TWI641653B - Carbon fiber reinforced resin composition, granules, molded articles, and electronic machine frames - Google Patents

Abstract

The present invention provides a carbon fiber reinforced resin composition, a granule, a molded article, and an electronic machine frame. The carbon fiber reinforced resin composition is blended with (B) carbon fiber in an amount of 60 to 200 parts by weight and (C) dendritic polyester in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the (A) semi-aromatic polyamide resin. The obtained (A) semi-aromatic polyamine resin is a dicarboxylic acid containing 60 to 100 mol% of p-citric acid in the total amount of dicarboxylic acid, and 1,9-壬2 in the total amount of diamine. A total of 60 to 100 mol% of a diamine of an amine and/or 2-methyl-1,8-octanediamine is obtained by polycondensation, and has a melting point of 220 to 300 °C.

The present invention provides a carbon fiber reinforced resin composition which is excellent in thermal stability, retention stability, fluidity, and sheet formability, and has the same degree of rigidity as the metal, excellent surface appearance and water absorption characteristics, and reduced warpage of the molded article. A material, a granular material, and a thin plate molded article for an electronic device frame obtained by injection molding.

Description

Carbon fiber reinforced resin composition, granules, molded articles, and electronic machine frames

The present invention relates to a carbon fiber reinforced resin composition, a granule formed therefrom, a molded article obtained by injection molding of a granulated product, and an electronic device casing.

Polyamine resin is excellent in mechanical properties such as rigidity and strength, heat resistance, and the like, and is widely used in various fields such as electric/electronics, automobiles, machinery, and building materials. Recently, there has been a resinization evolution that is used as a substitute for metal, and the resin is required to have mechanical properties such as rigidity and strength equivalent to metals. In particular, for home appliance parts such as frames of electronic equipment represented by OA equipment such as personal computers and mobile phones, excellent surface appearance, low water absorption, and thinness are required. Therefore, in addition to mechanical properties, the material is required. It has excellent surface appearance, water absorption properties and fluidity, and can reduce warpage.

In order to improve the mechanical properties of the polyamide resin, a fibrous filler such as a glass fiber or a carbon fiber is generally known. A general blending method is a method in which a fiber-reinforced resin composition is obtained by melt-kneading a polybenzamine resin and a cleavage (short fiber) of a fibrous filler in an extruder. In order to achieve the same rigidity of the metal, it is necessary to highly fill the fibrous filler, but in the case of using the glass fiber, it is necessary to blend a significant amount, which makes it difficult to achieve the same rigidity as the metal in reality. On the other hand, when carbon fiber is used, although the mechanical properties such as rigidity are significantly improved compared to those under the glass fiber, the molded article having a high carbon fiber filling is difficult because even high gloss still causes wavy irregularities. Both mechanical properties and surface appearance. Also, because of the large amount of carbon fiber blended, there will be: The carbon fiber is broken due to shearing during melt-kneading, and the mechanical properties are degraded. The shear heat generated by a large amount of carbon fibers causes the polyamide resin to be easily deteriorated, resulting in a decrease in thermal stability and a low fluidity, which makes it difficult to form a thin plate. .

[Previous Technical Literature] [Patent Literature]

On the other hand, in order to improve mechanical properties and surface appearance, it is proposed to obtain 20 to 160 parts by weight of carbon fibers having a tensile strength of 5.1 GPa or more with respect to 100 parts by weight of the thermoplastic polyamide resin. Carbon fiber reinforced resin composition (refer to Patent Document 1); and 100 parts by weight of the thermoplastic polyamidamide resin having a difference between the melting point and the temperature-lowering crystallization heat-generating peak temperature of 0 ° C or more and 50 ° C or less, and blending the carbon fiber 10~ A carbon fiber reinforced resin composition obtained by 300 parts by weight (see Patent Document 2).

Further, in terms of means for improving fluidity, mechanical properties, and surface appearance, there are proposals: 100 parts by weight of polyamine resin in a specific range by blending crystal melting heat, 0.01 to 100 parts by weight of a liquid crystalline resin, and an acid anhydride 0.01 ~5 parts by weight of the obtained polyamidamide resin composition (refer to Patent Document 3); and 100 parts by weight of the resin composition obtained by blending the thermoplastic resin and the dendritic polyester, blended into a fibrous form The long fiber reinforced resin granule obtained by 5 to 200 parts by weight of the filler (see Patent Document 4).

On the other hand, there is a proposal to use a polyamide resin having a relatively high crystallization rate to improve the formability, and the main component is a dicarboxylic acid component of citric acid and the main component is 1,8-octane. One or more kinds of diamine components are selected from the group consisting of diamine, 1,10-nonanediamine and 1,12-dodecyldiamine, and polyamine 100 having a degree of supercooling of 40 ° C or less is contained. The conductive polyamine resin composition of 5 to 50 parts by mass of the mass fraction and the conductivity imparting agent (see Patent Document 5), and the example of the use of 1,9-nonanediamine in the diamine component is described in the comparative example.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-255063

Patent Document 2: Japanese Patent Laid-Open Publication No. 2013-64106

Patent Document 3: Japanese Patent Laid-Open Publication No. 2000-313803

Patent Document 4: Japanese Patent Laid-Open Publication No. 2012-92303

Patent Document 5: Japanese Patent Laid-Open Publication No. 2013-60580

In the resin composition described in Patent Documents 1 and 2, although the mechanical properties and the surface appearance are improved, the fluidity of the carbon fiber-reinforced resin composition is lowered, which may cause problems in sheet formability.

In the resin composition described in Patent Documents 3 and 4, although the fluidity is improved, there is a problem that the water absorption property and the surface appearance are insufficient.

