Continuous fiber resin composite and method for manufacturing continuous fiber resin composite

Abstract

To provide a continuous fiber resin composite that has a good balance between flame retardancy and mechanical strength and contains a polyamide resin composition sufficiently impregnated into reinforced fiber.SOLUTION: A continuous fiber resin composite contains (A) polyamide, (B) organic phosphinate, (C) alkylene fatty acid amide, and (D) continuous reinforced fiber.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a continuous fiber resin composite.

Background Art

[0002] A continuous fiber resin composite, which is a polyamide resin composition containing reinforcing fibers, is widely used in various industrial applications such as automotive parts, aircraft parts, and railway parts because of its light weight and excellent heat resistance. In such various industrial applications, improvement of flame retardancy is strongly required to prevent ignition and spread of fire. For example, Patent Document 1 describes a polyamide resin composition containing phosphinates, melamine polyphosphate, and zinc borate as flame retardants and flame retardant aids, and glass fibers. Further, Patent Document 2 describes a flame-retardant polyamide composition containing ammelin and / or ammelide as a flame retardant and glass fibers. Further, Patent Document 3 describes a resin composition containing an aluminum salt of phosphonic acid as a flame retardant, and salts of one or more organic phosphinic acids and / or salts of one or more diphosphinic acids and carbon fibers. Further, Patent Document 4 describes a flame-retardant polyamide composition containing one or more thermoplastic polyamides, dialkyl phosphinates, salts of phosphorous acid, condensation products of melamine, fillers and / or reinforcing materials, phosphites or phosphonites or mixtures thereof, esters or salts of long-chain aliphatic carboxylic acids.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, although the polyamide resin compositions described in Patent Documents 1 to 4 above have improved flame retardancy, they have a high viscosity and do not sufficiently impregnate the fibers when used as a fiber-fiber resin composite, leaving room for improvement in terms of the mechanical strength required for various industrial applications. Therefore, an object of the present invention is to provide a continuous fiber resin composite having an excellent balance between flame retardancy and mechanical strength, in which the polyamide resin composition sufficiently impregnates the reinforcing fibers.

[0005] As a result of intensive studies to solve the above problems, the present inventor has found that the polyamide resin composition to be impregnated into the reinforcing fibers contains a polyamide, an organic phosphinate, and an alkylene fatty acid amide, and can solve the above problems, and has completed the present invention. That is, the present invention is as follows.

[0006] [1] A continuous fiber resin composite comprising (A) a polyamide, (B) an organic phosphinate, (C) an alkylene fatty acid amide, and (D) continuous reinforcing fibers.

[0007] [2] The continuous fiber resin composite according to [1] above, wherein the content of the (C) alkylene fatty acid amide is 0.001% by mass or more and 0.1% by mass or less.

[0008] [3] The continuous fiber resin composite according to [1] or [2] above, wherein the (A) polyamide contains (A1) an aliphatic polyamide.

[0009] [4] The continuous fiber resin composite according to any one of [1] to [3] above, wherein the (A) polyamide contains (A2) a semi-aromatic polyamide.

[0010] [5] The continuous fiber resin composite according to any one of the above [1] to [4], wherein the (B) organic phosphinate is aluminum diethylphosphinate.

[0011] [6] The continuous fiber resin composite according to any one of the above [1] to [5], wherein the (C) alkylene fatty acid amide is ethylenebisstearic acid amide.

[0012] [7] The continuous fiber resin composite according to any one of the above [1] to [6], wherein the (D) continuous reinforcing fibers are glass fibers and / or carbon fibers.

[0013] [8] The continuous fiber resin composite according to any one of the above [1] to [7], wherein the volume ratio Vf of the continuous reinforcing fibers (D) is 40% or more. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a continuous fiber resin composite that has an excellent balance between flame retardancy and mechanical strength, and in which the polyamide resin composition is sufficiently impregnated into the fibers. [Modes for carrying out the invention]

[0015] Embodiments of the present invention will be described below. The continuous fiber resin composite according to the present invention is characterized by comprising (A) polyamide, (B) organic phosphinate, (C) alkylene fatty acid amide, and (D) continuous reinforcing fiber.

[0016] <Polyamide resin composition> The continuous fiber resin composite of this embodiment is characterized by comprising (A) polyamide, (B) organic phosphinate, (C) alkylene fatty acid amide, and (D) continuous reinforcing fibers.

[0017] <Polyamide> The polyamide may be (A1) an aliphatic polyamide, (A2) a semi-aromatic polyamide, a mixture of both, or a copolymer.

[0018] (A1) Aliphatic polyamide The constituent units of the (A1) aliphatic polyamide (hereinafter also simply referred to as "component (A1)") contained in the continuous fiber resin composite of this embodiment preferably satisfy at least one of the following conditions (1) and (2). (1) Contains (A1-a) aliphatic dicarboxylic acid units and (A1-b) aliphatic diamine units. (2) (A1-c) Contains at least one selected from the group consisting of lactam units and aminocarboxylic acid units.

[0019] The continuous fiber resin composite of this embodiment may contain one or more polyamides as (A1) aliphatic polyamides that satisfy at least one of the conditions of (1) and (2) above. In particular, it is preferable that the constituent units of the (A1) aliphatic polyamide contained in the polyamide resin composition of this embodiment satisfy (1) above.

[0020] ((A1-a) Aliphatic dicarboxylic acid unit) (A1-a) The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, but examples include linear and branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms. Examples of linear saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, tetradecanediic acid, hexadecanedioic acid, octadecanediic acid, eicosanedioic acid, and diglycolic acid. Examples of branched-chain saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid. These (A1-a) aliphatic dicarboxylic acid units may be used individually or in combination of two or more types. In particular, polyamide resin compositions tend to exhibit superior heat resistance, fluidity, toughness, low water absorption, and rigidity, therefore, linear saturated aliphatic dicarboxylic acids having 6 to 20 carbon atoms are preferred as the aliphatic dicarboxylic acids constituting the (A1-a) aliphatic dicarboxylic acid unit.

[0021] Preferred linear saturated aliphatic dicarboxylic acids having 6 to 20 carbon atoms include, for example, adipic acid, sebacic acid, dodecanediic acid, tetradecanediic acid, hexadecanedioic acid, octadecanediic acid, and eicosanedioic acid. Among these, adipic acid, sebacic acid, and dodecanediic acid are preferred as linear saturated aliphatic dicarboxylic acids having 6 to 20 carbon atoms, from the viewpoint of heat resistance of the polyamide resin composition.

[0022] Furthermore, (A1) the aliphatic polyamide may optionally contain units derived from trivalent or higher polycarboxylic acids, to the extent that it does not impair the effects of the polyamide resin composition of this embodiment. Examples of polycarboxylic acids with a valency of three or more include trimellitic acid, trimesic acid, and pyromellitic acid. These polycarboxylic acids with a valency of three or more may be used individually or in combination of two or more.

[0023] ((A1-b) Aliphatic diamine units) (A1-b) The aliphatic diamines that constitute the aliphatic diamine unit are not limited to the following, but examples include linear saturated aliphatic diamines having 2 to 20 carbon atoms and branched saturated aliphatic diamines having 3 to 20 carbon atoms. Examples of linear saturated aliphatic diamines having 2 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine. Branched-chain saturated aliphatic diamines having 3 to 20 carbon atoms are not limited to the following, but examples include 2-methylpentamethylenediamine (also known as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also known as 2-methyloctamethylenediamine), and 2,4-dimethyloctamethylenediamine. These (A1-b) aliphatic diamine units may be used individually or in combination of two or more aliphatic diamines. In particular, the number of carbon atoms in the aliphatic diamine constituting the (A1-b) aliphatic diamine unit is preferably 6 to 12, and more preferably 6 to 10. When the number of carbon atoms in the aliphatic diamine constituting the (A1-b) aliphatic diamine unit is above the lower limit, the heat resistance of the polyamide resin composition tends to be better. On the other hand, when the number of carbon atoms is below the upper limit, the crystallinity and mold release properties of the polyamide resin composition tend to be better.

[0024] Preferred linear or branched saturated aliphatic diamines having 6 to 12 carbon atoms include, for example, hexamethylenediamine, 2-methylpentamethylenediamine, and 2-methyl-1,8-octanediamine. Among these, hexamethylenediamine and 2-methylpentamethylenediamine are preferred as linear or branched saturated aliphatic diamines having 6 to 12 carbon atoms. Including such (A1-b) aliphatic diamine units tends to improve the heat resistance and rigidity of the polyamide resin composition.

[0025] Furthermore, (A1) the aliphatic polyamide may optionally contain units derived from a trivalent or higher polyhydric aliphatic amine, to the extent that it does not impair the effects of the polyamide resin composition of this embodiment. Examples of a trivalent or higher polyhydric aliphatic amine include bishexamethylenetriamine.

