mass or more by the above method. .

  The compounding amount of the swellable layered silicate (A) treated with the aliphatic primary amine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyamide monomer. When the blending amount is less than 0.5 parts by mass, the mechanical strength is hardly improved. On the other hand, when the blending amount exceeds 20 parts by mass, the production efficiency of the polyamide polymer is lowered, which is not preferable.

  The polyamide resin in the present invention is a polymer having an amide bond in the main chain, the main raw material of which is aminocarboxylic acid, lactam or diamine and dicarboxylic acid (including a pair of salts thereof). Specific examples of the raw material include aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the lactam include ε-caprolactam, ω-undecanolactam, and ω-laurolactam. Examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, and dodecamethylene diamine. Examples of the dicarboxylic acid include adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like. These diamines and dicarboxylic acids can also be used as a pair of salts.

  Preferred examples of such polyamide resin include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polycaproamide / polyhexamethylene adipamide copolymer (Nylon 6/66), polyundecamide (nylon 11), polycaproamide / polyundecamide copolymer (nylon 6/11), polydodecamide (nylon 12), polycaproamide / polydodecamide copolymer (nylon 6/12), Examples include polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), and mixtures or copolymers thereof. Of these, nylon 6 and nylon 12 are particularly preferable.

The surface-treated glass fiber (B) used in the present invention is surface-treated with a sizing agent containing 0.01 to 1 part by mass of a silane coupling agent represented by the following formula (1) with respect to 100 parts by mass of the glass fiber. Need to be.
R ₁ Si (OR ₂ ) ₃ (1)
(In the formula, R ₁ is an alkyl group having 2 to 10 carbon atoms having an amino group or an epoxy group at the terminal, and R ₂ is a methyl group or an ethyl group)
Glass fiber used as a reinforcing agent for polyamide resin generally includes a composition represented by a coupling agent for improving adhesiveness with the resin, a film forming agent for bundling glass fiber and making it easy to handle, etc. (For example, JP-A-9-301745).

  As the silane coupling agent, vinyl silane, acryl silane, epoxy silane, amino silane, methacryloxy silane, mercapto silane, and the like are generally known. It is necessary to use a ring agent. When other coupling agents are used, the adhesion between the resin and the glass is not sufficient when the fracture surface of the sample after the tensile test is observed. For the film-forming agent, generally known urethane resins, epoxy resins, acrylic resins, and the like can be used.

  Further, the cross section of the glass fiber may be a general round shape, a rectangle, or other irregular cross section.

  The method for producing the polyamide resin composition (C) of the present invention basically comprises a predetermined amount of polyamide monomer in the presence of a swellable layered silicate having an aliphatic primary amine inserted between appropriately selected layers. After charging the autoclave, an initiator such as water is appropriately used, and the melt polycondensation method may be used within a range of a temperature of 240 to 300 ° C., a pressure of 0.2 to 3 MPa, and a time of 1 to 15 hours. Further, water or acid may be used as the polymerization initiator in accordance with the characteristics of the polyamide monomer. However, if water is used in an amount of 20 parts by mass or more based on 100 parts by mass of the polyamide monomer, the polymerization rate is lowered and the productivity is lowered, which is not preferable.

When the nylon 6 resin is polymerized, it is preferable to polymerize in 5 parts by mass of pure water, a temperature of 250 to 280 ° C., a pressure of 0.5 to 2 MPa, and a range of 1 to 5 hours.
Moreover, in order to remove the polyamide monomer remaining in the polyamide resin composition after polymerization, it is preferable to scour the pellets of the polyamide resin composition with hot water. In this case, the treatment is preferably performed in hot water at 90 to 100 ° C. for 8 hours or more.