When the resin composition described in Patent Document 5 is highly filled with carbon fibers, fluidity, sheet formability, and surface appearance are insufficient.

As described above, it is known that a carbon fiber reinforced resin composition is difficult to achieve both thermal stability, fluidity, sheet formability, mechanical properties, and surface appearance. Further, there is a problem that the molded article is likely to warp.

The present invention has been made to solve the above problems, and an object thereof is to provide heat stability, retention stability, fluidity, and sheet formability, and to have the same degree of rigidity as a metal, excellent surface appearance and water absorption characteristics, and to reduce warpage. The carbon fiber reinforced resin composition of the molded article and the thin plate molded article for an electronic device frame obtained by performing injection molding.

In order to solve the above problems, the carbon fiber reinforced resin composition of the present invention has the following constitution.

That is, a carbon fiber reinforced resin composition is blended with (B) carbon fiber 60 to 200 parts by weight, and (C) dendritic polyester 0.01 to 10 parts by weight with respect to 100 parts by weight of the (A) semi-aromatic polyamide resin. In the case of a part by weight, the (A) semi-aromatic polyamine resin is a dicarboxylic acid containing 60 to 100 mol% of p-citric acid in the total amount of dicarboxylic acid, and contains 1,9 in the total amount of diamine. - Diamine and / or 2-methyl-1,8-octanediamine in total 60 to 100 mol% of diamine, obtained by polycondensation, and having a melting point of 220 to 300 °C.

The granular material of the present invention has the following constitution. In other words, a granular material is a granular material obtained by molding the carbon fiber-reinforced resin composition described above, wherein the weight average fiber length of the carbon fibers in the granular material is 0.1 to 0.5 mm.

The molded article of the present invention has the following constitution. That is, a molded article is obtained by subjecting the granular material to injection molding.

The electronic device frame system of the present invention has the following configuration. That is, an electronic machine frame system obtains the pellets by injection molding.

The carbon fiber-reinforced resin composition of the present invention is preferably further blended with (D) an acid anhydride in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the (A) semi-aromatic polyamide resin.

The carbon fiber-reinforced resin composition of the present invention is preferably a (A) semi-aromatic polyamide resin having a limit viscosity measured in a concentration of 0.5 to 1.3 dL/g in 0.2 g/dL of concentrated sulfuric acid at 30 °C.

In the carbon fiber-reinforced resin composition of the present invention, it is preferred that the (A) semi-aromatic polyamide resin in the carbon fiber-reinforced resin composition has a terminal amine group concentration of 0.1 to 30 meq/kg per kg.

In the molded article of the present invention, it is preferred that the carbon fibers in the molded article have a weight average fiber length of 0.01 to 0.5 mm.

In the molded article of the present invention, the ratio of the weight average fiber length to the number average fiber length (Lw/Ln) of the carbon fibers is preferably 1.0 or more and less than 1.3.

The electronic device casing of the present invention preferably has an average wall thickness of 0.5 to 1.0 mm.

The carbon fiber reinforced resin composition of the present invention is excellent in thermal stability, retention stability, fluidity, and sheet formability, and has rigidity equivalent to metal, excellent surface appearance and water absorption characteristics, and can reduce warpage. Product. Therefore, it is suitable for an electronic device housing such as a personal computer or a mobile phone which is lightweight, high rigidity, thin plate formability, and good surface appearance.

Hereinafter, the carbon fiber reinforced resin composition of the present invention (hereinafter referred to as "resin composition") will be specifically described.

The resin composition of the present invention is blended with (A) a dicarboxylic acid containing 60 to 100 mol% of p-citric acid in the total amount of dicarboxylic acid, and 1,9-nonanediamine in a total amount of diamine and / or 2-methyl-1,8-octanediamine totaling 60 to 100 mol% of diamine, obtained by polycondensation, a semi-aromatic polyamide resin having a melting point of 220 to 300 ° C (hereinafter referred to as "(A It is obtained in the case of a semi-aromatic polyamide resin. By blending the (A) semi-aromatic polyamide resin, a carbon fiber-reinforced resin composition which is excellent in fluidity and sheet formability and which can improve mechanical properties such as rigidity and strength of a molded article and water absorption characteristics can be obtained.

The dicarboxylic acid constituting the (A) semi-aromatic polyamide resin uses p-citric acid. The total amount of the dicarboxylic acid must be 60 to 100 mol% of the citric acid, and the other dicarboxylic acid may be contained in the total amount of the dicarboxylic acid at 40 mol% or less. When the citrate component is less than 60% by mole, The thermal stability, retention stability, fluidity, and sheet formability of the resin composition, and the water absorption characteristics, surface appearance, chemical resistance, dimensional stability, and the like of the molded article obtained from the resin composition are deteriorated. The content of citric acid is preferably 75 mol% or more, more preferably 90 mol% or more, based on the total amount of the dicarboxylic acid.

Other dicarboxylic acid systems can be, for example, malonic acid, dimethylmalonic acid, succinic acid, Glutaric acid, adipic acid, 2-methyladipate, trimethyl adipate, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl succinic acid, bismuth An aliphatic dicarboxylic acid such as an acid, azelaic acid or suberic acid; an alicyclic dicarboxylic acid such as 1,3-cyclopentanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2 , 6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,4-phenylenedioxy diacetic acid, 1,3-phenylenedioxy diacetic acid, Biphenyl acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylindole-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylate An aromatic dicarboxylic acid such as an acid. These may also be used in two or more types. Among these, aromatic dicarboxylic acids are preferably used.

Furthermore, in addition to the dicarboxylic acids, in the range of melt forming, A polycarboxylic acid such as trimellitic acid, trimesic acid or pyromellitic acid can be used.

