JP2022059888A - Polyamide resin composition, molding prepared therewith, and method for producing polyamide resin composition - Google Patents

Abstract

To provide a polyamide resin composition that achieves improvement in the mechanical properties and thermal dimension stability of a molding as well as dischargeability in polymerization.SOLUTION: A polyamide resin composition contains a polyamide (A) 100 pts.mass, cellulose fibers (B) 0.1-50 pts.mass, and a fluorene compound represented by the general formula (1) (C) 0.1-30 pts.mass. (In the formula (1), ring Z is an aromatic hydrocarbon ring, R1 and R2 each denote a substituent, X is an amino group or a [(OR3)n-Y] group, Y is a hydroxyl group, a mercapto group, a glycidyloxy group or a (meth)acryloyloxy group, and R3 is an alkylene group.)SELECTED DRAWING: None

Description

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

In recent years, cellulose fibers have been used as a reinforcing material for polyamide. Cellulose fibers include those obtained from trees, those obtained from non-wood resources such as rice, cotton, kenaf, bagasse, abaca, and hemp, and bacterial cellulose produced by microorganisms. It is present in very large quantities. Cellulose fiber has excellent mechanical properties, and by containing it in the resin, it is expected to have the effect of improving the properties of the resin composition.

As a method for containing cellulose fibers in a thermoplastic resin, Patent Document 1 discloses a polyamide resin composition obtained by mixing a monomer constituting a polyamide and a cellulose fiber and carrying out a polymerization reaction. However, in the polyamide resin composition of Patent Document 1, the dispersibility of the cellulose fibers in the resin is still insufficient, and it cannot be said that the reinforcing effect of the cellulose fibers is completely exhibited, and the usage is limited. rice field. Further, there is a problem that the melt viscosity of the resin composition at the time of polymerization is high and the payout property is poor.

International Publication 2011/126038 Pamphlet

The present invention solves the above-mentioned problems, and is superior in mechanical properties and thermal dimensional stability of the obtained molded product as compared with the conventional polyamide resin composition containing cellulose fibers, and further, it is dispensed at the time of polymerization. It is an object of the present invention to provide an excellent polyamide resin composition.

As a result of diligent research to solve the above problems, the present inventors have achieved the above object by mixing a monomer constituting a polyamide, a cellulose fiber, and a specific fluorene-based compound and carrying out a polymerization reaction. We found that, and arrived at the present invention.

（上記一般式（１）中、環Ｚは芳香族炭化水素環、Ｒ^１およびＲ^２は置換基、Ｘはアミノ基または［（ＯＲ^３）_ｎ－Ｙ］基（前記式中、Ｙは、ヒドロキシル基、メルカプト基、グリシジルオキシ基または（メタ）アクリロイルオキシ基、Ｒ^３はアルキレン基、ｎは０以上の整数を示す。ｋは０～４の整数、ｍは０以上の整数、ｐは１以上の整数を示す。）
＜２＞下記式で示されるＭＤ方向における線膨張係数減少率（ＣＴＥＲ）の値が０＜ＣＴＥＲである＜１＞に記載のポリアミド樹脂組成物。
ＣＴＥＲ＝（ＣＴＥ_０－ＣＴＥ）／ＣＴＥ_０
（上記式中、ＣＴＥは、ポリアミド樹脂組成物のＭＤ方向における線膨張係数（ｐｐｍ／℃）を示し、ＣＴＥ_０は、前記ポリアミド樹脂組成物からフルオレン系化合物（Ｃ）を除いたポリアミド樹脂組成物のＭＤ方向における線膨張係数（ｐｐｍ／℃）を示す。）
＜３＞フルオレン系化合物（Ｃ）が、下記一般式（２）で表される化合物である＜１＞または＜２＞に記載のポリアミド樹脂組成物。

（上記一般式（２）中、Ｚ、Ｒ^１、Ｒ^２、Ｒ^３、ｎ、ｋ、ｍ、ｐは上記一般式（１）の場合と同一である。）
＜４＞フルオレン系化合物（Ｃ）が、９，９－ビス（４－ヒドロキシフェニル）フルオレンおよび／または９，９－ビス（４－ヒドロキシフェニル）フルオレンである＜１＞～＜３＞いずれかに記載のポリアミド樹脂組成物。
＜５＞セルロース繊維（Ｂ）の平均繊維径が１０μｍ以下である＜１＞～＜４＞いずれかに記載のポリアミド樹脂組成物。
＜６＞ポリアミド（Ａ）を構成するモノマーと、セルロース繊維（Ｂ）と、フルオレン系化合物（Ｃ）とを混合して重合反応をおこなう工程を含む＜１＞～＜５＞いずれかに記載のポリアミド樹脂組成物の製造方法。
＜７＞＜１＞～＜５＞いずれかに記載のポリアミド樹脂組成物を成形してなる成形体。 That is, the gist of the present invention is as follows.
<1> 100 parts by mass of the polyamide (A), 0.1 to 50 parts by mass of the cellulose fiber (B), and 0.1 to 30 parts by mass of the fluorene compound (C) represented by the following general formula (1). Polyamide resin composition contained.

(In the above general formula (1), ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is an amino group or a [(OR ³ ) _n −Y] group (in the above formula, Y is A hydroxyl group, a mercapto group, a glycidyloxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more. K is an integer of 0 to 4, m is an integer of 0 or more, and p is 1. The above integers are shown.)
<2> The polyamide resin composition according to <1>, wherein the value of the coefficient of linear expansion coefficient reduction (CTER) in the MD direction represented by the following formula is 0 <CTER.
CTER = (CTE ₀ -CTE) / CTE ₀
(In the above formula, CTE indicates the linear expansion coefficient (ppm / ° C.) of the polyamide resin composition in the MD direction, and CTE ₀ is the polyamide resin composition obtained by removing the fluorene compound (C) from the polyamide resin composition. Indicates the coefficient of linear expansion (ppm / ° C.) in the MD direction of.)
<3> The polyamide resin composition according to <1> or <2>, wherein the fluorene compound (C) is a compound represented by the following general formula (2).

(In the general formula (2), Z, R ¹ , R ² , R ³ , n, k, m, and p are the same as in the general formula (1).)
<4> The fluorene compound (C) is any of <1> to <3>, which is 9,9-bis (4-hydroxyphenyl) fluorene and / or 9,9-bis (4-hydroxyphenyl) fluorene. The polyamide resin composition according to the above.
<5> The polyamide resin composition according to any one of <1> to <4>, wherein the average fiber diameter of the cellulose fiber (B) is 10 μm or less.
<6> The invention according to any one of <1> to <5>, which comprises a step of mixing a monomer constituting the polyamide (A), a cellulose fiber (B), and a fluorene compound (C) to carry out a polymerization reaction. A method for producing a polyamide resin composition.
<7> A molded product obtained by molding the polyamide resin composition according to any one of <1> to <5>.

According to the present invention, a polyamide resin composition having excellent mechanical properties and thermal dimensional stability of the obtained molded product and further excellent in payout during polymerization as compared with the conventional polyamide resin composition containing cellulose fibers can be obtained. Can be provided.

[Polyamide resin composition]
The polyamide resin composition of the present invention contains a polyamide (A), a cellulose fiber (B), and a fluorene compound (C).