[0026] ((A1-c) At least one constituent unit selected from the group consisting of lactam units and aminocarboxylic acid units) (A1) Aliphatic polyamides may contain at least one constituent unit selected from the group consisting of (A1-c) lactam units and aminocarboxylic acid units. The inclusion of such units tends to result in better toughness of the polyamide resin composition. Note that "lactam unit" and "aminocarboxylic acid unit" refer to the polymerized (condensed) lactam and aminocarboxylic acid units.

[0027] The lactams that make up the lactam unit are not limited to the following, but examples include butyrolactam, pivalolactam, ε-caprolactam, capryloractam, enantractam, undecanolactam, and laurolactam (dodecanolactam). In particular, ε-caprolactam and laurolactam are preferred as lactams constituting the lactam unit, with ε-caprolactam being more preferred. The inclusion of such lactams tends to result in superior toughness of the polyamide resin composition.

[0028] The aminocarboxylic acids that constitute the aminocarboxylic acid unit are not limited to the following, but examples include ω-aminocarboxylic acids and α,ω-amino acids, which are compounds in which lactam rings have been opened. The aminocarboxylic acid constituting the aminocarboxylic acid unit is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms, in which the ω position is substituted with an amino group. Examples of such aminocarboxylic acids, though not limited to the following, include 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Other examples of aminocarboxylic acids include para-aminomethylbenzoic acid.

[0029] The lactam and aminocarboxylic acid that constitute at least one constituent unit selected from the group consisting of (A1-c) lactam units and aminocarboxylic acid units may be used individually or in combination of two or more types.

[0030] (A1) Specific examples of aliphatic polyamides include polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecaneamide), polyamide 12 (polydodecaneamide), polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, copolymer polyamides and polymer alloys containing these as constituent components. In particular, among the (A1) aliphatic polyamides, polyamides containing (A1-a) aliphatic dicarboxylic acid units and (A1-b) aliphatic diamine units are preferred from the viewpoint of mechanical properties, heat resistance, moldability, and toughness, and polyamide 66 is especially preferred. Polyamide 66 is suitable for automotive parts and the like because it has excellent mechanical properties, heat resistance, moldability, and toughness.

[0031] (A2) Semi-aromatic polyamide Semi-aromatic polyamides are polyamides that contain aromatic structural units. The (A2) semi-aromatic polyamide (hereinafter also simply referred to as "component (A2)") contained in the polyamide resin composition of this embodiment preferably has an aromatic component content of 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol% in the total constituent units of the (A2) semi-aromatic polyamide. Note that "aromatic constituent units" refer to aromatic diamine units and aromatic dicarboxylic acid units.

[0032] ((A2-a) dicarboxylic acid unit) (A2) The (A2-a) dicarboxylic acid units constituting the semi-aromatic polyamide are not particularly limited, and examples include aromatic dicarboxylic acid units, aliphatic dicarboxylic acid units, alicyclic dicarboxylic acid units, etc.

[0033] ((Aromatic dicarboxylic acid unit)) The aromatic dicarboxylic acids constituting the aromatic dicarboxylic acid unit are not limited to those listed below, but examples include dicarboxylic acids having aromatic groups such as a phenyl group and a naphthyl group. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have substituents. The substituents on the aromatic group of an aromatic dicarboxylic acid are not particularly limited, but examples include C1-C4 alkyl groups, C6-C10 aryl groups, C7-C10 arylalkyl groups, C7-C10 alkylaryl groups, halogen groups, C1-C6 silyl groups, sulfonic acid groups, and their salts (such as sodium salts).

[0034] Examples of alkyl groups having 1 to 4 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups. Examples of aryl groups having 6 to 10 carbon atoms include, but are not limited to, phenyl groups and naphthyl groups. Examples of arylalkyl groups having 7 to 10 carbon atoms include, but are not limited to, the benzyl group. Examples of alkylaryl groups having 7 to 10 carbon atoms include, but are not limited to, tolyl groups and xylyl groups. Examples of halogen groups include, but are not limited to, fluoro groups, chloro groups, bromo groups, and iodo groups. Silyl groups having 1 to 6 carbon atoms are not limited to the following, but examples include trimethylsilyl group and tert-butyldimethylsilyl group.

[0035] Among the aromatic dicarboxylic acids that constitute the above aromatic dicarboxylic acid unit, aromatic dicarboxylic acids having 8 to 20 carbon atoms that are unsubstituted or substituted with a predetermined substituent are preferred. Examples of unsubstituted or substituted C8-C20 aromatic dicarboxylic acids include, but are not limited to, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, and others, with isophthalic acid being particularly preferred.

[0036] The aromatic dicarboxylic acids that make up the aromatic dicarboxylic acid unit may be used individually or in combination of two or more types. In particular, the proportion of isophthalic acid units is preferably 50 mol% or more, more preferably 65 to 100 mol%, even more preferably 75 to 100 mol%, even more preferably 80 to 100 mol%, and most preferably 100 mol% relative to the total number of moles of (A2-a)dicarboxylic acid units. (A2-a) When the proportion of isophthalic acid units in dicarboxylic acid units is within the above range, a polyamide resin composition with excellent mechanical properties such as rigidity and fluidity can be obtained. Furthermore, the proportion of predetermined monomer units constituting (A2) semi-aromatic polyamides can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.

[0037] ((Aliphatic dicarboxylic acid unit)) The aliphatic dicarboxylic acids constituting the aliphatic dicarboxylic acid unit are not limited to the following, but examples include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.

[0038] Examples of linear saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, tetradecanediic acid, hexadecanedioic acid, octadecanediic acid, eicosanedioic acid, and diglycolic acid. Examples of branched-chain saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid. Furthermore, the aliphatic dicarboxylic acid that constitutes the aliphatic dicarboxylic acid unit may be used individually or in combination of two or more types.

[0039] ((Alicyclic dicarboxylic acid unit)) The alicyclic dicarboxylic acids that constitute the alicyclic dicarboxylic acid unit are not limited to the following, but examples include alicyclic dicarboxylic acids having 3 to 10 carbon atoms in the alicyclic structure. Among these, alicyclic dicarboxylic acids having 5 to 10 carbon atoms in the alicyclic structure are preferred. Examples of such alicyclic dicarboxylic acids include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Among these, 1,4-cyclohexanedicarboxylic acid is preferred as the alicyclic dicarboxylic acid. Furthermore, the alicyclic dicarboxylic acid that constitutes the alicyclic dicarboxylic acid unit may be used individually or in combination of two or more types.

[0040] The alicyclic group of an alicyclic dicarboxylic acid may be unsubstituted or substituted. Examples of substituents include C1-C4 alkyl groups. Examples of C1-C4 alkyl groups are the same as those exemplified in the "aromatic dicarboxylic acid unit" above.

[0041] (A2) In the semi-aromatic polyamide, the dicarboxylic acid constituting the (A2-a) dicarboxylic acid unit is not limited to the compounds described above as dicarboxylic acids, but may be equivalent compounds to the dicarboxylic acids. Furthermore, "compounds equivalent to dicarboxylic acids" refers to compounds that can have a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the above-mentioned dicarboxylic acid. Examples of such compounds, though not limited to those listed below, include anhydrides of dicarboxylic acids and halides of dicarboxylic acids.

[0042] Furthermore, (A2) the semi-aromatic polyamide may optionally contain units derived from trivalent or higher polycarboxylic acids, to the extent that it does not impair the effects of the polyamide resin composition of this embodiment. Examples of polycarboxylic acids with a valency of three or more include trimellitic acid, trimesic acid, and pyromellitic acid. These polycarboxylic acids with a valency of three or more may be used individually or in combination of two or more.

[0043] ((A2-b) diamine unit) (A2) The (A2-b) diamine units constituting the semi-aromatic polyamide are not particularly limited and include, for example, aromatic diamine units, aliphatic diamine units, alicyclic diamine units, etc.

[0044] ((Aromatic diamine unit)) The aromatic diamines that constitute the aromatic diamine unit are not limited to those listed below, as long as they are diamines containing aromatics, but examples include metaxylylenediamine.

[0045] ((Aliphatic diamine unit)) The aliphatic diamines that constitute the aliphatic diamine unit are not limited to the following, but examples include linear saturated aliphatic diamines having 4 to 20 carbon atoms. Examples of linear saturated aliphatic diamines having 4 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

[0046] ((Alicyclic diamine unit)) The alicyclic diamines that constitute the alicyclic diamine unit are not limited to the following, but examples include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine.