The diamine constituting the (A) semi-aromatic polyamide resin uses 1,9-nonanediamine And / or 2-methyl-1,8-octanediamine. Generally, the poly-amine resin exhibits a so-called "even-odd effect". In other words, when the number of carbon atoms of the diamine constituting the polyamide resin is an even number, the crystal structure tends to be more stable and the crystallinity tends to be improved compared to the case of an odd number. In the present invention, by using 1,9-nonanediamine and/or 2-methyl-1,8-octanediamine, the crystallization rate of the resin composition can be adjusted to an appropriate range, and a semi-aromatic can be utilized. The properties of the polysaccharide polyamide resin improve fluidity and sheet formability, and also reduce warpage of the molded article. In the present invention, the total amount of the diamine, the 1,9-nonanediamine and/or the 2-methyl-1,8-octanediamine must be 60-100 mol% in total, and the other diamines may also be in the diamine. Contains less than 40% by mole. In addition, when any of 1,9-nonanediamine or 2-methyl-1,8-octanediamine is contained, the content is as long as 60~100% of the moles can be used. When both are contained, the total content is only 60~100%. When the total content of 1,9-nonanediamine and/or 2-methyl-1,8-octanediamine is less than 60 mol%, thermal stability, fluidity, and sheet of the resin composition may occur. The moldability is lowered, and any of the chemical resistance, water absorption characteristics, and mechanical properties of the molded article obtained from the resin composition is lowered. The total content of 1,9-nonanediamine and/or 2-methyl-1,8-octanediamine is preferably 70 mol% or more, more preferably 80 mol% or more, based on the total amount of the diamine. . Further, the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine (1,9-nonanediamine: 2-methyl-1,8-octanediamine) Good system 30:70~90:10, better system 40:60~70:30. If the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is within this preferred range, the resin composition is excellent in fluidity, thermal stability, and retention stability. The balance between the surface appearance of the molded article obtained from the resin composition can be further improved.

Other diamines can be, for example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecyldiamine, 3-methyl-1,5-pentanediamine, 2, Aliphatic 2 such as 2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine An amine; an alicyclic diamine such as cyclohexanediamine, methylcyclohexanediamine or isophorone diamine; p-phenylenediamine, meta-phenylenediamine, xylenediamine, 4,4'-di An aromatic diamine such as aminodiphenylmethane, 4,4'-diaminodiphenyl hydrazine or 4,4'-diaminodiphenyl ether. These may also be used in two or more types.

Furthermore, the above (A) semi-aromatic polyamide resin enhances retention stability. The viewpoint is preferably that the terminal of the molecular chain is terminated by a terminal terminator, more preferably 40% or more of the terminal group is terminated, more than 60% of the terminal group of the superior system is terminated, and 70% or more of the terminal group of the optimal system is terminated. Was terminated.

The terminal terminator is in opposition to the amine or carboxyl group at the end of the polyamine. Under the premise of a suitable monofunctional compound, the rest is not particularly limited, and may be, for example, a single Carboxylic acid, monoamine, acid anhydride, monoisocyanate, monoacid halide, monoester, monool, and the like. These may also be used in two or more types. From the viewpoint of reactivity and termination end stability, a monocarboxylic acid or a monoamine is preferred, and a monocarboxylic acid is more preferable from the viewpoints of ease of handling and the like.

The monocarboxylic acid used as the terminal terminator is not particularly limited as long as it has reactivity with the amine group, and may be, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, and laurel. Aliphatic monocarboxylic acids such as acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, trimethylacetic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid An aromatic monocarboxylic acid such as α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid or phenylacetic acid. These may also be used in two or more types. From the viewpoints of reactivity, terminal stability, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, and stearic acid are preferred. Acid, benzoic acid.

The monoamine used as the terminal terminator is taken up before being reactive with the carboxyl group, and the rest is not particularly limited, and may, for example, be methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine or decylamine. , an aliphatic monoamine such as stearylamine, dimethylamine, diethylamine, dipropylamine or dibutylamine; an alicyclic monoamine such as cyclohexylamine or dicyclohexylamine; aniline, toluidine, diphenylamine, naphthylamine An aromatic monoamine or the like. These may also be used in two or more types. From the viewpoints of reactivity, boiling point, end-end stability, and price, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred.

The (A) semi-aromatic polyamine resin of the present invention can be obtained by polycondensation of the above dicarboxylic acid and diamine by any known method. More specifically, for example, a diamine and a dicarboxylic acid, an optional catalyst, and a terminal terminator are mixed to prepare a nylon salt, and the obtained nylon salt is heated at a temperature of 200 to 250 ° C to obtain a nylon salt. The prepolymer further has a method of subjecting the prepolymer to a high degree of polymerization.

When terminating the end of (A) semi-aromatic polyamide resin, the end is terminated The blending amount of the agent can be adjusted in accordance with the ultimate viscosity and terminal group termination rate of the finally obtained (A) semi-aromatic polyamide resin. The specific blending amount varies depending on the reactivity, boiling point, reaction device, reaction conditions, and the like of the terminal terminator used, and is usually 0.5 to 10 moles relative to the total number of moles of the dicarboxylic acid and the diamine. Blend within the ear % range.