Furthermore, with respect to 100 parts by mass of the polyamide resin composition (C) and 100 parts by mass of the glass fiber, surface treatment is performed with a sizing agent containing 0.01 to 1 part by mass of a silane coupling agent represented by the following formula (1). The surface-treated glass fiber (B) thus prepared is generally melt-kneaded, but is not limited to this method.
R ₁ Si (OR ₂ ) ₃ (1)
(In the formula, R ₁ is an alkyl group having 2 to 10 carbon atoms having an amino group or an epoxy group at the terminal, and R ₂ is a methyl group or an ethyl group)
In producing the polyamide resin composition of the present invention, as long as its properties are not significantly impaired, a heat stabilizer, an antioxidant, a reinforcing material, a pigment, an anti-coloring agent, a weathering agent, a flame retardant, a plasticizer, a crystal nucleus An agent, a release agent and the like may be added.

  Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and mixtures thereof.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, the raw material used for the Example and the comparative example and the physical property measuring method are as follows.
1 Raw material (A) Polyamide monomer ε-Caprolactam AH salt containing equimolar amounts of adipic acid and hexamethylenediamine ω-laurolactam

(B) Swellable layered silicate-Synthetic fluorine mica (ME-100 manufactured by Corp Chemical Chemical Co.)
・ Montmorillonite (Kunipia F manufactured by Kunipia)
(C) Interlayer treatment agent (1) Aliphatic primary amine-Stearylamine (2) Treatment agent other than aliphatic primary amine-6-aminocaproic acid (D) Glass fiber-Circular shape with a diameter of 10 µm and a length of 3 mm Glass fiber having cross section (E) Silane coupling agent Amino silane coupling agent: 3-aminopropyltrimethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Epoxy silane coupling agent: 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Methacryloxy silane coupling agent: 3-methacryloxypropylmethyldimethoxysilane (KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd.)
2 Measuring method (1) Tensile breaking strength Measured at 23 ° C. according to ISO527. 180 MPa or more was accepted.
(2) Adhesion state between resin and glass fiber The adhesion state between the glass and the resin on the fracture surface was determined by observation with an optical microscope.
Judgment criteria are as follows.
A: Resin and glass fiber are firmly attached.
○: Resin and glass fiber are adhered.
X: Resin and glass fiber are not adhered.

Reference examples A1 to A6
Table 1 shows the swellable layered silicates (A) obtained by treating the various swellable silicates with various designated amines. A swellable synthetic fluorine mica that has not been treated with amine is defined as (A6).

Reference examples B1 to B4
Table 2 shows the surface-treated glass fibers (B) surface-treated with the designated silane coupling agent.

Reference examples C1-12
Next, the polyamide resin composition (C) shown in Table 3 was polymerized using the organically treated swellable synthetic fluorine mica (A) shown in Table 1 and the untreated swelling synthetic fluorine mica. . For C1 to C4 and C7 to C12, with respect to 1 kg of ε-caprolactam, 50 ml of pure water and a predetermined amount of layer-treated swellable layered silicate were charged, at 260 ° C. under 0.7 MPa for 1 hour, Polymerization was performed at normal pressure for 1 hour. For C5, 50 kg of pure water and a predetermined layer-treated swellable layered silicate are charged in an amount of 1 kg of a salt (AH salt) in which equimolar amounts of adipic acid and hexamethylenediamine are blended, and 280 ° C. The polymerization was carried out at 1.8 MPa for 2 hours and at normal pressure for 2 hours. For C6, 1 kg of ω-laurolactam was charged with 50 ml of pure water and a predetermined amount of a layered swellable layered silicate, and polymerized at 260 ° C. under 2.0 MPa for 2 hours and at normal pressure for 6 hours. did.

Example 1
As shown in Table 4, with respect to 100 parts by mass of the polyamide resin composition (C1), 30 parts by mass of glass fiber (B1) surface-treated with an amino-based silane coupling agent was added at 260 ° C. to TEM37BS manufactured by Toshiba Machine Co., Ltd. Was melt kneaded. A tensile test was performed on the obtained resin composition. Tensile strength and fracture surface were observed. Table 4 shows the results of the tensile test. Glass fiber and resin were firmly attached, and the breaking strength was high.