[0047] Furthermore, the diamines constituting each of the above diamine units may be used individually or in combination of two or more types. Among these, the (A2-b) diamine unit is preferably an aliphatic diamine unit, more preferably a linear saturated aliphatic diamine unit having 4 to 10 carbon atoms, even more preferably a linear saturated aliphatic diamine unit having 6 to 10 carbon atoms, and particularly preferably a hexamethylenediamine unit. By using such diamines, a polyamide resin composition with excellent mechanical properties such as rigidity and fluidity can be obtained.

[0048] (A2) As semi-aromatic polyamides, polyamide 6I (polyhexamethylene isophthalamide), polyamide 9I, and polyamide 10I are preferred, with polyamide 6I being particularly preferred. Polyamide 6I is suitable for automotive parts and the like because it has excellent heat resistance, moldability, and flame retardancy.

[0049] The ends of the polyamides ((A1) aliphatic polyamide and (A2) semi-aromatic polyamide) contained in the polyamide resin composition of this embodiment may be end-capping with known end-capping agents. Such end-capturing agents can also be added as molecular weight modifiers when producing polyamides from the above-mentioned dicarboxylic acid and the above-mentioned diamine, or from at least one selected from the group consisting of the above-mentioned lactam and the above-mentioned aminocarboxylic acid.

[0050] Examples of end-captive agents include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides (such as phthalic anhydride), monoisocyanates, monoesters, and monoalcohols. Among these, monocarboxylic acids or monoamines are preferred as end-captive agents. The end-capturing agent may be used alone or in combination of two or more types. When the ends of polyamide are sealed with an end-sealing agent, the polyamide resin composition tends to have superior heat resistance, fluidity, toughness, low water absorption, and rigidity, and the molded articles obtained from the polyamide resin composition tend to have superior thermal stability.

[0051] Any monocarboxylic acid that can be used as a terminal encapsulant is acceptable as long as it is reactive with the amino group that may be present at the terminal end of the polyamide. Examples of monocarboxylic acids are not limited to those listed below, but include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aromatic monocarboxylic acids, etc. Examples of aliphatic monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Examples of alicyclic monocarboxylic acids include cyclohexanecarboxylic acid. Examples of aromatic monocarboxylic acids include benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. These monocarboxylic acids may be used individually or in combination of two or more types. In particular, the ends of the (A2) semi-aromatic polyamide are preferably sealed with acetic acid from the viewpoint of fluidity and mechanical strength.

[0052] Any monoamine that can be used as a terminal encapsulant is one that is reactive with carboxyl groups that may be present at the ends of a polyamide. Examples of monoamines, but not limited to those listed below, include aliphatic monoamines, alicyclic monoamines, and aromatic monoamines. Examples of aliphatic monoamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Examples of alicyclic monoamines include cyclohexylamines and dicyclohexylamines. Examples of aromatic monoamines include aniline, toluidine, diphenylamine, and naphthylamine. These monoamines may be used individually or in combination of two or more types.

[0053] Method for producing polyamide The method for producing polyamide is not limited to the following, but includes, for example, the polymerization step of (1) or (2) below. (1) A step of polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit to obtain a polymer. (2) A step of polymerizing one or more selected from the group consisting of lactams that constitute lactam units and aminocarboxylic acids that constitute aminocarboxylic acid units to obtain a polymer.

[0054] Furthermore, the method for producing polyamide preferably includes a step after the polymerization step to increase the degree of polymerization of the polyamide. Additionally, if necessary, a sealing step may be included after the polymerization step and the sealing step to seal the ends of the obtained polymer with a terminal sealant.

[0055] Specific methods for producing polyamide include various methods, as illustrated in 1) to 4) below. 1) A method of polymerization by heating one or more aqueous solutions or aqueous suspensions selected from the group consisting of dicarboxylic acid-diamine salts, mixtures of dicarboxylic acid and diamine, or lactams and aminocarboxylic acids, while maintaining a molten state (hereinafter also referred to as "thermal fusion polymerization"). 2) A method for increasing the degree of polymerization of polyamide obtained by thermal fusion polymerization while maintaining a solid state at a temperature below the melting point (hereinafter also referred to as "thermal fusion polymerization / solid-phase polymerization"). 3) A method for polymerizing one or more substances selected from the group consisting of dicarboxylic acid-diamine salts, mixtures of dicarboxylic acid and diamine, or lactams and aminocarboxylic acids, while maintaining a solid state (hereinafter also referred to as "solid-phase polymerization"). 4) A method of polymerization using a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component (hereinafter also referred to as the "solution method").

[0056] In particular, a manufacturing method including thermal fusion polymerization is preferred for producing polyamides. Furthermore, when producing polyamides by thermal fusion polymerization, it is preferable to maintain the molten state until polymerization is complete. In order to maintain the molten state, it is necessary to manufacture the polyamide resin composition under polymerization conditions suitable for it. Examples of polymerization conditions include those listed below. First, the polymerization pressure in the fusion polymerization method should be 14-25 kg / cm². 2 The pressure inside the tank is controlled to atmospheric pressure (gauge pressure is 0 kg / cm²), and heating continues. Then, the pressure inside the tank is controlled to atmospheric pressure (gauge pressure is 0 kg / cm²). 2 The blood pressure is lowered over a period of 30 minutes or more until it reaches 30°C.

[0057] In the method for producing polyamide, the polymerization method is not particularly limited and may be a batch method or a continuous method. The polymerization apparatus used in the production of polyamide is not particularly limited, and known apparatus can be used. Specific examples of polymerization apparatus include autoclave reactors, tumbler reactors, and extruder reactors (such as kneaders).

[0058] The following describes a method for producing polyamides using a batch-type thermal fusion polymerization method, but the method of producing polyamides is not limited to this. First, an aqueous solution containing 40-60% by mass of the raw material components for polyamide (a combination of dicarboxylic acid and diamine, and, if necessary, at least one selected from the group consisting of lactam and aminocarboxylic acid) is prepared. Next, the aqueous solution is concentrated to 65-90% by mass in a concentration tank operated at a temperature of 110-180°C and a pressure of 0.035-0.6 MPa (gauge pressure) to obtain a concentrated solution. Next, the concentrated solution is transferred to an autoclave and heated until the pressure in the autoclave reaches 1.2 to 2.2 MPa (gauge pressure). Next, in the autoclave, the pressure is maintained at 1.2 to 2.2 MPa (gauge pressure) while removing at least one of the water and gas components. Then, when the temperature reaches 220 to 260°C, the pressure is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure inside the autoclave to atmospheric pressure, the by-product water can be effectively removed by reducing the pressure as needed. Next, the autoclave is pressurized with an inert gas such as nitrogen, and the molten polyamide is extruded from the autoclave as a strand. The extruded strand is cooled and cut to obtain polyamide pellets.

[0059] (B) Organic phosphinates Examples of the (B) organic phosphonate (hereinafter also simply referred to as the "(B) component") contained in the polyamide resin composition of the present embodiment include, but are not limited to, for example, an organic phosphonate represented by the following general formula (1) (hereinafter also referred to as "phosphonate (1)"), an organic diphosphonate represented by the following general formula (2) (hereinafter also referred to as "diphosphonate (2)"), and at least one organic phosphonate selected from the group consisting of condensates thereof.

[0060]

Chemical formula

[0061]

Chemical formula

[0062] (R 11 , R 12 , R 21 , and R 22 ) R 11 , R 12 , R 21 , and R 22 These are, independently, alkyl groups with 1 to 6 carbon atoms and aryl groups with 6 to 10 carbon atoms. There are multiple R groups. 11 and R 12 These may be the same or different, but it is preferable that they be the same because it is easier to manufacture. Also, if n is 2 or 3, there may be multiple R 21 and R 22 These may be identical or different, but it is preferable that they be identical because it makes manufacturing easier. The alkyl group may be linear or cyclic, but it is preferably linear. The linear alkyl group may be linear or branched. Examples of linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group. Examples of branched alkyl groups include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, and 1,1,2-trimethylpropyl group. Examples of aryl groups include phenyl groups and naphthyl groups. Alkyl and aryl groups may have substituents. Examples of substituents on alkyl groups include aryl groups having 6 to 10 carbon atoms. Examples of substituents on aryl groups include alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having substituents include, for instance, the benzyl group. Examples of substituted aryl groups include tolyl groups and xylyl groups. Among them, R 11 , R 12 , R 21 , and R 22 Preferably, the alkyl group has 1 to 6 carbon atoms, and more preferably, a methyl group or an ethyl group.