The (A) semi-aromatic polyamine resin of the present invention has a melting point of 220 to 300 °C. If When the melting point is less than 220 ° C, the mechanical properties and water absorption properties of the molded article obtained from the resin composition are lowered. It is preferably 230 ° C or higher, more preferably 240 ° C or higher. On the other hand, when the melting point exceeds 300 ° C, the fluidity, thermal stability, and retention stability of the resin composition are lowered, and the sheet formability and surface appearance of the molded article are lowered. It is preferably 290 ° C or lower, more preferably 280 ° C or lower. Here, the "melting point of (A) semi-aromatic polyamide resin" of the present invention can be measured using a differential scanning calorimeter (DSC). Using DSC and EXSTAR 6000 manufactured by Seiko Instruments Co., Ltd., the polyamide resin was kept at 330 ° C for 5 minutes, and then cooled to 23 ° C at a rate of 10 ° C / minute, and the melting endotherm at a temperature of 10 ° C / minute was used. The peak is set to "melting point". Further, a method of adjusting the melting point of the semi-aromatic polyamide resin to the above range may, for example, appropriately adjusting the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine. And a method of performing copolymerization of other diamines.

The (A) semi-aromatic polyamide resin of the present invention is preferably at 0.2 g/dL of concentrated sulfur. In the acid, the ultimate viscosity measured at 30 ° C is in the range of 0.5 to 1.3 dL / g. If the ultimate viscosity is 0.5 dL/g or more, the mechanical properties of the molded article can be further improved. More preferably, it is 0.6 dL/g or more, and particularly preferably 0.7 dL/g or more. On the other hand, when the ultimate viscosity is 1.3 dL/g or less, the fluidity of the resin composition, the sheet formability, and the surface appearance of the molded article can be further improved, and the warpage of the molded article can be further reduced. More preferably, it is 1.2 dL/g or less, and the best system is 1.1 dL/g or less.

Setting the ultimate viscosity of the semi-aromatic polyamide resin to the range within the range For example, the pressure, temperature, and temperature at which the semi-aromatic polyamide resin is produced can be appropriately adjusted. a method of polymerization conditions such as polymerization time; and a method of adjusting a composition of a raw material such as a dicarboxylic acid, a diamine, or a terminal blocking agent.

The resin composition of the present invention is obtained by blending (B) carbon fibers. By blending (B) carbon fibers, mechanical properties such as rigidity and strength of the molded article can be improved.

The carbon fiber (B) of the present invention is not particularly limited, and various carbon fibers can be known, for example, carbon fibers, graphite fibers, etc. produced using polyacrylonitrile (PAN), pitch, hydrazine, lignin, hydrocarbon gas, or the like. . It is also possible to use fibers in which the fibers are coated with a metal such as nickel, copper or ruthenium. Among them, PAN-based carbon fibers are preferred from the viewpoint of excellent mechanical property improvement effect. (B) The carbon fiber is usually in the form of a tang, a strand, a milled fiber, etc., and the diameter is generally 15 μm or less, preferably 5 to 10 μm.

The form of the carbon fiber of the present invention (B) is not particularly limited, and is preferably a carbon fiber bundle composed of thousands to hundreds of thousands of carbon fibers or a ground form in which it is pulverized. The relevant carbon fiber bundle system can be used: a direct-use continuous fiber obtained by a yarn bundle method, or a cut strand cut to a predetermined length.

The carbon fiber (B) of the present invention is preferably a stranded yarn, and the number of filaments of the carbon fiber strand yarn belonging to the conjugated carbon fiber precursor is preferably 1,000 to 150,000. If the number of filaments of the carbon fiber yarn is 1,000 to 150,000, the manufacturing cost can be suppressed, and the stability in the production step can be ensured.

The carbon fiber of the present invention (B) preferably has a strand elastic modulus of 150 GPa or more, more preferably 220 GPa or more. On the other hand, the yarn elastic modulus is preferably 1,000 GPa or less, more preferably 500 GPa or less. When the strand modulus of the carbon fiber is within this preferred range, the fluidity of the resin composition and the sheet formability can be further improved, the rigidity and surface appearance of the molded article can be further improved, and warpage can be further alleviated.

The strength of the strand of the carbon fiber of the present invention (B) is preferably 1 GPa or more, more preferably 3GPa or more. On the other hand, the strand strength is preferably 10 GPa or less, more preferably 5 GPa or less. When the strand strength of the carbon fiber is within the preferred range, the mechanical properties of the molded article can be further improved, and the wavy irregularities on the surface of the molded article can be alleviated, and the surface appearance can be further improved.

Here, the term "strand elastic modulus and yarn strength" means carbon fiber A value obtained by tensile test of a strand test piece in accordance with JIS R 7601, in a continuous fiber bundle composed of 1,000 to 150,000 individual fibers, which is impregnated with an epoxy resin and hardened to produce a strand. .

The (B) carbon fiber of the present invention is upgraded between (A) semi-aromatic polyamide resin For the adhesion, surface oxidation treatment can also be performed. The surface oxidation treatment may be, for example, a surface oxidation treatment performed by an energization treatment, an oxidation treatment performed in an oxidizing gas atmosphere such as ozone, or the like.

Furthermore, (B) carbon fiber can also attach a coupling agent, a sizing agent, etc. to the surface, and Improve the wettability and handleability of (A) semi-aromatic polyamide resin. The coupling agent may, for example, be an amine-based, epoxy-based, chlorine-based, thiol-based or cationic decane coupling agent, and an amine-based decane-based coupling agent may preferably be used. The sizing agent may be, for example, a maleic anhydride-based compound, an amine ester-based compound, an acrylic compound, an epoxy-based compound, a phenol-based compound, or a derivative of such a compound, and the like, and an amine ester-based compound may preferably be used. A sizing agent for an epoxy compound. (B) The coupling agent and the sizing agent in the carbon fiber are preferably 0.1 to 10% by weight. When the sizing agent content is 0.1 to 10% by weight, carbon fibers having more excellent wettability and handleability of the (A) semi-aromatic polyamide resin can be obtained. More preferably, it is 0.5 to 6% by weight.