The polyamide (A) used in the present invention is a polymer having an amide bond formed from an amino acid, lactam, or a diamine and a dicarboxylic acid.

Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid.

Examples of the lactam include ε-caprolactam and ω-laurolactam.

Examples of the diamine include tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5 -Methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5 -Trimethylcyclohexane, 3,8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) Examples include propane and bis (aminopropyl) piperazine.

Examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid and 5-methylisophthalic acid. , 5-Sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycolic acid and the like.

Specific examples of the polyamide (A) used in the present invention include, for example, polycaproamide (polyamide 6), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), and polyhexamethylene se. Bacamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), polyhexamethylene dodecamide (polyamide 612), polyundecamethylene adipamide (polyamide 116), polydodecamethylene adipamide (polyamide 126) , Polydodecamethylene sebacamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polytrimethylhexamethylene terephthalamide (polyamide TMHT), poly Hexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene terephthal / isophthalamide (polyamide 6T / 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polybis (4-Aminocyclohexyl) methanedodecamide (polyamide PACM12), polybis (3-methyl-4-aminocyclohexyl) methanedodecamide (polyamide dimethyl PACM12), polymethoxylylen adipamide (polyamide MXD6), polynonamethylene terephthalamide (Polyamide 9T), Polynonamethylene Hexahydroterephthalamide (Polyamide 9T (H)), Polydecamethylene terephthalamide (Polyamide 10T), Polydecamethylene decamide (Polyamide 1010), Polydecamethylene dodecamide (Polyamide 1012) , Polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)). The polyamide (A) may be either a copolymer of two or more kinds of monomers constituting these polymers or a mixture of two or more kinds of polymers selected from these polymers. Among them, from the viewpoints of improving the mechanical properties and thermal dimensional stability of the obtained molded product and improving the payout property at the time of polymerization, the polyamide 6, polyamide 66, polyamide 11, polyamide 12 and copolymers and mixtures thereof are used. One or more kinds of polyamides selected from the group consisting of polyamide 6, polyamide 66 and copolymers thereof and mixtures thereof are more preferable, and polyamide 6 is further preferable.

The molecular weight of the polyamide (A) is not particularly limited, and for example, it may have a molecular weight such that the relative viscosity described later is achieved.

The relative viscosity of the polyamide (A) was set at a temperature of 25 ° C. using 96% sulfuric acid as a solvent from the viewpoint of improving the mechanical properties and thermal dimensional stability of the obtained molded product and improving the dispenseability during polymerization. When measured at a concentration of 1 g / 100 mL, it is preferably 1.5 to 5.0, and more preferably 1.7 to 4.0. When the cellulose fibers are dispersed in the polyamide in advance as described later, it is preferable that the relative viscosity of the polyamide in which the cellulose fibers are dispersed is within the above range.

The polyamide (A) can be produced by a known polycondensation method or a method using a solid phase polymerization method in combination.

The cellulose fiber (B) used in the present invention includes, for example, those derived from plants such as wood, rice, cotton, kenaf, bagasse, abaca, and hemp, and those derived from organisms such as bacterial cellulose, baronia cellulose, and squirrel cellulose. , Regenerated cellulose and cellulose derivatives.

By containing the cellulose fiber (B), the resin composition of the present invention can improve the mechanical properties and thermal dimensional stability of the obtained molded product. In order to sufficiently improve the mechanical properties and thermal dimensional stability, it is preferable to uniformly disperse the cellulose fibers in the resin without agglomerating them. The surface area of the cellulose fiber is preferably large because the more hydroxyl groups on the surface of the cellulose fiber in contact with the polyamide, the easier it is to disperse. Therefore, the cellulose fiber (B) is preferably as fine as possible. The cellulose fiber used is not particularly limited as long as it can be uniformly dispersed in the resin composition, and may be chemically unmodified or chemically modified.

The average fiber diameter of the cellulose fiber (B) in the resin composition of the present invention is not particularly limited, but is preferably 10 μm or less, preferably 1 μm or less, from the viewpoint of improving the mechanical properties and thermal dimensional stability of the obtained molded product. The following is more preferable, 500 nm or less is further preferable, 1 to 400 nm is sufficiently preferable, 5 to 100 nm is particularly preferable, and 20 to 100 nm is most preferable. On the other hand, the lower limit of the average fiber diameter is preferably 4 nm or more in consideration of the productivity of the cellulose fiber. In the embodiment in which the cellulose fibers are added during the polymerization of the polyamide (A) as described later, the average fiber diameter of the cellulose fibers after the melt polymerization of the polyamide (A) or when the molded product is formed is determined by the melt polymerization or molding. The cellulose fibers are subjected to shearing force and tend to be smaller than the used cellulose fibers. In order to make the average fiber diameter of the cellulose fiber (B) in the molded body 10 μm or less, a cellulose fiber having an average fiber diameter of 10 μm or less may be used.

The average fiber length of the cellulose fiber (B) in the resin composition of the present invention is not particularly limited, but is preferably 0.2 μm or more from the viewpoint of improving the mechanical properties and thermal dimensional stability of the obtained molded product. , 0.5 μm or more, more preferably 0.8 μm or more. The upper limit of the average fiber length of the cellulose fiber (B) is not particularly limited, and the average fiber length is usually preferably 100 μm or less, which improves the mechanical properties and thermal dimensional stability of the obtained molded product and polymerizes. From the viewpoint of improving the payout property at the time, it is more preferably 50 μm or less, further preferably 30 μm or less, and particularly preferably 10 μm or less. In the embodiment in which the cellulose fibers are added during the polymerization of the polyamide (A) as described later, the average fiber length of the cellulose fibers after the melt polymerization of the polyamide (A) or when the molded product is formed is determined by the melt polymerization or molding. The cellulose fibers are subjected to shearing force and tend to be smaller than the used cellulose fibers. In order to make the average fiber length of the cellulose fiber (B) in the molded product 0.2 μm or more, a cellulose fiber having an average fiber length of 0.2 μm or more may be used.

In the present invention, the average fiber diameter and the average fiber length of the cellulose fiber (B) in the resin composition refer to the average fiber diameter and the average fiber length in the molded product obtained by using the resin composition. Specifically, it refers to the average fiber diameter and the average fiber length measured by the measuring method described later. The average fiber diameter of the cellulose fiber (B) in the resin composition is almost the same as the average fiber diameter and the average fiber length in the molded product obtained by using the resin composition.

In order to make the average fiber diameter of the cellulose fiber 10 μm or less, it is preferable to use a cellulose fiber having an average fiber diameter of 10 μm or less as the cellulose fiber to be blended in the polyamide. Cellulose fibers (B) having an average fiber diameter of 10 μm or less can be obtained by tearing the cellulose fibers into microfibrils. As a means for making microfibrils, various crushing devices such as a ball mill, a stone mill crusher, a high-pressure homogenizer, and a mixer can be used. Examples of commercially available products of the above-mentioned aqueous dispersion of microfibrillated cellulose fibers include "Cerish" manufactured by Daicel FineChem and "Nanoforest" manufactured by Chuetsu Pulp & Paper Co., Ltd.