[0063] (R 23 ) R 23 R is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. If n is 2 or 3, there are multiple R groups. 23These may be identical or different, but it is preferable that they be identical because it makes manufacturing easier. The alkylene group may be linear or cyclic, but it is preferable to be linear. The linear alkylene group may be straight or branched. Examples of straight alkylene groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups. Examples of branched alkylene groups include 1-methylethylene and 1-methylpropylene groups. Examples of arylene groups include phenylene groups and naphthylene groups. The alkylene group and the arylene group may have substituents. Examples of substituents on the alkylene group include aryl groups having 6 to 10 carbon atoms. Examples of substituents on the arylene group include alkyl groups having 1 to 6 carbon atoms. Examples of alkylene groups having substituents include, for example, phenylmethylene group, phenylethylene group, phenyltrimethylene group, and phenyltetramethylene group. Examples of substituent arylene groups include methylphenylene group, ethylphenylene group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, and tert-butylnaphthylene group. Among them, R 23 Preferably, the alkylene group has 1 to 10 carbon atoms, and more preferably, a methylene group or an ethylene group.

[0064] (M 1 and M 2 ) M 1 and M 2 These are, independently, ions of elements belonging to Group 2 or Group 15 of the periodic table, ions of transition elements, zinc ions, or aluminum ions. Examples of ions of elements belonging to Group 2 of the periodic table include calcium ions and magnesium ions. Examples of ions of elements belonging to Group 15 of the periodic table include bismuth ions. Also, if j is 2, there are multiple M 2 They may be the same or different, but it is preferable that they be the same because it is easier to manufacture. Among them, M 1 and M 2 Calcium, zinc, or aluminum are preferred, with calcium or aluminum being more preferred.

[0065] (j) j is M 2 This represents the number of elements, which is either 1 or 2. j is M 2 Depending on the type and the number of diphosphinic acids, they can be selected as appropriate.

[0066] (m and n) m represents the number of phosphinic acid molecules, which is either 2 or 3. 1 Depending on the type and valency, it can be selected as appropriate. n represents the number of diphosphinic acid molecules and is an integer between 1 and 3. 2 Depending on the type and valency, it can be selected as appropriate.

[0067] (a and b) a is M 1 It represents the valence, which is either 2 or 3. b is M 2 It represents the valence, which is either 2 or 3. n, b, and j are integers that satisfy the relationship 2n = b × j.

[0068] Preferred phosphinates (1) specifically include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, methane (methylphosphinate) Examples include calcium, magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), calcium benzene-1,4-(dimethylphosphinate), magnesium benzene-1,4-(dimethylphosphinate), aluminum benzene-1,4-(dimethylphosphinate), zinc benzene-1,4-(dimethylphosphinate), calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate. Among these, metal diethylphosphinate salts are preferred from the viewpoint of flame retardancy, compatibility with polyamides, and ease of obtaining raw materials, and aluminum diethylphosphinate is particularly preferred.

[0069] Preferred diphosphinates (2) specifically include, for example, calcium methanedi(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), calcium benzene-1,4-di(methylphosphinate), magnesium benzene-1,4-di(methylphosphinate), aluminum benzene-1,4-di(methylphosphinate), and zinc benzene-1,4-di(methylphosphinate).

[0070] There are no particular limitations on the method for producing phosphinates, but examples include the method described in Japanese Patent Application Publication No. 2005-179362, European Patent Application Publication No. 699708, and Japanese Patent Application Publication No. 08-073720. Specifically, they are produced in aqueous solution using phosphinic acid and a metal carbonate, metal hydroxide, or metal oxide. These are essentially monomeric compounds, but depending on the reaction conditions, polymeric phosphinates with a degree of condensation of 1 to 3 may also be included depending on the environment.

[0071] (B) The content of organic phosphinates is, per 100% by mass of the continuous fiber resin composite, Preferably, it is 0.5 to 20% by mass, more preferably 1 to 6% by mass, and even more preferably 1.2 to 3% by mass. (B) When the content of the organic phosphinate is within the above range, a polyamide composition with excellent flame retardancy can be obtained without impairing the properties of the polyamide resin, and the reduction in mechanical strength is reduced, so a continuous fiber resin composite with an excellent balance between flame retardancy and mechanical strength can be obtained.

[0072] (C) Alkylene fatty acid amide Examples of alkylene fatty acid amides include methylene fatty acid amides such as methylenebisstearate, methylenebisbeheninate, methylenebismyristicate, methylenebiscaproate, and methylenebisbeheninate, and ethylene fatty acid amides such as ethylenebisstearate, ethylenebisbeheninate, ethylenebismyristicate, ethylenebiscaproate, and ethylenebisbeheninate. Among these, ethylenebisstearamide is preferred because it exhibits excellent interaction with metal elements in flame retardants and has excellent compatibility with polyamides.

[0073] (C) The content of alkylene fatty acid amide is preferably 0.001% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.06% by mass or less, and even more preferably 0.02% by mass or more and 0.04% by mass or less, based on 100% by mass of the continuous fiber resin composite. (C) When the content of alkylene fatty acid amide is within the above range, a continuous fiber resin composite with excellent flexural strength can be obtained.

[0074] Generally, adding flame retardants to resins significantly increases viscosity, posing a challenge in forming continuous fiber resin composites, as it makes it difficult for the resin to impregnate the continuous reinforcing fibers. Fluidity at the temperature during press molding is particularly important.

[0075] As a result of diligent research by the inventor, it was found that when using an organic phosphinate as a flame retardant, the viscosity increase can be suppressed by using an alkylene fatty acid amide in combination, making it possible to impregnate the continuous reinforcing fibers with resin. The reason for this is not clear, but it is presumed to be as follows. In other words, while the addition of flame retardants alone can inhibit fluidity and reduce interaction with the glass surface due to the coordination of ionic components to the polyamide functional groups, it is believed that the metal ions contained in the organophosphinate form coordination bonds with the two nitrogen atoms contained in the alkylene fatty acid amide, thereby creating a complex-like structure that suppresses the coordination of metal ions to the polyamide functional groups. Therefore, when applied to continuous reinforced fiber materials, flame retardancy can be imparted without impairing impregnation or interaction with the fiber surface. Furthermore, the introduction of long-chain alkyl groups increases compatibility with the resin, allowing the alkylene fatty acid amide to move easily within the resin, thus enabling the above effects to be obtained even with a small amount of alkylene fatty acid amide compared to flame retardants.

[0076] (B) The ratio of moles of organic phosphinate (MB) to (C) the ratio of moles of alkylene fatty acid amide (MC) is preferably MB:MC = 1000:1 to 50:1. This range is preferable because it sufficiently inhibits the coordination of metal ions to the polyamide functional groups and reduces the amount of alkylene fatty acid amide relative to the entire composite material, resulting in excellent impregnation into continuous reinforcing fibers and interaction with the fiber surface, and suppressing a decrease in the mechanical properties of the resin.

[0077] (B) Flame retardants other than organophosphinates The continuous fiber resin composite of this embodiment may further contain flame retardants other than the above-mentioned (B) organic phosphinate, if necessary.

[0078] Flame retardant additive The continuous fiber resin composite of this embodiment may further contain a flame retardant additive as needed. Flame retardant additives include, but are not limited to, antimony oxides such as antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate; tin oxides such as tin monoxide and tin dioxide; iron oxides such as ferric oxide and γ-iron oxide; zinc oxide, calcium oxide, aluminum oxide (alumina), aluminum oxide (boehmite), silicon oxide (silica), titanium oxide, zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, and other oxides. Examples include copper, tungsten oxide and other metal oxides; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; metal powders such as aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate, and barium carbonate; metal borates such as zinc borate, magnesium borate, calcium borate, and aluminum borate; metal phosphates such as aluminum phosphite; and silicones.

[0079] Additives The continuous fiber resin composite of this embodiment may contain additives as needed. Examples of additives include anti-aging agents, antioxidants, weathering agents, metal deactivators, light stabilizers, heat stabilizers, ultraviolet absorbers, antibacterial and antifungal agents, deodorants, conductivity imparters, dispersants, softeners, plasticizers, crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanizing aids, foaming agents, foaming aids, colorants, vibration damping agents, nucleating agents, neutralizing agents, lubricants, anti-blocking agents, dispersants, flow improvers, and release agents.

[0080] (D) Continuous Reinforced Fiber The (D) continuous reinforcing fibers (hereinafter also simply referred to as "component (D)") included in the continuous fiber resin composite of this embodiment can be those commonly used as fiber-reinforced composite materials, such as glass fibers, carbon fibers, aramid fibers, ultra-high-strength polyethylene fibers, polybenzazole fibers, liquid crystal polyester fibers, polyketone fibers, metal fibers, and ceramic fibers. From the viewpoint of mechanical properties, thermal properties, and versatility, glass fibers, carbon fibers, and aramid fibers are preferred, while from the viewpoint of economics, glass fibers are preferred. (D) Continuous reinforcing fibers may be used individually or in combination of two or more types.