(B) carbon fiber blending amount in the resin composition of the present invention, relative to (A) half 100 parts by weight of the aromatic polyamide resin is 60 to 200 parts by weight. When the amount of the carbon fiber (B) is less than 60 parts by weight, the rigidity (flexural modulus of elasticity), strength, and impact resistance of the molded article are lowered, and it is not suitable for use in an electronic device housing. More preferably 70 parts by weight or more, more preferably It is 80 parts by weight or more. On the other hand, when the amount of the (B) carbon fiber blended exceeds 200 parts by weight, the thermal stability is remarkably impaired, and a carbon fiber-reinforced resin composition excellent in surface appearance and fluidity cannot be obtained, and productivity is also remarkably lowered. It is preferably 180 parts by weight or less, more preferably 150 parts by weight or less.

The resin composition of the present invention is obtained by blending (C) dendritic polyester. By By blending the (C) dendritic polyester, it is possible to suppress the decomposition of the (A) aromatic polyester resin in the production of the resin composition, and to greatly improve the fluidity, sheet formability, and thermal stability of the resin composition. Moreover, the warpage of the molded article can be reduced.

The (C) dendritic polyester of the present invention preferably contains: an aromatic oxycarbonyl unit (P), an aromatic and/or aliphatic dioxy unit (Q), an aromatic dicarbonyl unit (R), and a trifunctional or higher organic residue (S), and the (S) content is relative to the composition The dendritic polyester has a molten liquid crystalline dendritic polyester in the range of 7.5 to 50 mol% of the whole single system.

Among them, aromatic oxycarbonyl unit (P), aromatic and / or aliphatic dioxy The base unit (Q) and the aromatic dicarbonyl unit (R) are each preferably a structural unit represented by the following general formula (3).

Wherein R ₁ and R ₃ are each an aromatic residue. R ₂ is an aromatic residue or an aliphatic residue. R ₁ , R ₂ and R ₃ may each contain a plurality of structural units.

The aromatic residue may be, for example, a substituted or unsubstituted phenylene group, an extended naphthyl group, a stretched phenyl group or the like; and the aliphatic residue may be, for example, an ethyl group, a propyl group, a butyl group or the like. R ₁ , R ₂ and R ₃ are each preferably selected from at least one of the structural units represented by the following structural formula (4).

In the formula, Y is at least one selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. Where n is an integer from 2 to 8.

The basic skeleton of the dendritic polyester of the present invention is a trifunctional or higher organic residue (S) which is bonded to each other by ester bonding and/or guanamine bonding, or via the above-mentioned P, Q and R which are part of the branched structural moiety. The structural unit is composed of three branches and more branched structures. It is not necessary for the polymer to be entirely composed of the basic skeleton, and for example, the terminal may be terminated at the end and the other structure may be contained at the terminal. In the dendritic polyester, a structure in which all of the functional groups of (S) are reacted, a structure in which only two reactions are carried out, and a structure in which only one reaction is carried out may be used. Mixed. The structure in which all of the functional groups (S) have been reacted is preferably 15 mol% or more, more preferably 30 mol% or more, based on the total of (S).

The (C) dendritic polyester of the present invention preferably has a molten liquid crystalline property. Here, "the molten liquid crystal property" means a liquid crystal state which is present in a certain temperature range when the temperature is raised from room temperature. The "liquid crystal state" refers to a state in which optical anisotropy is formed under shear.

The trifunctional organic residue (S) is preferably an organic residue of a compound having a carboxyl group, a hydroxyl group or an amine group. It may also be an organic residue of a compound having two or more such groups. Preferably, for example, an aliphatic compound such as glycerol, 1,2,3-tricarboxypropane, diaminopropanol or diaminopropionic acid; trimesic acid, trimellitic acid or 4-hydroxyl can be used. -1,2-benzenedicarboxylic acid, phloroglucinol, resorcylic acid, tricarboxynaphthalene, dihydroxynaphthoic acid, amino decanoic acid, 5-aminoisodecanoic acid, amino-p-citric acid Residues of aromatic compounds such as diaminobenzoic acid and melamine. More preferably, it is a residue of the aromatic compound represented by the following general formula (5).

Specific examples of the trifunctional organic residue are preferably phloroglucinol, trimesic acid, trimellitic acid, trimellitic anhydride, α-tellreic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, and the like. The residue is more preferably a residue of trimesic acid.

Further, the aromatic hydroxycarbonyl unit (P), the aromatic and/or aliphatic dioxy unit (Q), and the aromatic dicarbonyl unit (R) of the dendritic polyester constitute a branch between the dendritic polyester branches. The unit of the branch structure part. p, q, and r are the average contents (mole ratio) of the structural units P, Q, and R, respectively, and 1 mol of the (S) content d, preferably p+q+r=1~10 Ear range, better 2 to 6 mole range. If the length of the branched chain is within the above range, The straight and dense tree structure fully achieves the effects of shear responsiveness.

The p, q and r values are, for example, from dissolving the dendritic polyester in the pentafluorophenol 50 weight Amount %: A solution of 50% by weight of a mixed solvent of heavy chloroform was obtained by a peak intensity ratio derived from each structural unit in a nuclear magnetic resonance spectrum of a proton nucleus at 40 °C. The average content ratio was calculated from the peak area intensity ratio of each structural unit, and the third decimal place was rounded off. From the area intensity ratio between the peaks when the branch structure F contains the amount f, the average chain length of the branched structure portion is calculated and set to the p+q+r value. This situation is also the third decimal place rounded off.