As the cellulose fiber (B) having an average fiber diameter of 10 μm or less, finely divided cellulose can also be used. The finely divided cellulose can be produced, for example, by oxidizing the cellulose fibers in an aqueous solution containing an N-oxyl compound, an copolymer and an alkali metal bromide, and then washing and defibrating the cellulose fibers. Examples of the N-oxyl compound include 2,2,6,6-Tetrapiperidine-1-oxyl radical, and examples of the copolymer include sodium hypochlorite and sodium chlorite. The reaction is carried out after adding an alkaline compound such as an aqueous sodium hydroxide solution to bring the pH to around 10 until no change in pH is observed. The reaction temperature is preferably room temperature. After the reaction, it is preferable to remove the N-oxyl compound, the copolymer, and the alkali metal bromide remaining in the system. Examples of the washing method include filtration and centrifugation. Examples of the defibration method include the methods using various pulverizers mentioned in the above-mentioned microfibrillation.

As the cellulose fiber (B) having an average fiber diameter of 10 μm or less, an aggregate of cellulose fibers produced as waste yarn can also be used in the manufacturing process of a fiber product using the cellulose fibers. Examples of the textile product manufacturing process include spinning, woven fabric, non-woven fabric manufacturing, and processing of textile products. Since the aggregate of these cellulose fibers is a waste thread after the cellulose fibers have undergone these steps, the cellulose fibers are made finer.

As the cellulose fiber (B) having an average fiber diameter of 10 μm or less, bacterial cellulose produced by bacteria can also be used. Examples of the bacterial cellulose include those produced by producing acetic acid bacteria of the genus Acetobacter. Cellulose in plants is formed by converging the molecular chains of cellulose and is formed by bundling very fine microfibrils, whereas cellulose produced by acetic acid bacteria originally has a width of 20 to 50 nm. It is ribbon-shaped and forms an extremely fine mesh compared to plant cellulose. Bacterial cellulose may coexist with acetic acid because the bacteria produce acetic acid with the cellulose. In that case, it is preferable to replace the solvent with water.

Further, the cellulose fiber may be an unmodified cellulose fiber in which the cellulose-derived hydroxyl group is not modified by any substituent, or the cellulose-derived hydroxyl group (particularly a part thereof) is modified (or substituted). It may be a modified cellulose fiber. The substituent introduced into the hydroxyl group derived from cellulose is not particularly limited, and examples thereof include a hydrophilic substituent and a hydrophobic substituent. In the modified cellulose fiber, the hydroxyl group modified (or substituted) by the substituent is a part of the hydroxyl groups derived from cellulose, and the degree of substitution thereof is preferably 0.05 to 2.0. It is more preferably 1 to 1.0, and even more preferably 0.1 to 0.8. The degree of substitution represents the number of introduced substituents per unit structure (glucopyranose ring) constituting cellulose. That is, it is defined as "the value obtained by dividing the number of moles of the introduced substituent by the total number of moles of the glucopyranose ring". Since pure cellulose has three substitutable hydroxyl groups per unit structure (glucopyranose ring), the theoretical maximum value of the degree of substitution of the cellulose fiber of the present invention is 3, and the theoretical minimum value is 0. Examples of the hydrophilic substituent include a carboxyl group, a carboxymethyl group, a phosphate ester group and the like. Examples of the hydrophobic substituent include a silyl ether group, an alkyl ether group, and an alkyl ester group.

The cellulose fiber (B) is an unmodified cellulose fiber or a cellulose modified with a hydrophilic substituent from the viewpoint of improving the mechanical properties and thermal dimensional stability of the obtained molded product and improving the dispenseability at the time of polymerization. It is preferably a fiber or a mixed fiber thereof, and more preferably an unmodified cellulose fiber.

The aspect ratio (average fiber length / average fiber diameter) of the cellulose fiber (B) in the molded product of the present invention is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more. , 50 or more is particularly preferable. By setting the aspect ratio to 10 or more, the upper limit of the aspect ratio of the cellulose fiber (B) is set from the viewpoint of improving the mechanical properties and thermal dimensional stability of the obtained molded product and improving the payout property at the time of polymerization. The aspect ratio is not particularly limited, and is preferably 200 or less, more preferably 100 or less.

In the polyamide resin composition of the present invention, the content of the cellulose fiber (B) needs to be 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyamide (A), and the obtained molded product has a content of 0.1 to 50 parts by mass. From the viewpoint of improving mechanical properties and thermal dimensional stability and improving payout property during polymerization, the content is preferably 0.5 to 20 parts by mass, more preferably 1 to 12 parts by mass, and 1 to 1 to 12 parts by mass. It is more preferably 10 parts by mass, particularly preferably 1 to 8 parts by mass, and most preferably 1 to 4 parts by mass. When the content of the cellulose fiber is less than 0.1 part by mass with respect to 100 parts by mass of the polyamide (A), the effect of improving the mechanical properties and thermal dimensional stability of the obtained molded product is reduced, which is not preferable. On the other hand, when the content of the cellulose fiber (B) exceeds 50 parts by mass with respect to 100 parts by mass of the polyamide (A), it becomes difficult to contain the cellulose fiber (B) in the resin composition, or the molten resin. Since the fluidity of the resin is deteriorated, the moldability of the resin composition is deteriorated, and the cellulose fibers are raised on the resin surface, which is not preferable because the surface appearance is deteriorated.

（上記一般式（１）中、環Ｚは芳香族炭化水素環、Ｒ^１およびＲ^２は置換基、Ｘはアミノ基または［（ＯＲ^３）_ｎ－Ｙ］基（前記式中、Ｙは、ヒドロキシル基、メルカプト基、グリシジルオキシ基または（メタ）アクリロイルオキシ基、Ｒ^３はアルキレン基、ｎは０以上の整数を示す。ｋは０～４の整数、ｍは０以上の整数、ｐは１以上の整数を示す。） The fluorene-based compound (C) used in the present invention is a fluorene-based compound represented by the following general formula (1) (hereinafter, simply referred to as “fluorene-based compound”).

(In the above general formula (1), ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is an amino group or a [(OR ³ ) _n −Y] group (in the above formula, Y is A hydroxyl group, a mercapto group, a glycidyloxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more. K is an integer of 0 to 4, m is an integer of 0 or more, and p is 1. The above integers are shown.)

In the above general formula (1), the ring Z is an aromatic hydrocarbon ring, and examples thereof include a benzene ring, an indene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, a terphenyl ring, and a binaphthyl ring. Of these, a benzene ring, a naphthalene ring, and a biphenyl ring are preferable, and a benzene ring is more preferable. The two rings Z may be the same ring or different rings.

Examples of the substituent R ¹ include a cyano group, a halogen atom, a hydrocarbon group, and an acyl group. The substitution number k is an integer of 0 to 4, preferably 0 to 1, and more preferably 0. The two substitution numbers k may be the same or different.

Examples of the substituent ^R2 to be substituted with the ring Z include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclohexyl group, a phenyl group, a trill group, a xsilyl group, a naphthyl group, a benzyl group and a phenethyl group. Group, methoxy group, ethoxy group, cyclohexyloxy group, phenoxy group, benzyloxy group, methylthio group, acetyl group, methoxycarbonyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, cyano group, substituted amino The group is mentioned. The substitution number m is selected according to the type of ring Z, and is an integer of 0 or more, preferably 0 to 8, more preferably 0 to 4, and even more preferably 0. In the two rings Z, the substitution number m may be the same or different.