[0081] - Stimulant - When glass fibers are selected as the continuous reinforcing fibers, a sizing agent may be used. The sizing agent may contain one or more selected from the group consisting of silane coupling agents, lubricants, and binding agents, and it is preferable that it contains at least a binding agent or a silane coupling agent. Furthermore, the sizing agent may consist of a silane coupling agent and a binding agent, or it may consist of a silane coupling agent, a lubricant, and a binding agent. By acting as a sizing agent that creates a strong bond between glass fibers and the resin coating surrounding them, it is possible to obtain a continuous fiber resin composite with low porosity. The sizing agent may be added externally to the material being used, or it may be contained internally within the material being used. For example, a lubricant may be included in a commercially available thermoplastic resin being used.

[0082] --Silane coupling agent-- Silane coupling agents are typically used as surface treatment agents for glass fibers and contribute to improving interfacial adhesion strength. Examples of silane coupling agents include, but are not limited to, aminosilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes; maleic acids, etc. When using polyamide as the thermoplastic resin, it is preferable to select one that readily bonds with the carboxyl group or amino group, which are terminal groups of the polyamide resin, and aminosilanes are preferred.

[0083] --Lubricant-- The lubricant contributes to improving the fiber-opening properties of glass fibers. As a lubricant, any ordinary liquid or solid lubricating material can be used depending on the purpose, as long as it does not inhibit the silane coupling agent and binding agent. Examples of such lubricants include, but are not limited to, animal or plant-based or mineral waxes such as carnauba wax and lanolin wax; and surfactants such as fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers.

[0084] --Binding agent-- The binding agent contributes to improving the bundleability of glass fibers and enhancing the interfacial adhesion strength. As a binding agent, a polymer suitable for the purpose, or a thermoplastic resin other than the thermoplastic resin used as the main material in a continuous fiber resin composite, can be used. Polymers used as binders are not limited to the following, but examples include homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines. In addition, polyurethane resins synthesized from isocyanates such as m-xylylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate, and polyester or polyether diols are also suitably used. The acrylic acid homopolymer preferably has a weight-average molecular weight of 1,000 to 90,000, and more preferably 1,000 to 25,000. The copolymerizable monomers constituting the copolymer of acrylic acid and other copolymerizable monomers are not limited to the following, but include, for example, one or more monomers having a hydroxyl group and / or carboxyl group, selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid (except in the case of acrylic acid alone). It is preferable to have one or more ester monomers as copolymerizable monomers. The salts of acrylic acid homopolymers and copolymers with primary, secondary, and tertiary amines are not limited to the following, but examples include triethylamine salts, triethanolamine salts, and glycine salts. The degree of neutralization is preferably 20-90%, and more preferably 40-60%, from the viewpoint of improving the stability of the mixed solution with other concomitant agents (such as silane coupling agents) and reducing amine odor. The weight-average molecular weight of the acrylic acid polymer that forms the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. From the viewpoint of improving the bundling properties of the glass fibers, it is preferable to have a molecular weight of 3,000 or more, and from the viewpoint of improving the properties when a composite molded article is formed, it is preferable to have a molecular weight of 50,000 or less. When using polyamide as the thermoplastic resin, it is preferable to use a resin with good wettability or a surface tension similar to that of the polyamide resin as the binding agent. Specifically, for example, polyurethane resin emulsions, polyamide resin emulsions, or modified versions thereof can be selected.

[0085] Examples of thermoplastic resins used as binding agents include, but are not limited to, polyolefin resins, polyamide resins, polyurethane resins, polyacetal resins, polycarbonate resins, polyester resins, polyether ketones, polyether ether ketones, polyether sulfones, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluorine resins, and modified thermoplastic resins obtained by modifying these. It is preferable that the thermoplastic resin used as a binding agent is the same type of thermoplastic resin and / or modified thermoplastic resin as the resin covering the continuous reinforcing fibers, as this improves the adhesion between the glass fibers and the thermoplastic resin after the composite is formed.

[0086] Furthermore, to further improve the adhesion between the continuous reinforcing fibers and the thermoplastic resin coating them, and to allow for a reduction in the ratio of emulsifier components or even elimination of the need for emulsifiers when the sizing agent is attached to the glass fibers as an aqueous dispersion, a modified thermoplastic resin is preferred as the thermoplastic resin used as the sizing agent. Here, a modified thermoplastic resin refers to a thermoplastic resin in which, in addition to the monomer components that can form the main chain of the thermoplastic resin, different monomer components are copolymerized with the purpose of changing the properties of the thermoplastic resin, thereby modifying its hydrophilicity, crystallinity, thermodynamic properties, etc. Modified thermoplastic resins used as binding agents are not limited to the following, but examples include modified polyolefin resins, modified polyamide resins, and modified polyester resins.

[0087] Modified polyolefin resins used as binding agents are copolymers of olefin monomers such as ethylene and propylene with monomers copolymerizable with olefin monomers, such as unsaturated carboxylic acids and / or their esters, or homopolymers of monomers copolymerizable with olefin monomers, such as unsaturated carboxylic acids and / or their esters, and can be produced by known methods. They may be random copolymers obtained by copolymerizing olefin monomers with unsaturated carboxylic acids and / or their esters, or graft copolymers obtained by grafting unsaturated carboxylic acids onto olefins. Examples of olefin monomers include, but are not limited to, ethylene, propylene, and 1-butene. These may be used individually or in combination of two or more. Examples of monomers copolymerizable with olefin monomers include unsaturated carboxylic acids such as acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, as well as esterified products of these unsaturated carboxylic acids (methyl esters, ethyl esters, etc.). These may be used individually or in combination of two or more. When a modified polyolefin resin is a copolymer of an olefin monomer and a monomer copolymerizable with the olefin monomer, the monomer ratio is preferably 60-95% by mass of the olefin monomer and 5-40% by mass of the monomer copolymerizable with the olefin monomer, with the total mass of the copolymer being 100% by mass, and more preferably 70-85% by mass of the olefin monomer and 15-30% by mass of the monomer copolymerizable with the olefin monomer. If the olefin monomer is 60% by mass or more, the affinity with the matrix is ​​good, and if the mass percentage of the olefin monomer is 95% by mass or less, the water dispersibility of the modified polyolefin resin is good, making it easy to uniformly apply it to continuous reinforcing fibers.

[0088] Modified polyolefin resins used as binding agents may have modified groups, such as carboxyl groups, introduced by copolymerization, neutralized with a basic compound. Examples of basic compounds, though not limited to the following, include alkalis such as sodium hydroxide and potassium hydroxide; ammonia; and amines such as monoethanolamine and diethanolamine. The weight-average molecular weight of the modified polyolefin resin used as a binding agent is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. From the viewpoint of improving the bundling properties of glass fibers, a molecular weight of 5,000 or more is preferred, and from the viewpoint of emulsification stability when water dispersibility is required, a molecular weight of 200,000 or less is preferred.

[0089] Modified polyamide resins used as binding agents are modified polyamide compounds in which hydrophilic groups such as polyalkylene oxide chains or tertiary amine components are introduced into the molecular chain, and can be manufactured by known methods. When introducing polyalkylene oxide chains into the molecular chain, for example, they are produced by copolymerizing a part or all of polyethylene glycol or polypropylene glycol modified with a diamine or dicarboxylic acid. When introducing tertiary amine components, for example, they are produced by copolymerizing aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam, etc.

[0090] Modified polyester resins used as binding agents are copolymers of polycarboxylic acid or its anhydride with polyols, and are resins having hydrophilic groups in their molecular skeleton, including the terminals, and can be manufactured by known methods. Examples of hydrophilic groups include polyalkylene oxide groups, sulfonates, carboxyl groups, and their neutralized salts. Examples of polycarboxylic acids or their anhydrides include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and polycarboxylic acids with three or more functions. Examples of aromatic dicarboxylic acids include, but are not limited to, phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride. Examples of sulfonate-containing aromatic dicarboxylic acids include, but are not limited to, sulfoterephthalate, 5-sulfoisophthalate, and 5-sulforthophthalate. Examples of aliphatic dicarboxylic acids or alicyclic dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, maleic anhydride, and the like. Examples of polycarboxylic acids with three or more functionalities include, but are not limited to, trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride. Among these, from the viewpoint of improving the heat resistance of the modified polyester resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component is an aromatic dicarboxylic acid. Furthermore, from the viewpoint of emulsification stability when the modified polyester resin is dispersed in water, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.

[0091] Examples of polyols that make up modified polyester resins include diols and polyols with three or more functionalities. Examples of diols, but not limited to those listed below, include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or its alkylene oxide adducts. Examples of polyols with three or more functions include trimethylolpropane, glycerin, and pentaerythritol.