The ratio of p to q and the ratio of p to r (p/q, p/r) are preferred. In the range of 5/95~95/5, the best is 20/80~80/20. By setting the ratio of p/q and p/r to 95/5 or less, the melting point of the dendritic polyester can be set to an appropriate range. Further, by setting p/q and p/r to 5/95 or more, the molten liquid crystallinity of the dendritic polyester can be more effectively exhibited.

It is preferable that q and r are substantially the same, but in order to control the terminal group, any one of them may be excessively added. The ratio of q/r is preferably in the range of 0.7 to 1.5, and more preferably in the range of 0.9 to 1.1. Here, "equivalent" means that the molar amount in the repeating unit is equal, and the end structure is not included. The term "end structure" as used herein refers to the end of the branched structure portion, and when the end is blocked, the end portion of the branched structure portion closest to the end is referred to.

In the above general formula (3), R ₁ is a structural unit derived from an aromatic oxycarbonyl unit, and specific examples thereof may be, for example, a structural unit derived from p-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid. It is preferably a structural unit derived from p-hydroxybenzoic acid, and a part thereof may be used in combination with a structural unit derived from 6-hydroxy-2-naphthoic acid. Further, a structural unit derived from an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid or hydroxycaproic acid may be contained within the range which does not impair the effects of the present invention.

R ₂ is a structural unit derived from an aromatic and/or aliphatic dioxy unit, and may, for example, be derived from 4,4′-dihydroxybiphenyl, hydroquinone, 3,3′,5,5′-tetramethyl -4,4'-dihydroxybiphenyl, tert-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-dual ( A structural unit such as 4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, ethylene glycol, 1,3-propanediol, or 1,4-butanediol. From the viewpoint of liquid crystal control, it is preferred to contain a structural unit derived from 4,4'-dihydroxybiphenyl and hydroquinone or a structural unit derived from 4,4'-dihydroxybiphenyl and ethylene glycol.

R ₃ is a structural unit derived from an aromatic dicarbonyl unit, and may be derived, for example, from p-nonanoic acid, isodecanoic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2 - bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-di A structural unit such as phenylene ether dicarboxylic acid. It is preferred to use a structural unit derived from citric acid or isodecanoic acid, particularly in the case where both are used in combination, and the melting point adjustment can be easily carried out, which is preferable. Further, a part thereof may contain a structural unit derived from an aliphatic dicarboxylic acid such as sebacic acid or adipic acid.

The branched structure portion of the (C) dendritic polyester of the present invention is preferably mainly composed of a polyester skeleton, and can also introduce a carbonate structure, a guanamine structure, an amine ester structure, etc., to the extent that the properties are not greatly affected. . By incorporating such other bonds, the compatibility with a wide variety of thermoplastic resins can be adjusted. Among them, it is preferred to introduce a guanamine structure. The method of introducing a guanamine bond can be, for example, a method of copolymerizing an aliphatic, alicyclic or aromatic amine compound. The aliphatic amine compound may be, for example, butanediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, decanediamine, undecyldiamine, ten Dimethylenediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, 5-methylnonanediamine, and the like. The alicyclic amine compound may be, for example, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminemethyl-3, 5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl) Propane, bis(aminopropyl)per Aminoethylperazine Wait. The aromatic amine compound may, for example, be p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine or meta-phenylenediamine. These may also be used in two or more types. Among them, an aminophenol or a p-aminobenzoic acid is preferred.

Specific examples of the branched structure portion of the dendritic polyester may be, for example, derived from a structural unit of hydroxybenzoic acid and a structural unit derived from 6-hydroxy-2-naphthoic acid; a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 6-hydroxy-2-naphthoic acid, a source a structural unit derived from 4,4'-dihydroxybiphenyl, and a structural unit derived from citric acid; a structural unit derived from p-hydroxybenzoic acid derived from 4,4'-dihydroxybiphenyl a structural unit, a structural unit derived from citric acid, and a structural unit derived from isodecanoic acid; a structural unit derived from 4,4'-dihydroxybiphenyl derived from a structural unit derived from p-hydroxybenzoic acid a structural unit derived from hydroquinone, a structural unit derived from citric acid, and a structural unit derived from isodecanoic acid; a structural unit derived from a structural unit derived from p-hydroxybenzoic acid derived from ethylene glycol And a structural unit derived from a decanoic acid; a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from ethylene glycol, a structural unit derived from 4,4'-dihydroxybiphenyl, and From the constituent units of citric acid; from structural units derived from p-hydroxybenzoic acid, structural units derived from hydroquinone, derived from 4,4'-dihydroxybiphenyl a structural unit, a structural unit derived from citric acid, and a structural unit derived from 2,6-naphthalene dicarboxylic acid; a structural unit derived from p-hydroxybenzoic acid derived from 6-hydroxy-2-naphthalene A structural unit of formic acid, a structural unit derived from hydroquinone, and a constituent derived from a structural unit derived from citric acid.

Among these, it is preferably composed of the following structural units (I), (II), (III), (IV) and (V); or the following structural units (I), (II), ( VI) and (IV) constituents.

[Chemical 4]

When the branched structure portion is composed of the above structural units (I), (II), (III), (IV) In the case of the (V) configuration, the content p of the structural unit (I) is preferably 30 to 70 mol%, more preferably 45 to 60 mol%, based on the total p+q+r of each structural unit. Further, the content q (II) of the structural unit (II) is preferably 60 to 75 mol%, more preferably 65 to 73 mol%, based on the total content q of the structural units (II) and (III). . Further, the content r(IV) of the structural unit (IV) is preferably 60 to 92 mol%, more preferably 60 to 70 mol%, based on the total content r of the structural units (IV) and (V). , especially good 62~68 moles. This situation can further improve liquidity.

According to the above, the total contents q, and (IV) of the structural units (II) and (III) And the total content r of (V) is preferably substantially the same as the molar amount, and any one of the components may be excessively added.