Examples of the alkylene group represented by R3 in X of the general formula ( ¹ ) include an ethylene group, a propylene group, a trimethylene group, a 1,2-butanjiyl group, a tetramethylene group and the like. When n is 2 or more, the type of the alkylene group may be composed of the same alkylene group or may be composed of different alkylene groups. Further, in the two rings Z ^, the types of R3 may be the same or different.

The number (number of added moles) n of the oxyalkylene group (OR ³ ) may be 0 or more, preferably 0 to 15, more preferably 0 to 10, and preferably 0 to 5. More preferred. When the substitution number p is 2 or more, the substitution number n may be the same or different in the 2 or more [(OR ³ ) _n −Y] groups substituted with the ring Z.

X is an amino group or a [(OR ³ ) _n —Y] group. Y is a hydroxyl group, a mercapto group, a glycidyloxy group or a (meth) acryloyloxy group. Of these, a hydroxyl group is preferable. In the general formula (1), the compound in which Y is a hydroxyl group and the alkylene oxide adduct of these compounds are represented by the following general formula (2).

（上記一般式（２）中、Ｚ、Ｒ^１、Ｒ^２、Ｒ^３、ｎ、ｋ、ｍ、ｐは上記一般式（１）の場合と同一である。）

(In the general formula (2), Z, R ¹ , R ² , R ³ , n, k, m, and p are the same as in the general formula (1).)

The number of substitutions p of X is 1 or more, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. The number of substitutions p may be the same or different in each ring Z, but it is preferable that they are the same.

In the above general formula (1) or the above general formula (2), the substitution position of X is not particularly limited, and it may be substituted with an appropriate substitution position of the ring Z. For example, when the ring Z is a benzene ring, X may be substituted at the 2- to 6-position of the phenyl group, preferably at the 4-position.

Examples of fluorene compounds include 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxynaphthyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, and 9,9-. Examples include bis (hydroxy (poly) alkoxynaphthyl) fluorenes. These compounds include compounds in which the hydroxyl group is replaced with a mercapto group, a glycidyloxy group or a (meth) acryloyloxy group.

Examples of 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-. Bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9 -Bis (2,4-dihydroxyphenyl) fluorene can be mentioned.

The 9,9-bis (hydroxynaphthyl) fluorene corresponds to the above-mentioned 9,9-bis (hydroxyphenyl) fluorene, and a compound in which the phenyl group is replaced with a naphthyl group, for example, 9,9-bis (6-). Hydroxy-2-naphthyl) fluorene and 9,9-bis (5-hydroxy-1-naphthyl) fluorene can be mentioned.

Examples of 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorene include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 9,9-bis [4- (2-hydroxy). Phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-Bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9- Examples thereof include bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene and 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene.

The 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes correspond to the above-mentioned 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, and a compound in which the phenyl group is replaced with a naphthyl group, for example. Examples thereof include 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene and 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene.

As the fluorene-based compound (C), one of the above-mentioned fluorene-based compounds may be used alone, or a plurality of kinds may be used in combination.

By containing the fluorene compound (C), the polyamide resin composition of the present invention has improved mechanical properties and thermal dimensional stability of the obtained molded product, and further has excellent payout property during polymerization. can do. If only the cellulose fiber (B) is contained in the polyamide resin composition, the obtained molded product cannot obtain sufficient mechanical properties and thermal dimensional stability, and the payout property at the time of polymerization is not sufficient. Further, even if the polyamide resin composition contains only the fluorene compound (C), sufficient mechanical properties and thermal dimensional stability cannot be obtained. Since the polyamide resin composition of the present invention contains the fluorene compound (C), the fluidity is improved, so that the processing temperature during the melt processing can be lowered, and the heat deterioration during the melt processing can be performed. Can be suppressed.

In the polyamide resin composition of the present invention, the content of the fluorene-based compound (C) needs to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyamide (A), and the obtained molded product From the viewpoint of further improving the mechanical properties and thermal dimensional stability of the above, and improving the payout property at the time of polymerization, the content is preferably 0.5 to 25 parts by mass, more preferably 1 to 15 parts by mass. It is more preferably 1 to 5 parts by mass. When the content of the fluorene compound (C) is less than 0.1 parts by mass, the mechanical properties and thermal dimensional stability of the obtained molded product are not improved, and the payout property at the time of polymerization is not improved, which is not preferable. On the other hand, when the mass of the fluorene compound (C) exceeds 30 parts by mass, the effects of improving mechanical properties, thermal dimensional stability and payout property are saturated, and no further effect can be expected, and the resin is not only The molded product of the composition is not preferable because the fluorene compound bleeds out on the surface and the appearance is impaired and the mechanical properties are insufficient. When a plurality of fluorene compounds (C) are used in combination, the total content thereof may be within the above range.

The polyamide resin composition of the present invention is a layered silicate, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, a mold release agent, a lubricant, and an antistatic agent as long as the effects of the present invention are not impaired. It may contain additives such as agents and crystal nucleating agents.

The polyamide resin composition of the present invention preferably has a bending strength of 115 MPa or more, more preferably 120 MPa or more, and even more preferably 125 MPa or more, which indicates the mechanical properties of the molded product.

The polyamide resin composition of the present invention preferably has a linear expansion coefficient of 75 ppm / ° C. or lower, more preferably 65 ppm / ° C. or lower, and 55 ppm / ° C. or lower, which indicates the thermal dimensional stability of the molded product. Is even more preferable. Further, the value of CTER obtained by the measurement method described later, which shows the improvement rate of thermal dimensional stability with the conventional polyamide resin composition containing cellulose fibers, is preferably more than 0, preferably 0.10 or more. Is more preferable, and 0.15 or more is further preferable.

In the polyamide resin composition of the present invention, the yield showing the payout property of the melt polymer is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more.

[Manufacturing method of polyamide resin composition]
The method for producing the polyamide resin composition of the present invention is not particularly limited, and for example, it can be produced by adding a cellulose fiber and a fluorene compound during the polymerization of the polyamide (A). In the method for producing a polyamide resin composition of the present invention, more specifically, a monomer constituting the polyamide, an aqueous dispersion of cellulose fibers, and a fluorene-based compound are mixed, and if necessary, a catalyst is added to polymerize (for example, melt). Polymerization) is performed to produce a polyamide containing a cellulose fiber and a fluorene-based compound (hereinafter, abbreviated as "polyamide X"). The resin composition may have a so-called pellet form. The time of polymerization of the polyamide (A) includes not only the time of polymerization using a monomer constituting the polyamide (A) but also the time of polymerization using a prepolymer capable of forming a polyamide.

Polyamide X is, for example, made into a uniform dispersion by stirring a mixture of a monomer or prepolymer constituting the polyamide (A), an aqueous dispersion of cellulose fibers, and a fluorene-based compound with a mixer or the like, and the mixture is obtained. Can be obtained by heating and heating the temperature to 150 to 270 ° C. to melt-polymerize while evaporating water. The water dispersion of the cellulose fibers used for melt polymerization can be obtained by stirring purified water and the cellulose fibers with a mixer or the like. The solid content of the cellulose fiber in the aqueous dispersion is preferably 0.01 to 50% by mass.