[0092] The copolymerization ratio of polycarboxylic acid or its anhydride and polyol constituting the modified polyester resin is preferably 40-60% by mass of polycarboxylic acid or its anhydride and 40-60% by mass of polyol, with the total mass of copolymerized components being 100% by mass, and more preferably 45-55% by mass of polycarboxylic acid or its anhydride and 45-55% by mass of polyol. The weight-average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000. From the viewpoint of improving the bundling properties of glass fibers, a molecular weight of 3,000 or more is preferred, and from the viewpoint of emulsification stability when water dispersibility is required, a molecular weight of 100,000 or less is preferred.

[0093] The polymers and thermoplastic resins used as binding agents may be used individually or in combination of two or more types. It is preferable to use 50% or more by mass of one or more polymers selected from acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines, with the total amount of the binding agent being 100% by mass, and more preferably 60% or more by mass.

[0094] When the sizing agent consists of a silane coupling agent and a binding agent, the sizing agent is applied and attached to the glass fibers in an amount of 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and even more preferably 0.2 to 1% by mass, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent and binding agent. From the viewpoint of controlling the bundling properties of the glass fibers and improving the interfacial adhesion strength, it is preferable that the amount of sizing agent applied is 0.1% by mass or more, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent and binding agent, and from the viewpoint of ease of handling the yarn, it is preferable that it is 3% by mass or less. Furthermore, when the sizing agent consists of a silane coupling agent, a lubricant, and a binder, the sizing agent is applied and attached in an amount of 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and even more preferably 0.2 to 1% by mass, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent, lubricant, and binder. From the viewpoint of controlling the bundling properties of the glass fibers and improving the interfacial adhesion strength, it is preferable that the amount of sizing agent applied is 0.1% by mass or more, based on 100% by mass of glass fibers, as the total mass of the silane coupling agent, lubricant, and binder, and from the viewpoint of ease of handling the yarn, it is preferable that it is 3% by mass or less.

[0095] --Composition of fiber optic sizing agent-- The amount of silane coupling agent in a sizing agent for glass fibers is preferably 0.1 to 2% by mass, more preferably 0.1 to 1% by mass, and even more preferably 0.2 to 0.5% by mass, from the viewpoint of improving the bundling ability of glass fibers, improving interfacial adhesion strength, and improving the mechanical strength of the composite molded article. The amount of lubricant in a fiber sizing agent for glass fibers is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of providing sufficient lubricity, and preferably 1% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of improving interfacial adhesion strength and the mechanical strength of the composite molded article. The amount of binding agent in a sizing agent for glass fibers is preferably 1 to 25% by mass, more preferably 3 to 15% by mass, and even more preferably 3 to 10% by mass, from the viewpoint of controlling the sizing properties of glass fibers, improving interfacial adhesion strength, and improving the mechanical strength of the composite molded article.

[0096] When glass fibers are used as continuous reinforcing fibers, and the sizing agent consists of a silane coupling agent, a lubricant, and a binder, it is preferable that the glass fiber sizing agent contains 0.1 to 2% by mass of the silane coupling agent, 0.01 to 1% by mass of the lubricant, and 1 to 25% by mass of the binder, respectively, and it is preferable to dilute these components with water to adjust the total mass to 100% by mass.

[0097] --Methods of use for fiber optic scrubbers-- The sizing agent for glass fibers may be prepared in any form, such as an aqueous solution, a colloidal dispersion, or an emulsion using an emulsifier, depending on the intended use. However, from the viewpoint of improving the dispersion stability and heat resistance of the sizing agent, it is preferable to use it in the form of an aqueous solution. The glass fibers, which constitute the continuous fiber resin composite of this embodiment, are obtained continuously by applying the above-mentioned sizing agent to the glass fibers using a known method such as a roller-type applicator in a known glass fiber manufacturing process, and then drying the manufactured glass fibers.

[0098] Similarly, when carbon fibers are selected as the continuous reinforcing fibers, a sizing agent may also be used, and the sizing agent preferably consists of a coupling agent, a lubricant, and a binding agent. The coupling agent can be selected to have good compatibility with the hydroxyl groups present on the surface of the carbon fibers, the binding agent can be selected to have good wettability with the selected thermoplastic resin or to have a similar surface tension, and the lubricant can be selected to not inhibit the coupling agent and binding agent. There are no particular restrictions on the type of sizing agent used for carbon fibers; known types can be used. Specifically, for example, those described in Japanese Patent Publication No. 2015-101794 can be used.

[0099] When using other continuous reinforcing fibers, the type and amount of sizing agent that can be used with glass fibers and carbon fibers should be appropriately selected according to the characteristics of the continuous reinforcing fibers, and it is preferable to use a type and amount of sizing agent similar to that used with carbon fibers.

[0100] (Shape of continuous reinforcing fibers) Continuous reinforcing fibers are multifilaments consisting of multiple filaments, and the number of single filaments is preferably 30 to 15,000 from the viewpoint of handling. The single filament diameter R of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, even more preferably 6 to 20 μm, and most preferably 8 to 18 μm, from the viewpoint of strength and handling. Single filament diameter R (μm) and density D (g / cm³) of continuous reinforced fibers. 3 The product RD of the ) is preferably 5 to 100 μm·g / cm² from the viewpoint of the handling of the continuous reinforcing fibers and the strength of the composite. 3 More comfortably, 10-50 μm·g / cm² 3 More preferably 15-45 μm·g / cm² 3 More preferably 20-45 μm·g / cm² 3 That is the case.

[0101] Density D can be measured using a hydrometer. On the other hand, the diameter of the single filament R (μm) is equal to the density D (g / cm³).3 From the ) and fineness (dtex) and number of single filaments (strands), the following formula is used:

number

[0102] To set the product RD of continuous reinforcing fibers within a specified range, the fineness (dtex) and number of single fibers (strands) should be appropriately selected from commercially available continuous reinforcing fibers according to the density of the continuous reinforcing fibers. For example, when using glass fibers as continuous reinforcing fibers, the density is approximately 2.5 g / cm³. 3 Therefore, it is sufficient to select fibers with a single filament diameter of 2 to 40 μm. Specifically, if the single filament diameter of the glass fiber is 9 μm, selecting glass fibers with a fineness of 660 dtex and 400 single filaments will result in a product RD of 23. Also, if the single filament diameter of the glass fiber is 17 μm, selecting glass fibers with a fineness of 11,500 dtex and 2,000 single filaments will result in a product RD of 43. When using carbon fiber as the continuous reinforcing fiber, the density is approximately 1.8 g / cm³. 3 Therefore, it is sufficient to select fibers with a single filament diameter of 2.8 to 55 μm. Specifically, if the single filament diameter of the carbon fiber is 7 μm, selecting a carbon fiber with a fineness of 2,000 dtex and 3,000 single filaments will result in a product RD of 13. When using aramid fiber as the continuous reinforcing fiber, the density is approximately 1.45 g / cm³. 3 Therefore, it is sufficient to select fibers with a single filament diameter of 3.4 to 68 μm. Specifically, if the single filament diameter of the aramid fiber is 12 μm, selecting an aramid fiber with a fineness of 1,670 dtex and 1,000 single filaments will result in a product RD of 17.

[0103] Continuous reinforced fibers, such as glass fibers, are manufactured by weighing and mixing raw glass, melting it in a melting furnace to form molten glass, spinning it into glass filaments, applying a sizing agent, and then passing it through a spinning machine to produce winding forms such as direct-wound roving (DWR), cakes, or twisted yarn. The continuous reinforcing fibers can be in any form, but it is preferable if they are wound into yarn, cake, or DWR, as this increases productivity and production stability during the resin coating process. From a productivity standpoint, DWR is the most preferable.

[0104] The form of the continuous reinforcing fibers is not particularly limited and can take various forms such as woven fabrics, knitted fabrics, braided cords, pipe-shaped materials, non-crimped fabrics, and unidirectional materials. Preferably, the form is that of a woven fabric, non-crimped fabric, or unidirectional material.

[0105] The volume percentage Vf of (D) continuous reinforcing fibers in the continuous fiber resin composite is preferably 40% or more, more preferably 45-60%, and even more preferably 47-55%, from the viewpoint of mechanical strength. Furthermore, (D) the content of continuous reinforcing fibers is preferably 60 to 84% by mass, more preferably 65 to 77% by mass, and even more preferably 67 to 73% by mass, based on 100% by mass of the continuous fiber resin composite, from the viewpoint of mechanical strength.