When the branched structure portion is composed of the above structural units (I), (II), (VI) and (IV) In the case of the constitution, the content p of the structural unit (I) is preferably 30 to 90 mol%, more preferably 40 to 80 mol%, based on p+q+r. Further, the content q (VI) of the structural unit (VI) is preferably from 5 to 70 mol%, more preferably from 8 to 60 mol%, based on the total content q of (II) and (VI). In the above, the content r of the structural unit (IV) is preferably substantially the same as the total content q of the structural units (II) and (VI), but any of the components may be excessively added.

Further, the terminal of the (C) dendritic polyester of the present invention is preferably a carboxyl group, a hydroxyl group or an amine. a residue of a base or such a derivative. The hydroxy or carboxylic acid derivative may, for example, be an alkyl ester such as a methyl ester or an aromatic ester such as a phenyl ester or a benzyl ester.

Furthermore, a monofunctional epoxy compound, The oxazoline compound, the acid anhydride compound, and the like are subjected to terminal blocking. The method of end-capping can be, for example, a method of pre-adding a monofunctional organic compound at the time of synthesis of a dendritic polyester; and a method of adding a monofunctional organic compound at a stage of forming a dendritic polyester skeleton to some extent. Wait.

Specifically, when the hydroxyl end and the ethoxy group end are blocked, Preferably, for example, benzoic acid, 4-tert-butylbenzoic acid, 3-tert-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4-methylbenzoic acid, 3-methyl group are added. Benzoic acid, 3,5-dimethylbenzoic acid, and the like.

Furthermore, when the carboxy terminus is capped, it is preferred to add acetamidine. Oxybenzene, 1-ethoxycarbonyl-4-t-butylbenzene, 1-ethyloxy-3-tert-butylbenzene, 1-ethyloxy-4-chlorobenzene, 1-ethyl hydrazine Oxy-3-chlorobenzene, 1-ethyloxy-4-cyanobenzene, and the like.

Theoretically, by using the organic compound used when the above end is blocked, An amount equivalent to the terminal group to be blocked is added, and end capping can be performed. Effectively The end of the row end is equivalent to the amount of the terminal group to be blocked, and the organic compound used for the end capping is preferably 1.005 equivalents or more, more preferably 1.008 equivalents or more. On the other hand, from the viewpoint of suppressing a decrease in the reaction rate and gas generation due to the excessive terminal blocking agent remaining in the system, the amount of the organic compound to be used in the end capping is preferably 1.5 equivalents or less.

Further, the content of the organic residue (S) is 7.5 mol% or more, preferably 20 mol% or more, based on the total monomer content of the dendritic polyester. In this case, it is preferred that the chain length of the branched chain structure portion is a preferred length for forming the dendritic polyester into a tree-like form. The upper limit of the content of the organic residue (S) is 50 mol% or less, preferably 40 mol% or less.

Further, the (C) dendritic polyester of the present invention may partially have a crosslinked structure insofar as it does not affect the properties.

In the present invention, the method for producing the (C) dendritic polyester is not particularly limited, and it can be produced by a polycondensation method of a known polyester. For example, a method of reacting a monomer containing the structural unit represented by the above R ₁ , a monomer containing the structural unit represented by the above R ₂ , a monomer containing the structural unit represented by the above R ₃ , and a trifunctional monomer, The method of adding the amount of the trifunctional monomer (mol) to the total monomer (mol) constituting the dendritic polyester is preferably 7.5 mol% or more. The amount of the trifunctional monomer to be added is more preferably 20 mol% or more.

In addition, when the above reaction is carried out, a monomer containing at least one selected from the structural units represented by R ₁ , R ₂ and R _{3 is} subjected to deuteration, and then the trifunctional monomer is reacted. It is also preferred. Further, it is also preferable to include a monomer selected from at least one of the structural units represented by R ₁ , R ₂ and R ₃ and a trifunctional monomer to carry out a polymerization reaction.

Manufacturing by the above structural units (I), (II), (III), (IV) and (V), and The case of a dendritic polyester composed of a residue of trimellitic acid is exemplified, and a preferred production method will be described.

(1) From p-ethoxylated benzoic acid, 4,4'-diethyloxybiphenyl, diethyl hydrazine A method in which a phthalic acid and an isononanoic acid are synthesized by a polycondensation reaction of a deacetic acid to synthesize a liquid crystalline polyester oligomer, and then trimellitic acid is added, followed by a deacetalization polycondensation reaction.

(2) From p-ethoxybenzoic acid, 4,4'-diethyloxybiphenyl, diethyl hydrazine A method of producing oxybenzene, p-citric acid, isophthalic acid, and trimesic acid by a polycondensation reaction.

(3) making p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, p-nonanoic acid and isoindole A method in which an acid is reacted with acetic anhydride, and a phenolic hydroxyl group is deuterated, and then a liquid crystalline polyester oligomer is synthesized by a polyacetal polycondensation reaction, and trimellitic acid is further added to carry out a deacetation polycondensation reaction.

(4) make p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, p-nonanoic acid, isoindole A method in which an acid and trimesic acid are reacted with acetic anhydride to form a phenolic hydroxyl group and then subjected to a polyacetal polycondensation reaction.

(5) Phenyl ester of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, p-citric acid A method in which diphenyl ester and diphenyl isononate are synthesized by a polyphenol polycondensation reaction, and then a trimellitic acid is added to carry out a dephenolization polycondensation reaction.

(6) Phenyl ester of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, p-citric acid A method in which diphenyl ester, diphenyl isononate, and phenyl ester of trimesic acid are produced by a polyphenol polycondensation reaction.