Example 2
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition was changed to C2. Table 4 shows the results of the tensile test. The adhesion between the glass fiber and the resin was good.

Example 3
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition was changed to C3. Table 4 shows the results of the tensile test. The adhesion between the glass fiber and the resin was good.

Example 4
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition was changed to C4. Table 4 shows the results of the tensile test. The adhesion between the glass fiber and the resin was good.

Example 5
A resin composition was obtained in the same manner as in Example 1 except that the amount of the surface-treated glass fiber (B1) was 100 parts by mass. Table 4 shows the results of the tensile test. The adhesion between the glass fiber and the resin was good.

Example 6
A resin composition was obtained in the same manner as in Example 1 except that the surface-treated glass fiber was changed to B2. Table 3 shows the results of the tensile test. The adhesion between the glass fiber and the resin was good.

Example 7
When the polyamide resin composition was C5 and melt kneaded with the surface-treated glass fiber (B1), a resin composition was obtained in the same manner as in Example 1 except that the temperature was 280 ° C. Table 4 shows the results of the tensile test. The adhesion between the glass fiber and the resin was good.

Example 8
When the polyamide resin composition was C6 and melt kneaded with the surface-treated glass fiber (B1), a resin composition was obtained in the same manner as in Example 1 except that the temperature was 220 ° C. Table 4 shows the results of the tensile test. The adhesion between the glass fiber and the resin was good.

Comparative Example 1
A resin composition was obtained in the same manner as in Example 1 except that no glass fiber was blended. Table 5 shows the results of the tensile test.

Comparative Example 2
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition C12 containing no swellable layered silicate was used. Table 5 shows the results of the tensile test. It was a reinforced product of ordinary glass fiber alone, and the adhesion between glass and resin was good.

Comparative Example 3
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition (C11) using the swellable synthetic fluorine mica not subjected to the surface treatment was used. Table 5 shows the results of the tensile test. Since the surface treatment of the swellable synthetic fluorinated mica was not performed, the adhesion between the glass fiber and the resin was poor, and the tensile strength was inferior to that of Example 1 having almost the same composition.

Comparative Example 4
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition (C9) in which the organic treatment amount of the swellable synthetic fluorinated mica was 0.1 parts by mass was used. Table 5 shows the results of the tensile test. Since the amount of stearylamine treated with the swellable fluorine mica was small, the adhesion between the glass fiber and the resin was poor, and the tensile strength was inferior to that of Example 1 having almost the same composition.

Comparative Example 5
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition (C10) in which the compounding amount of the swellable synthetic fluorine mica (A1) was 0.1 parts by mass was used. Table 5 shows the results of the tensile test. Since the compounding amount of the swellable synthetic fluorinated mica was too small, no synergistic effect of the glass fiber and the swellable synthetic fluorinated mica was found on the obtained resin composition.

Comparative Example 6
A resin composition was obtained in the same manner as in Example 1 except that the polyamide resin composition (C7) obtained by treating the swellable synthetic fluorine mica with 6-aminocaproic acid was used. Table 5 shows the results of the tensile test. There was no synergistic effect between the glass fiber and the swellable synthetic fluorine mica, and the adhesion between the glass fiber and the resin was also poor.

Comparative Example 7
A resin composition was prepared in the same manner as in Example 1 except that 300 parts by weight of the surface-treated glass fiber (B1) was added to the polyamide resin composition (C1). Table 5 shows the results of the tensile test. There were too many compounding quantities of glass fiber, there existed a problem in operativity, and the resin pellet could not be obtained.

Comparative Example 8
A resin composition was obtained in the same manner as in Example 1 except that the surface-treated glass (B3) using a methacryloxy silane coupling agent was used. Table 5 shows the results of the tensile test. Since a glass fiber surface treatment agent other than amino and epoxy was used, the adhesion between the resin and the glass fiber was poor.