In order to increase the polymerization efficiency, a polymerization catalyst may be used. The polymerization catalyst may be added in any of the steps of before melt polymerization, during melt polymerization, before scouring, during scouring, and after scouring, but it is preferably added before melt polymerization. The polymerization catalyst is not particularly limited as long as it is usually used for melt polymerization of polyamide. At the time of polymerization, a catalyst such as phosphoric acid or phosphorous acid may be added as needed.

When bacterial cellulose is used as the cellulose fiber, a solution obtained by immersing the bacterial cellulose in purified water and substituting with a solvent may be used as the aqueous dispersion of the cellulose fiber. When a solvent-substituted bacterial cellulose is used, it is preferable to mix the one adjusted to a predetermined concentration after the solvent substitution with the monomers constituting the polyamide and proceed with the polymerization reaction in the same manner as described above.

In the above method, the cellulose fibers having an average fiber diameter of 10 μm or less are subjected to the polymerization reaction as they are in an aqueous dispersion, and a fluorene-based compound is added. Therefore, the cellulose fibers are polymerized in a state of good dispersibility. Can be subjected to a reaction. Furthermore, the cellulosic fibers subjected to the polymerization reaction have improved dispersibility by interacting with the monomers, water, and fluorene-based compounds during the polymerization reaction, and by stirring under the above-mentioned temperature conditions, and the fibers are improved in dispersibility. It is possible to obtain a resin composition in which cellulose fibers having a small average fiber diameter are well dispersed without agglomeration. According to the above method, the average fiber diameter of the cellulose fibers contained in the resin composition after the completion of the polymerization reaction may be smaller than that of the cellulose fibers added before the polymerization reaction.

By such a method, the cellulose fibers can be uniformly dispersed in the polyamide with a relatively small average fiber diameter without agglomeration. The monomer polymerized in the presence of cellulose fibers may be a prepolymer. Here, the prepolymer is an intermediate product in the process of polymerizing the monomer.

At the time of the polymerization reaction (for example, before the polymerization reaction, during the polymerization reaction or after the polymerization reaction), an additive which may be added to the above-mentioned resin composition may be added.

In the above method, the step of drying the cellulose fibers becomes unnecessary, and the production can be performed without going through the step of causing the scattering of fine cellulose fibers, so that the polyamide or polyamide resin composition can be obtained with good operability. Further, since it is not necessary to replace water with an organic solvent for the purpose of uniformly dispersing the monomer and the cellulose fiber, it is excellent in handling and can suppress the discharge of chemical substances during the manufacturing process.

After completion of melt polymerization, the obtained polyamide X is preferably dispensed and then cut into pellets. The size of the pellet is not particularly limited, but from the viewpoint of handling and the efficiency of refining described later, it is preferably 2 to 5 mm in diameter and 3 to 6 mm in length, and 3 to 4 mm in diameter and 4 to 5 mm in length. Is more preferable.

Polyamide X is preferably refined by immersing it in water at 90 to 100 ° C. in order to remove unreacted monomers and oligomers.

Polyamide X after melt polymerization, or polyamide X after scouring if necessary, is heated at a temperature below the melting point of polyamide X for 30 minutes or more under an inert gas flow or under reduced pressure in order to further increase the degree of polymerization. May be solid-phase polymerization. If the heating temperature is lower than (melting point of polyamide X −75 ° C.), the reaction rate may slow down, and the polyamide may be fused or colored near the melting point of polyamide X. ..

The polyamide resin composition of the present invention is excellent in mechanical properties and thermal dimensional stability, and can obtain a molded product having excellent payout property at the time of polymerization.

[Molded product]
The molded product of the present invention can be obtained by molding the above-mentioned polyamide resin composition of the present invention by a known molding method. Known molding methods include, for example, injection molding, blow molding, extrusion molding, inflation molding, vacuum molding after sheet processing, pneumatic molding, and vacuum pneumatic molding. Molding made by processing from an injection-molded molded body, an extrusion-molded film or sheet (hereinafter referred to as "film or the like"), these films or the like, or a stretched film or the like by the above-mentioned molding method. A body, a hollow body formed by blow molding, a molded body processed from this hollow body, a filament (fiber) obtained by melt spinning, and a filament formed by stretching the filament are obtained through a 3D printer. It is possible to obtain a molded product to be obtained, a molded product obtained by passing pellets or crushed products through a 3D printer, and the like.

Among the molding methods described above, injection molding is preferable. As injection molding, in addition to general injection molding, gas injection molding, injection press molding and the like can also be adopted. The injection molding machine is not particularly limited, and examples thereof include a screw in-line type injection molding machine and a plunger type injection molding machine. The polyamide resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled and solidified in a predetermined shape, and then molded from the mold. Taken out. The resin temperature at the time of injection molding is preferably equal to or higher than the melting point of the polyamide resin composition, particularly polyamide, and is preferably less than "melting point + 100 ° C.". When the polyamide resin composition is heated and melted, it is preferable to use a sufficiently dried polyamide resin composition. If the amount of water contained is large, the resin may foam in the cylinder of the injection molding machine, making it difficult to obtain an optimum molded product. The water content of the resin composition used for injection molding is preferably less than 0.3% by mass, more preferably less than 0.1% by mass.

As the injection molding conditions of the polyamide resin composition of the present invention, the cylinder temperature is preferably equal to or higher than the melting point or the flow start temperature of the resin composition, more preferably 190 to 270 ° C., and the mold temperature is "resin". The melting point of the composition is preferably −20 ° C. or lower. If the molding temperature is too low, the moldability may become unstable, such as a short circuit in the molded product, or the surface glossiness of the obtained molded product may be lost. On the other hand, if the molding temperature is too high, the polyamide resin composition may be decomposed, which may cause a decrease in the strength of the obtained molded product or a decrease in the surface glossiness.

Since the molded body of the present invention is excellent in mechanical properties and thermal dimensional stability of the obtained molded body, it can be suitably used for various automobile parts, electric and electronic parts. Automotive parts include, for example, speedometers on instrument panels, tachometers, fuel gauges, water temperature gauges, distance meters and other instruments, car stereos, navigation systems, various switches around air conditioners, buttons, and center consoles. Examples include shift levers, side brake grips, door trims, armrests, and door levers. Examples of electric and electronic parts include various parts and housings around personal computers, mobile phone parts and housings, and other OA equipment parts.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

A. Measuring method (1) Average fiber diameter and average fiber length of cellulose fibers in the test piece The multipurpose test piece A type obtained in (2) described later was used as the test piece.
From the test piece, a section having a thickness of 100 nm was taken using a frozen ultramicrotome, the section was stained with _OsO4 (osmium tetroxide), and then observed using a transmission electron microscope (JEM-1230 manufactured by JEOL Ltd.). Was done. From the electron microscope image, the length in the direction perpendicular to the longitudinal direction and the length in the longitudinal direction of the cellulose fiber (single fiber) were measured. At this time, the maximum length in the vertical direction was defined as the fiber diameter. In the same manner, the fiber diameter and fiber length of 10 cellulose fibers (single fibers) were measured, and the average value of 10 fibers was calculated and used as the average fiber diameter and average fiber length. For cellulose fibers with a large fiber diameter and average fiber length, observe them using a stereoscopic microscope (OLYMPUS SZ-40) with a 10 μm section cut out with a microtome or with the test piece as it is. Then, the fiber diameter and the fiber length were measured from the obtained images in the same manner as above, and the average fiber diameter and the average fiber length were obtained.