[0106] <Porosity> The continuous fiber resin composite of this embodiment is a continuous fiber resin composite consisting of a resin composition and continuous reinforcing fibers having a substantially circular cross-section. At the polar interface between a single continuous reinforcing fiber and the synthetic resin in a cross-section perpendicular to the longitudinal direction of the continuous reinforcing fiber, there exist continuous reinforcing fibers in a peripheral outer region (also called the polar interface region) that is radially located at 1 / 10 of the radius r of the continuous reinforcing fiber (i.e., r / 10) from the periphery of the continuous reinforcing fiber, where the porosity is 10% or less, and the number of such fibers is 10% or more of the total number of continuous reinforcing fibers. It is preferable that the cross-section of the continuous reinforcing fiber be substantially circular, but it may also be elliptical as shown in Figure 1. In that case, "radius" is defined as the shortest distance from the center of the fiber cross-section toward the periphery.

[0107] The void ratio in the peripheral outer region, located at a distance of one-tenth the radius of the continuous reinforcing fiber from the periphery of the continuous reinforcing fiber, observed at the polar interface between a single continuous reinforcing fiber and the synthetic resin in a cross section perpendicular to the longitudinal direction of the continuous reinforcing fiber, is, for example, calculated by applying 400 g / cm² to the polished surface of a cross section perpendicular to the longitudinal direction of the continuous reinforcing fiber of a continuous fiber resin composite cut to a 1 cm square using a band saw or the like. 2 The polishing table was rotated at 100 rpm to apply the required force, and the samples were polished in the following order: 10 minutes with #220 grit waterproof sandpaper, 2 minutes with #400 grit waterproof sandpaper, 5 minutes with #800 grit waterproof sandpaper, 10 minutes with #1200 grit waterproof sandpaper, 15 minutes with #2000 grit waterproof sandpaper, 15 minutes with 9 μm particle size silicon carbide film, 15 minutes with 5 μm particle size alumina film, 15 minutes with 3 μm particle size alumina film, 15 minutes with 1 μm particle size alumina film, and 10 minutes with 0.1 μm particle size colloidal silica (Baicalox 0.1CR) using foamed polyurethane buffing paper. Water was added at approximately 7 mL / min during each polishing step. The polished samples were observed with a scanning electron microscope (SEM), and image analysis was performed using software such as ImageJ to obtain the following formula: Porosity (%) = (Area of ​​voids in the outer peripheral region at a distance of 1 / 10th of the radius of the continuous reinforcing fiber from the periphery) / (Area of ​​the outer peripheral region at a distance of 1 / 10th of the radius of the continuous reinforcing fiber from the periphery) × 100 This can be determined by [method].

[0108] First, the porosity in the peripheral outer region (also simply called the "region of one-tenth the diameter of the continuous reinforcing fiber" or the "polar interface region"), which is a distance of one-tenth the radius from the peripheral edge of a single continuous reinforcing fiber with an arbitrary approximately circular cross-section, is determined and observed for any 100 fibers. In the molded article of this embodiment, from the viewpoint of increasing the rigidity and strength of the molded article, at least 10 out of 100 fibers have a porosity of 10% or less in the region of one-tenth the diameter of the continuous reinforcing fiber, i.e., 10% or more, preferably 20% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 90% or more. Furthermore, in the molded article of this embodiment, from the viewpoint of increasing the rigidity and strength of the molded article, the porosity in the region of one-tenth the diameter of the continuous reinforcing fibers is preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less.

[0109] In order for 10% or more of the continuous reinforcing fibers to have a void ratio of 10% or less in the region of one-tenth of the diameter of each fiber, for example, if the continuous reinforcing fibers are glass fibers, it is preferable to select a sizing agent (sizing agent) that has good compatibility with the synthetic resin, where the μ-drop generation coefficient between the sizing agent (sizing agent) applied during the manufacture of the glass fibers and the synthetic resin is 10 or more, and to select a molding method that can seal the inside of the mold during molding, such as an inlay mold, or a molding method using a double belt press with adjusted pressure, thereby preventing resin leakage, minimizing the change in the volume occupied by the glass fibers (Vf, also called volume content) of the continuous fiber resin composite before and after molding, and molding under temperature conditions suitable for the sizing agent. [Examples]

[0110] The present invention will be described in detail below with reference to examples and comparative examples, but it goes without saying that the present invention is not limited to these examples and can be implemented with various modifications within the scope of the gist of the present invention.

[0111] First, we will explain the methods used for various measurements in the examples and comparative examples described later.

[0112] (Bending strength) Strip-shaped test pieces measuring 100 mm in length, 10 mm in width, and 2 mm in thickness were cut from a continuous fiber resin composite. The bending strength (MPa) was measured using an Instron universal testing machine with a three-point bending jig, with the span set to 32 mm, at a speed of 1 mm / min, 23°C, and 50% RH.

[0113] (Measuring the melting point) Using a differential scanning calorimeter (DSC: PERKINELMER DSC8500), the melting point [°C] was measured by the peak top temperature of the endothermic peak that appeared when the temperature was increased from 23°C at a heating rate of 10°C / min. If two or more endothermic peaks appeared, the peak top temperature of the hottest endothermic peak was measured as the melting point.

[0114] (Evaluation of flame retardancy) A gas burner was positioned vertically to the ground, and a test piece measuring 100mm in length, 100mm in width, and 2mm in height was placed parallel to the ground at a height of 5cm, the height at which the gas burner's temperature reached 1000℃. A test piece that developed a hole within 90 seconds of contact with the flame was marked with an "X," and a test piece that did not develop a hole even after 90 seconds or more of contact with the flame was marked with an "O."

[0115] The materials used in the examples and comparative examples are as follows:

[0116] (thermoplastic resin) Aliphatic polyamides Polyamide 66: Leona 1300S (Asahi Kasei Corporation, melting point 265°C) Polyamide 610: Leona 3100 (Asahi Kasei Corporation, melting point 220°C) Semi-aromatic polyamide Polyamide 6I: Leona R16024 (Asahi Kasei Corporation, glass transition temperature 130°C)

[0117] (Alkylene bisaliphatic amide) Ethylene bis-stearamide: EPL-8 (manufactured by Dainichi Chemical Industry Co., Ltd.)

[0118] (Flame retardant) Aluminum diethylphosphinate: Exolit OP1230 (manufactured by Clariant)

[0119] (Pellet preparation) Manufactured by Toshiba Machine Co., Ltd., TEM35mm 2Using a spool extruder (set temperature: melting point of aliphatic polyamide + 15°C, screw rotation speed 300 rpm), (A-1) aliphatic polyamide, and optionally (A-2) semi-aromatic polyamide, and optionally (B) alkylene bisaliphatic amide were supplied from the top feed port located at the uppermost part of the extruder. In addition, (C) flame retardant was supplied from the side feed port on the downstream side of the extruder (when the resin supplied from the top feed port was sufficiently melted). Next, the molten mixture extruded from the die head was cooled in strand form and pelletized to obtain polyamide composition pellets.

[0120] (Preparation of polyamide film) The pelletized polyamide composition described above was molded using a T-die extrusion molding machine (manufactured by Soken Co., Ltd.) to obtain a film. The thickness of the obtained film was 180 μm.

[0121] (Continuous reinforced fiber) Glass fiber: ER1200T-423 (Nippon Electric Glass Co., Ltd.) Carbon fiber (Taiwan plastic TAIRYFIL T-C33 1.5k) -Preparation of glass cloth- Glass cloth was manufactured by weaving using the above-mentioned glass fibers as warp and weft threads on a rapier loom (weaving width 2m). The resulting glass cloth had a 2-2 twill weave, a weave density of 6.5 threads / 25mm, and a weight of 600g / m². 2 That was the case. - Fabrication of carbon fiber fabric - Carbon fibers with a fineness of 8000 dtex and 12000 single filaments were manufactured by attaching 2.8% by mass of polyvinylpyrrolidone to them, and then woven (2-2 twill weave) using a rapier loom.

[0122] (Fabrication of continuous fiber resin composites) A continuous fiber resin composite was obtained by molding a glass cloth or carbon fiber fabric and a polyamide film as follows. A hydraulic molding machine with a maximum clamping force of 50 tons (Shoji Co., Ltd.) was used as the molding machine. A mold with an interlocking structure was prepared to obtain a flat, continuous fiber resin composite (200 mm long, 100 mm wide, 2 mm thick). Five sheets of glass cloth or carbon fiber fabric and six sheets of polyamide film were prepared. Each was cut to match the shape of the mold, and then they were stacked alternately with the polyamide film facing outwards and placed inside the mold. The mass of the resin and the mass of the reinforcing fibers were adjusted so that there were 230 parts by mass of reinforcing fibers for every 100 parts by mass of resin. The molding machine was heated to 330°C, then clamped with a clamping force of 5 MPa, and compression molding was performed. The molding time was 20 seconds after the aliphatic polyamide reached its melting point. After rapidly cooling the mold to 25°C, it was released, and the continuous fiber resin composite was removed.