Comparative Example 9
A resin composition was obtained in the same manner as in Example 1 except that the concentration of the aminosilane coupling agent in the glass fiber surface treatment agent was 0.001% by mass. Table 5 shows the results of the tensile test. Since the concentration of the aminosilane coupling agent was low, the adhesion between the resin and the glass fiber was poor, and the tensile strength was also low.

Comparative Example 10
Example 1 except that a polyamide resin composition (C7) using a swellable synthetic fluoromica treated with 6-aminocaproic acid and a glass fiber (B3) surface-treated with a methacryloxy silane coupling agent were used. A resin composition was obtained. Table 5 shows the results of the tensile test. The adhesion between the resin and the glass fiber was poor, and the tensile strength was low.

Comparative Example 11
A resin composition was obtained in the same manner as in Example 7 except that the glass fiber (B3) surface-treated with a methacryloxy silane coupling agent was used. Table 5 shows the results of the tensile test. Also in the case of nylon 66, when the surface treatment material of methacryloxy silane coupling agent is used, the synergistic effect of the swellable synthetic fluorine mica and the glass fiber is not observed, and the tensile strength is lower than that in Example 7, and the resin and the glass fiber. The adhesion was also poor.

Comparative Example 12
A resin composition was obtained in the same manner as in Example 8, except that glass fiber (B3) surface-treated with a methacryloxy silane coupling agent was used. Table 5 shows the results of the tensile test. Also in the case of nylon 12, when the surface treatment material of the methacryloxy silane coupling agent is used, the synergistic effect of the swellable synthetic fluorine mica and the glass fiber is not observed, and the tensile strength is lower than in Example 8, and the resin and the glass fiber. The adhesion was also poor.

Claims (4)

For 100 parts by mass of the swellable layered silicate, with respect to 100 parts by mass of the swellable layered silicate (A) in which 0.5 to 30 parts by mass of an aliphatic primary amine is inserted between the layers, A polyamide resin composition comprising a surface-treated glass fiber (B) surface-treated with a sizing agent containing 0.01 to 1% by mass of a silane coupling agent represented by the following formula (1): A polyamide resin composition (100 parts by mass) obtained by polymerizing a polyamide monomer after coexisting with 0.5 to 20 parts by mass of a swellable layered silicate represented by (A) and 0 to 20 parts by mass of pure water. C) A polyamide resin composition comprising 100 parts by mass and 5 to 200 parts by mass of the surface-treated glass fiber represented by (B).
R ₁ Si (OR ₂ ) ₃ (1)
(In the formula, R ₁ is an alkyl group having 2 to 10 carbon atoms having an amino group or an epoxy group at the terminal, and R ₂ is a methyl group or an ethyl group) Aliphatic primary amine is formed by mixing one or more of octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, stearylamine, and oleylamine. The polyamide resin composition according to claim 1, which is a mixture. The polyamide resin composition according to any one of claims 1 to 2, wherein the swellable layered silicate is represented by the following formula (2).
M _α (Mg _X Li _β ) Si ₄ O _Y F _Z (2)
(In the formula, M represents an ion-exchangeable cation, specifically sodium or lithium. Α, β, X, Y, and Z each represents a coefficient, and 0 ≦ α ≦ 1.0. 0 ≦ β ≦ 1.0, 2.5 ≦ X ≦ 4, 10 ≦ Y ≦ 15, 1.0 ≦ Z ≦ 2.0) The polyamide resin composition according to any one of claims 1 to 2, wherein the swellable layered silicate is represented by the following formula (3).
M _a Si (Al _2-a Mg) O ₁₀ (OH) ₂ .nH ₂ O (3)
(In the formula, M represents a cation such as sodium, and 0.25 ≦ a ≦ 0.7. The number of water molecules bonded to the interlayer ion-exchangeable cation depends on conditions such as cation species and humidity. (It is expressed as nH ₂ O in the formula)