(2) Mechanical characteristics (bending strength)
The sufficiently dried resin composition was injection molded using an injection molding machine (NEX110-12E manufactured by Nissei Resin Industry Co., Ltd.) to obtain a multipurpose test piece A type conforming to ISO standard 3167. The conditions for injection molding were a resin temperature of 250 ° C., a mold temperature of 70 ° C., a holding pressure of 30 to 100 MPa, an injection speed of 10 to 150 mm / s, and a cooling time of 20 seconds.
The bending strength of the obtained multipurpose test piece was measured by an ISO178-compliant three-point support bending method (distance between fulcrums: 64 mm, test speed: 2 mm / min, test atmosphere: 23 ° C, 50% RH, absolute dry state). bottom. Bending strength was evaluated according to the following criteria.
⊚: 125 MPa ≤ bending strength (best);
◯: 120 MPa ≤ bending strength <125 MPa (good);
Δ: 115 MPa ≤ bending strength <120 MPa (no problem in practical use);
X: Bending strength <115 MPa (there is a problem in practical use).

(3) Thermal dimensional stability (coefficient of linear expansion)
The test piece obtained in (2) was cut into 10 mm × 4 mm × 4 mmt so that the flow direction (MD direction) of the resin at the time of injection molding was the longitudinal direction. The coefficient of linear expansion in the MD direction of the sample was measured with a standard expansion probe using a TMA2940 Thermomechanical Analyzer manufactured by TA Instruments based on JIS K 7197. It is assumed that a load of 50 mN is applied by nitrogen flow and the measurement is performed at a temperature rise of 5 ° C./min from 10 ° C. to 150 ° C. At this time, the average value in the region of 20 to 150 ° C. is calculated (n = 3). The coefficient of linear expansion was evaluated according to the following criteria according to the following criteria.
⊚: 55 ppm / ° C ≧ coefficient of linear expansion (best);
◯: 65 ppm / ° C ≧ coefficient of linear expansion> 55 ppm / ° C (good);
◯: 75 ppm / ° C ≧ coefficient of linear expansion> 65 ppm / ° C (no problem in practical use);
X: Coefficient of linear expansion> 75 ppm / ° C (There is a problem in practical use).

(4) Mechanical properties (CTER)
In Examples 1 to 16, the same operation was carried out except that the fluorene compound was not contained, and dried polyamide X pellets were obtained.
Using the obtained sufficiently dried resin composition, a sample cut out was obtained from the multipurpose test piece A type obtained by performing the same operation as in (2) by performing the same operation as in (3). CTE ₀ (ppm / ° C.).
The coefficient of linear expansion obtained in (3) above was defined as CTE (ppm / ° C.), and the value of CTER was obtained from the following formula.
CTER = (CTE ₀ -CTE) / CTE ₀
(In the above formula, CTE indicates the linear expansion coefficient (ppm / ° C.) of the polyamide resin composition in the MD direction, and CTE ₀ is the polyamide resin composition obtained by removing the fluorene compound (C) from the polyamide resin composition. Indicates the coefficient of linear expansion (ppm / ° C.) in the MD direction of.)
CTER was evaluated according to the following criteria.
⊚: 0.15 ≦ CTER (best);
◯: 0.10 ≦ CTER <0.15 (good);
Δ: 0 <CTER <0.10 (no problem in practical use);
X: CTER ≦ 0 (there is a practical problem).

(6) Yield (delivery property)
The melt polymer was extruded at a nitrogen pressure of 0.7 MPa, and the yield of the recovered resin composition was calculated with respect to the theoretical yield calculated from the charged monomer. Yields were evaluated according to the following criteria.
⊚: 90% ≤ yield (best);
◯: 85% ≤ yield <90% (good);
Δ: 80% ≤ Yield <85% (no problem in practical use);
X: Yield <80% (there is a problem in practical use).

(7) Comprehensive evaluation Examples 1 to 16 were comprehensively evaluated based on the evaluation results of mechanical properties and thermal dimensional stability.
⊚: All evaluation results for the above characteristics were ◎;
◯: Of all the evaluation results for the above characteristics, the lowest evaluation result was ◯;
Δ: Of all the evaluation results for the above characteristics, the lowest evaluation result was Δ;
X: Of all the evaluation results for the above-mentioned characteristics, the lowest evaluation result was ×.

B. Raw Materials The raw materials used in Examples and Comparative Examples are shown below.

(1) Polyamide monomer component ・ ε-caprolactam: Polyamide 66 salt (hexamethylenediamine-adipic acid isomol salt, polyamide prepolymer) manufactured by Ube Corporation.

(2) Cellulose fiber ・ KY100G: Serish KY100G manufactured by Daicel FineChem, which contains 10% by mass of unmodified cellulose fiber having an average fiber diameter of 125 nm.
KY100S: Serish KY100S manufactured by Daicel FineChem, which contains 25% by mass of unmodified cellulose fibers having an average fiber diameter of 140 nm.
KY110N: Serish KY110N manufactured by Daicel FineChem, which contains 15% by mass of unmodified cellulose fibers having an average fiber diameter of 125 nm.

・ Bacterial cellulose (unmodified cellulose)
50 mL of a medium having a composition of 0.5% by mass glucose, 0.5% by mass polypeptone, 0.5% by mass yeast extract, and 0.1% by mass magnesium sulfate heptahydrate was dispensed into a 200 mL Erlenmeyer flask. It was sterilized by steam at 120 ° C. for 20 minutes in an autoclave. Gluconacetobacter xylinus (NBRC 16670) grown on a test tube slope agar medium was inoculated into one loop loop and statically cultured at 30 ° C. for 7 days. After 7 days, a white gel film-like bacterial cellulose was formed on the upper layer of the culture solution.
The obtained bacterial cellulose was crushed with a mixer, then immersed in water and washed repeatedly to replace with water, and a product containing 4.1% by mass of bacterial cellulose having an average fiber diameter of 60 nm was prepared.

-Scrap yarn Purified water was added to the aggregate of cellulose fibers produced as scrap yarn in the manufacturing process of the non-woven fabric and stirred with a mixer to prepare an aqueous dispersion containing 3% by mass of cellulose fibers having an average fiber diameter of 120 nm. ..

TEMPO-catalyzed cellulose fiber (cellulose fiber in which some of the hydroxyl groups derived from cellulose are modified with hydrophilic substituents):
500 g (absolutely dry) of unbleached coniferous unbeaten kraft pulp (whiteness 85%) was added to 500 mL of an aqueous solution containing 780 mg of TEMPO and 75.5 g of sodium bromide, and the mixture was stirred until the pulp was uniformly dispersed. .. The oxidation reaction was started by adding an aqueous sodium hypochlorite solution to the solution so as to have a concentration of 6.0 mmol / g. Since the pH in the system decreased during the reaction, 3M aqueous sodium hydroxide solution was sequentially added to adjust the pH to 10. The reaction was terminated when sodium hypochlorite was consumed and the pH in the system did not change. The mixture after the reaction was filtered through a glass filter to separate the pulp, and the pulp was thoroughly washed with water to obtain oxidized pulp. The oxidized pulp obtained in the above step is adjusted to 1.0% (w / v) with water, treated three times with an ultra-high pressure homogenizer (20 ° C., 150 MPa), and TEMPO-catalyzed oxidation having an average fiber diameter of 10 nm. An aqueous dispersion containing 1.0% by mass of cellulose fibers was prepared.
When the TEMPO-catalyzed cellulose oxide fiber was analyzed by ¹ H-NMR, ¹³ C-NMR, FT-IR, and neutralization titration, a part of the hydroxyl group derived from cellulose was replaced with a carboxyl group, and the degree of substitution was It was confirmed that it was 0.3.