[0123] (Comparative Example 1) A continuous fiber resin composite was prepared using PA66 as the aliphatic polyamide, glass fiber as the continuous reinforcing fiber, and aluminum diethylphosphinate as the flame retardant, with the mass fractions of each component in the composite being aliphatic polyamide: 29.4%, glass fiber: 67.7%, and flame retardant: 2.9%. The volume percentage Vf of the glass fiber was 50.7%. The flexural strength of the prepared composite was 520 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Comparative Example 1 are shown in Table 1.

[0124] [Table 1]

[0125] (Comparative Example 2) A continuous fiber resin composite was prepared using the above method, with PA66 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, and aluminum diethylphosphinate as the flame retardant. The mass fractions of each component in the composite were aliphatic polyamide: 23.5%, semi-aromatic polyamide: 5.9%, glass fiber: 67.7%, and flame retardant: 2.9%. The volume percentage Vf of the glass fiber was 50.7%. The flexural strength of the prepared composite was 550 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Comparative Example 2 are shown in Table 1.

[0126] (Comparative Example 3) A continuous fiber resin composite was prepared using the above method, with PA610 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, and aluminum diethylphosphinate as the flame retardant. The mass fractions of each component in the composite material were aliphatic polyamide: 23.5%, semi-aromatic polyamide: 5.9%, glass fiber: 67.7%, and flame retardant: 2.9%. The volume percentage Vf of the glass fiber was 49.7%. The flexural strength of the prepared composite material was 460 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Comparative Example 3 are shown in Table 1.

[0127] (Comparative Example 4) A continuous fiber resin composite was prepared using the above method, with PA66 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, and aluminum diethylphosphinate as the flame retardant. The mass fractions of each component in the composite material were aliphatic polyamide: 22.9%, semi-aromatic polyamide: 5.7%, glass fiber: 65.7%, and flame retardant: 5.7%. The volume percentage Vf of the glass fiber was 50.7%. The flexural strength of the prepared composite material was 440 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Comparative Example 4 are shown in Table 1.

[0128] (Comparative Example 5) A continuous fiber resin composite was prepared using the above method, with PA66 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, and aluminum diethylphosphinate as the flame retardant. The mass fractions of each component in the composite were aliphatic polyamide: 24%, semi-aromatic polyamide: 6%, glass fiber: 68.8%, and flame retardant: 1.2%. The volume percentage Vf of the glass fiber was 50.6%. The flexural strength of the prepared composite was 570 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Comparative Example 5 are shown in Table 1.

[0129] (Comparative Example 6) A continuous fiber resin composite was prepared using PA66 as the aliphatic polyamide, carbon fiber as the continuous reinforcing fiber, and aluminum diethylphosphinate as the flame retardant, with the mass fractions of each component in the composite being aliphatic polyamide: 37.0%, carbon fiber: 60.1%, and flame retardant: 2.9%. The volume percentage Vf of the glass fiber was 48.8%. The flexural strength of the prepared composite was 820 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Comparative Example 6 are shown in Table 1.

[0130] (Example 1) A continuous fiber resin composite was prepared using PA66 as the aliphatic polyamide, glass fiber as the continuous reinforcing fiber, aluminum diethylphosphinate as the flame retardant, and ethylenebisstearamide as the alkylene bisaliphatic amide, with the mass fractions of each component in the composite being: aliphatic polyamide: 29.4%, glass fiber: 67.7%, flame retardant: 2.9%, and alkylene bisaliphatic amide: 0.03%. The volume percentage Vf of the glass fiber was 50.7%. The flexural strength of the prepared composite was 820 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Example 1 are shown in Table 1.

[0131] (Example 2) A continuous fiber resin composite was prepared using the above method, with PA66 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, aluminum diethylphosphinate as the flame retardant, and ethylenebisstearate as the alkylene bisaliphatic amide. The mass fractions of each component in the composite were: aliphatic polyamide: 23.5%, semi-aromatic polyamide: 5.9%, glass fiber: 67.7%, flame retardant: 2.9%, and alkylene bisaliphatic amide: 0.03%. The volume percentage Vf of the glass fiber was 50.7%. The flexural strength of the prepared composite was 850 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Example 2 are shown in Table 1.

[0132] (Example 3) A continuous fiber resin composite was prepared using the above method, with PA610 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, aluminum diethylphosphinate as the flame retardant, and ethylenebisstearamide as the alkylene bisaliphatic amide. The mass fractions of each component in the composite material were: aliphatic polyamide: 23.5%, semi-aromatic polyamide: 5.9%, glass fiber: 67.7%, flame retardant: 2.9%, and alkylene bisaliphatic amide: 0.03%. The volume percentage Vf of the glass fiber was 49.7%. The flexural strength of the prepared composite material was 720 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Example 3 are shown in Table 1.

[0133] (Example 4) A continuous fiber resin composite was prepared using the above method, with PA66 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, aluminum diethylphosphinate as the flame retardant, and ethylenebisstearate as the alkylene bisaliphatic amide. The mass fractions of each component in the composite were as follows: aliphatic polyamide: 22.9%, semi-aromatic polyamide: 5.7%, glass fiber: 65.7%, flame retardant: 5.7%, and alkylene bisaliphatic amide: 0.06%. The volume percentage Vf of the glass fiber was 50.7%. The flexural strength of the prepared composite was 670 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Example 4 are shown in Table 1.

[0134] (Example 5) A continuous fiber resin composite was prepared using the above method, with PA66 as the aliphatic polyamide, PA6I as the semi-aromatic polyamide, glass fiber as the continuous reinforcing fiber, aluminum diethylphosphinate as the flame retardant, and ethylenebisstearate as the alkylene bisaliphatic amide. The mass fractions of each component in the composite were: aliphatic polyamide: 24%, semi-aromatic polyamide: 6%, glass fiber: 68.8%, flame retardant: 1.2%, and alkylene bisaliphatic amide: 0.01%. The volume percentage Vf of the glass fiber was 50.7%. The flexural strength of the prepared composite was 870 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Example 5 are shown in Table 1.

[0135] (Example 6) A continuous fiber resin composite was prepared using the above method, with PA66 as the aliphatic polyamide, carbon fiber as the continuous reinforcing fiber, and aluminum diethylphosphinate as the flame retardant, such that the mass fractions of each component in the composite material were: aliphatic polyamide: 37.0%, carbon fiber: 60.1%, flame retardant: 2.9%, and alkylene bisaliphatic amide: 0.03%. The volume percentage Vf of the glass fiber was 48.8%. The flexural strength of the prepared composite material was 1150 MPa. The flame retardancy evaluation result was ○. Details and flexural strength of the continuous fiber resin composite of Example 6 are shown in Table 1. [Industrial applicability]

[0136] According to the present invention, it is possible to provide a continuous fiber resin composite that has an excellent balance between flame retardancy and mechanical strength, and in which the polyamide resin composition is sufficiently impregnated into the reinforcing fibers.

Claims

1. (A) a polyamide resin composition comprising a polyamide, (B) an organic phosphinate, and (C) an alkylene fatty acid amide, and (D) continuous reinforcing fibers, The polyamide resin composition is impregnated into the (D) continuous reinforcing fiber, A continuous fiber resin composite characterized in that the form of the (D) continuous reinforcing fiber is a woven fabric or a non-crimped fabric.

2. The continuous fiber resin composite according to claim 1, wherein the content of (C) alkylene fatty acid amide is 0.001% by mass or more and 0.1% by mass or less.

3. The continuous fiber resin composite according to claim 1 or 2, wherein the (A) polyamide comprises (A1) aliphatic polyamide.

4. The continuous fiber resin composite according to any one of claims 1 to 3, wherein the (A) polyamide comprises (A2) semi-aromatic polyamide.

5. The continuous fiber resin composite according to any one of claims 1 to 4, wherein the (B) organic phosphinate is aluminum diethylphosphinate.

6. The continuous fiber resin composite according to any one of claims 1 to 5, wherein the (C) alkylene fatty acid amide is ethylenebisstearic acid amide.

7. The continuous fiber resin composite according to any one of claims 1 to 6, wherein the (D) continuous reinforcing fiber is glass fiber and / or carbon fiber.

8. The continuous fiber resin composite according to any one of claims 1 to 7, wherein the volume ratio Vf of the continuous reinforcing fibers (D) is 40% or more.

9. A method for producing a continuous fiber resin composite according to claim 1, A method for producing a continuous fiber resin composite, comprising compression molding a film made of a polyamide resin composition containing (A) polyamide, (B) organic phosphinate, and (C) alkylene fatty acid amide, and (D) continuous reinforcing fibers, thereby impregnating the (D) continuous reinforcing fibers with the polyamide resin composition.

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