-Ether-modified cellulose fiber (cellulose fiber in which some of the hydroxyl groups derived from cellulose are modified with hydrophobic substituents):
19.94 kg of water was added to 600 g of softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., solid content 25%) to prepare an aqueous suspension having a solid content concentration of 0.75% by mass. The obtained slurry was mechanically defibrated using a bead mill (NVM-2 manufactured by IMEX) to obtain cellulose fibers (zirconia bead diameter 1 mm, bead filling amount 70%, rotation speed 2000 rpm, number of treatments 2 times). ). 100 g of the obtained cellulose fiber aqueous dispersion was placed in one centrifuge tube, and centrifugation (7000 rpm, 20 minutes) was performed to remove the supernatant, and the precipitate was taken out. 100 g of acetone was added to each centrifuge tube, stirred well, dispersed in acetone, centrifuged, the supernatant was removed, and the precipitate was taken out. The above operation was repeated twice to obtain a cellulose fiber acetone slurry having a solid content of 5% by mass.
The obtained cellulose fiber acetone slurry was put into a four-necked 1L flask equipped with a stirring blade so that the solid content of the cellulose fiber was 5 g. 500 mL of N-methyl-2-pyrrolidone (NMP) and 250 mL of toluene were added, and the cellulose fibers were dispersed in NMP / toluene with stirring. A cooler was attached, and the dispersion was heated to 150 ° C. under a nitrogen atmosphere, and acetone and water contained in the dispersion were distilled off together with toluene. Then, the dispersion was cooled to 40 ° C., 15 mL of pyridine and 25 g of hexamethyldisilazane (silyl etherifying agent) were added and reacted under a nitrogen atmosphere for 90 minutes to prepare an NMP dispersion of ether-modified cellulose fibers.
The obtained NMP dispersion of the ether-modified cellulose fiber was replaced with water by precipitating the cellulose fiber by a centrifuge. This was repeated 3 times to prepare an aqueous dispersion containing 1.0% by mass of ether-modified cellulose fibers having an average fiber diameter of 100 nm.
When the ether-modified cellulose fiber was analyzed by ¹ H-NMR, ¹³ C-NMR, and FT-IR, a part of the hydroxyl group derived from cellulose was replaced with a hydrophobic silyl ether group, and the degree of substitution was 0. It was confirmed that it was 0.3.

(3) Fluorene compound, BPEF, manufactured by Tokyo Chemical Industry Co., Ltd., 9,9-bis [4- (2-hydroxyethoxy) phenyl] Fluorene, BPF, manufactured by Tokyo Chemical Industry Co., Ltd., 9,9-bis (4-hydroxyphenyl) Fluorene

Example 1
As an aqueous dispersion of cellulose fibers, Serish KY100G was used, purified water was added thereto, and the mixture was stirred with a mixer to prepare an aqueous dispersion having a cellulose fiber content of 3% by mass. 66.67 parts by mass of the aqueous dispersion of the cellulose fibers, 100 parts by mass of ε-caprolactam, and 5 parts by mass of BPEF were further stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion was charged into the polymerization apparatus and then heated to 240 ° C. with stirring, and the pressure was increased from 0 MPa to 0.5 MPa while gradually releasing water vapor. After that, the pressure was released to atmospheric pressure, and the polymerization reaction was carried out at 240 ° C. for 1 hour. When the polymerization was completed, the resin composition was dispensed into a strand shape and cut to obtain a pellet of polyamide X in which cellulose fibers were blended with polyamide.
The obtained pellets were treated with hot water at 95 ° C., refined, dried, and dried polyamide X pellets were obtained.

Examples 2-4, Comparative Examples 16 and 17
The same operation as in Example 1 was carried out except that the blending amount of BPEF used was changed so as to have the content of BPEF in Table 1, and dried polyamide X pellets were obtained.

Examples 5 and 6
The same operation as in Example 1 was carried out except that the fluorene compound was changed to the fluorene compound shown in Table 1, to obtain dried polyamide X pellets.

Examples 7-12
The same operation as in Example 1 was carried out except that the dispersion liquid of the cellulose fibers used was changed to the dispersion liquid of the cellulose fibers shown in Table 1, to obtain dried polyamide X pellets.

Examples 13 to 15
The same operation as in Example 1 was carried out except that the blending amount of Serish KY100G used was changed so as to have the content of the cellulose fiber in Table 1, and dried polyamide X pellets were obtained.

Example 16
66.67 parts by mass of the aqueous dispersion having a cellulose fiber content of 3% by mass obtained in Example 1, 100 parts by mass of a 66 salt of polyamide, and 5 parts by mass of BPEF are stirred with a mixer until a uniform solution is obtained. , Mixed. Subsequently, the mixed solution was heated with stirring at 230 ° C. until the internal pressure reached 1.5 MPa. After reaching that pressure, heating was continued to maintain that pressure while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and polymerization was further carried out for 1 hour. When the polymerization was completed, the resin composition was dispensed into a strand shape and cut to obtain a pellet of polyamide X in which cellulose fibers were blended with polyamide. The obtained pellets were treated with hot water at 95 ° C., refined, dried, and dried polyamide X pellets were obtained. The polyamide 66 salt is an equimolar salt of hexamethylenediamine-adipic acid and is a polyamide prepolymer.

Example 17
The same operation as in Example 16 was carried out except that the blending amount of BPEF used was changed so as to have the content of BPEF in Table 1, and dried polyamide X pellets were obtained.

Comparative Example 1
After charging ε-caprolactam into the polymerization apparatus, the mixture was heated to 240 ° C. with stirring, and the pressure was increased from 0 MPa to 0.5 MPa while gradually releasing water vapor. After that, the pressure was released to atmospheric pressure, and the polymerization reaction was carried out at 240 ° C. for 1 hour. When the polymerization was completed, the resin was dispensed into strands and cut to obtain pellets of polyamide 6.
The obtained pellets were treated with hot water at 95 ° C., refined, dried, and dried PA6 resin pellets were obtained.

Comparative Example 2
The polyamide 66 salt was heated at 230 ° C. until the internal pressure reached 1.5 MPa. After reaching that pressure, heating was continued to maintain that pressure while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and polymerization was further carried out for 1 hour. When the polymerization was completed, the resin was dispensed into strands and cut to obtain pellets of polyamide 66.
The obtained pellets were treated with hot water at 95 ° C., refined, dried, and dried polyamide 66 resin pellets were obtained.

Comparative Example 3
After putting ε-caprolactam and 5 parts by mass of BPEF into the polymerization apparatus, the mixture was heated to 240 ° C. with stirring, and the pressure was increased from 0 MPa to 0.5 MPa while gradually releasing water vapor. After that, the pressure was released to atmospheric pressure, and the polymerization reaction was carried out at 240 ° C. for 1 hour. When the polymerization was completed, the resin was dispensed into strands and cut to obtain pellets of polyamide 6.
The obtained pellets were refined with hot water at 95 ° C. and then dried to obtain dried polyamide X pellets.

Comparative Example 4
The polyamide 66 salt and 5 parts by mass of BPEF were heated at 230 ° C. until the internal pressure reached 1.5 MPa. After reaching that pressure, heating was continued to maintain that pressure while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and polymerization was further carried out for 1 hour. When the polymerization was completed, the resin was dispensed into strands and cut to obtain pellets of polyamide 66.
The obtained pellets were treated with hot water at 95 ° C., refined, dried, and dried polyamide X pellets were obtained.

Comparative Example 5
66.67 parts by mass of the aqueous dispersion of cellulose fibers obtained in Example 1 and 100 parts by mass of ε-caprolactam were further stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion was charged into the polymerization apparatus and then heated to 240 ° C. with stirring, and the pressure was increased from 0 MPa to 0.5 MPa while gradually releasing water vapor. After that, the pressure was released to atmospheric pressure, and the polymerization reaction was carried out at 240 ° C. for 1 hour. When the polymerization was completed, the resin composition was dispensed into a strand shape and cut to obtain a pellet of polyamide X in which cellulose fibers were blended with polyamide.
The obtained pellets were treated with hot water at 95 ° C., refined, dried, and dried polyamide X pellets were obtained.

Comparative Examples 6 to 11
The same operation as in Comparative Example 5 was carried out except that the dispersion liquid of the cellulose fibers used was changed to the dispersion liquid of the cellulose fibers shown in Table 1, to obtain dried polyamide X pellets.

Comparative Examples 12-14, 18
The same operation as in Comparative Example 5 was carried out except that the blending amount of Serish KY100G used was changed so as to have the content of the cellulose fiber in Table 1, and dried polyamide X pellets were obtained.

Comparative Example 15
66.67 parts by mass of the aqueous dispersion having a cellulose fiber content of 3% by mass and 100 parts by mass of the polyamide 66 salt obtained in Example 1 were stirred and mixed with a mixer until a uniform solution was obtained. Subsequently, the mixed solution was heated with stirring at 230 ° C. until the internal pressure reached 1.5 MPa. After reaching that pressure, heating was continued to maintain that pressure while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and polymerization was further carried out for 1 hour. When the polymerization was completed, the resin composition was dispensed into a strand shape and cut to obtain a pellet of polyamide X in which cellulose fibers were blended with polyamide. The obtained pellets were treated with hot water at 95 ° C., refined, dried, and dried polyamide X pellets were obtained. The polyamide 66 salt is an equimolar salt of hexamethylenediamine-adipic acid and is a polyamide prepolymer.

Comparative Example 19
40 parts by mass of the aqueous dispersion having a cellulose fiber content of 3% by mass, 2 parts by mass of ε-caprolactam, and 5 parts by mass of BPEF obtained in Example 1 are further stirred with a mixer until a uniform dispersion is obtained. , Mixed. Subsequently, the mixed dispersion was charged into the polymerization apparatus and then heated to 240 ° C. with stirring, and the pressure was increased from 0 MPa to 0.5 MPa while gradually releasing water vapor. After that, the pressure was released to atmospheric pressure, and the polymerization reaction was carried out at 240 ° C. for 1 hour. At the time when the polymerization was completed, an attempt was made to dispense the resin composition into strands, but the pellets could not be obtained due to the high content of the cellulose fibers.

Table 1 shows the resin composition and evaluation results of the polyamide resin compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 19.

The polyamide resin compositions of Examples 1 to 17 have improved mechanical properties and thermal dimensional stability of the obtained molded product as compared with the conventional polyamide resin compositions polymerized without blending a fluorene-based compound, and are further polymerized. Time payout has improved.
By comparing the polyamide resin compositions of Examples 1 to 6, 7 to 12, 13 to 15, 16 to 17, and the polyamide resin compositions of Comparative Examples 5, 6 to 11, 12 to 14, 15 respectively, It can be seen that the addition of the fluorene-based compound at the time of polymerization improves the mechanical properties and thermal dimensional stability, and further improves the payout property.
Since the polyamide resin compositions of Comparative Examples 1 and 2 did not use cellulose fibers and fluorene compounds, the bending strength was low and the linear expansion coefficient was high.
Since the polyamide resin compositions of Comparative Examples 3 and 4 did not use cellulose fibers, the bending strength was low and the linear expansion coefficient was high.
The polyamide resin composition of Comparative Example 16 had a low content of fluorene-based compounds, so that the bending strength, CTER and yield were low.
The polyamide resin composition of Comparative Example 17 had a high content of fluorene-based compounds, and therefore had low bending strength and CTER.
The polyamide resin composition of Comparative Example 18 had a low bending strength and a high coefficient of linear expansion because the content of the cellulose fibers was low.
The polyamide resin composition of Comparative Example 19 had a high content of cellulose fibers, so that pellets could not be obtained.

Claims (7)

Polyamide containing 100 parts by mass of polyamide (A), 0.1 to 50 parts by mass of cellulose fiber (B), and 0.1 to 30 parts by mass of fluorene compound (C) represented by the following general formula (1). Resin composition.

(In the above general formula (1), ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is an amino group or a [(OR ³ ) _n −Y] group (in the above formula, Y is A hydroxyl group, a mercapto group, a glycidyloxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is an integer of 0 or more. K is an integer of 0 to 4, m is an integer of 0 or more, and p is 1. The above integers are shown.) The polyamide resin composition according to claim 1, wherein the value of the coefficient of linear expansion reduction (CTER) in the MD direction represented by the following formula is 0 <CTER.
CTER = (CTE ₀ -CTE) / CTE ₀
(In the above formula, CTE indicates the linear expansion coefficient (ppm / ° C.) of the polyamide resin composition in the MD direction, and CTE ₀ is the polyamide resin composition obtained by removing the fluorene compound (C) from the polyamide resin composition. Indicates the coefficient of linear expansion (ppm / ° C.) in the MD direction of.) The polyamide resin composition according to claim 1 or 2, wherein the fluorene compound (C) is a compound represented by the following general formula (2).

(In the general formula (2), Z, R ¹ , R ² , R ³ , n, k, m, and p are the same as in the general formula (1).) The polyamide resin composition according to any one of claims 1 to 3, wherein the fluorene compound (C) is 9,9-bis (4-hydroxyphenyl) fluorene and / or 9,9-bis (4-hydroxyphenyl) fluorene. thing. The polyamide resin composition according to any one of claims 1 to 4, wherein the cellulose fiber (B) has an average fiber diameter of 10 μm or less. The polyamide resin composition according to any one of claims 1 to 5, which comprises a step of mixing a monomer constituting the polyamide (A), a cellulose fiber (B), and a fluorene compound (C) to carry out a polymerization reaction. Production method. A molded product obtained by molding the polyamide resin composition according to any one of claims 1 to 5.