(7) making p-hydroxybenzoic acid, p-citric acid, isophthalic acid, and trimesic acid, and A method in which diphenyl carbonate is reacted to form a phenyl ester, and then 4,4'-dihydroxybiphenyl or hydroquinone is added, and the product is produced by a polyphenol polycondensation reaction.

Among them, the manufacturing method of the preferred systems (1) to (5) is controlled from the chain length and the three-dimensional The rule of view is better than the manufacturing method of the system (3).

(3) In the manufacturing method, the blending amount of acetic anhydride is controlled from the viewpoint of chain length control The point is preferably 0.95 equivalent or more and 1.10 equivalent or less, more preferably 1.02 equivalent or more and 1.05 equivalent or less in total of the phenolic hydroxyl group. The terminal group can be adjusted by adjusting the amount of acetic anhydride, excessively blending a dihydroxy monomer, and a dicarboxylic acid monomer.

In order to increase the molecular weight, it is preferred to use a carboxylic acid which is exactly equivalent to trimesic acid. The amount of the dihydroxy monomer such as hydroquinone or 4,4'-dihydroxybiphenyl is excessively added to the dicarboxylic acid monomer to match the carboxylic acid of the all monomer with the hydroxyl equivalent. On the other hand, in the case where the carboxylic acid is deliberately left at the terminal group, it is preferable to carry out excessive addition of the dihydroxy monomer as described above. Further, when the hydroxyl group is intentionally left at the terminal, it is preferred to add the dihydroxy monomer to the carboxylic acid equivalent of the trimesic acid in excess, and the amount of the acetic anhydride to be used is less than 1.00 equivalent of the phenolic hydroxyl group.

By the methods, the (C) dendritic polyester of the present invention can be selectively designed and used Invention (A) A terminally-reactive terminal structure of a semi-aromatic polyamide resin. However, since the structure of the (A) semi-aromatic polyamide resin suppresses excessive reactivity, the terminal is blocked by a monofunctional epoxy compound or the like, and it is easier to control the dispersion state.

When the deacetalization polycondensation reaction is carried out, it is preferable to melt the dendritic polyester. At the melting temperature, the reaction is carried out under reduced pressure, and a certain amount of acetic acid is distilled off to complete a polycondensation reaction. Specifically, for example, the following method. A predetermined amount of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, p-nonanoic acid, isodecanoic acid and acetic anhydride are charged with a stirring wing and a distilling tube, and the lower portion is provided with spit. Export to the reaction vessel. The mixture in the reaction vessel was heated while stirring under a nitrogen atmosphere to distill the hydroxyl group, and then the temperature was raised to 200 to 350 ° C to carry out a deacetic acid polycondensation reaction, and acetic acid was distilled off. During the 50% phase of acetic acid distillation to the theoretical distillation amount, the same amount of trimesic acid is added, and the acetic acid is distilled to the theoretical distillation. The reaction was completed by 91% of the output.

In terms of the acetylation reaction conditions, the reaction temperature is preferably 130 to 170 ° C. It is better to range from 135 to 155 °C. The reaction time is preferably 0.5 to 6 hours, more preferably 1 to 2 hours.

The polycondensation reaction temperature is a temperature at which the dendritic polyester melts, preferably a dendrimer The melting point of the ester is +10 ° C or higher. Specifically, for example, it is in the range of 200 to 350 ° C, preferably 240 to 280 ° C. The environment in which the polycondensation is carried out is not problematic even under normal pressure nitrogen. However, if the pressure is reduced, the reaction is accelerated and the residual acetic acid in the system is reduced, which is preferable. The degree of pressure reduction is preferably 0.1 mmHg (13.3 Pa) to 200 mmHg (26,600 Pa), more preferably 10 mmHg (1,330 Pa) to 100 mmHg (13,300 Pa). Further, the acetylation and polycondensation may be carried out continuously in the same reaction vessel, or the acetalization and polycondensation may be carried out using different reaction vessels.

After the completion of the polycondensation reaction, it is preferred to keep the inside of the reaction vessel at a temperature at which the dendritic polyester melts, and pressurize it to, for example, 0.01 to 1.0 kg/cm ² (0.001 to 0.1 MPa) from the discharge port provided at the lower portion of the reaction vessel. The dendritic polyester is spun in a strand form. It is also possible to provide a mechanism for intermittent opening and closing in the discharge port, and discharge it in a droplet shape. Generally, the dendritic polyester which is discharged is cooled by air or water, and then cut or pulverized as needed.

The obtained granular, granular or powdery dendritic polyester is preferably further improved It is necessary to remove water, acetic acid, etc. by heat drying and vacuum drying. Further, solid phase polymerization may be carried out in order to finely adjust the degree of polymerization or to further increase the degree of polymerization. The solid phase polymerization method may, for example, be a dendritic polyester obtained as described above, under a nitrogen stream or under reduced pressure, at a melting point of a dendritic polyester of from -5 ° C to a melting point of -50 ° C (for example, 200 to 300 ° C). Inside, heat for 1 to 50 hours.

The polycondensation reaction of the dendritic polyester is carried out even without a catalyst, but it can also be A metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate, sodium acetate, antimony trioxide, or magnesium metal is used.

The number average molecular weight of the (C) dendritic polyester used in the present invention is preferably 1,000 to 40,000, more preferably 1,000 to 5,000. Further, the number average molecular weight is a dendritic phenol/chloroform=35/65 wt% mixed solvent capable of dissolving a solvent of a dendritic polyester, and a dendritic polyester solution adjusted to a concentration of 0.08% (wt/vol). The value of the absolute molecular weight was measured by GPC-LS (gel permeation chromatography-light scattering) method. The measurement conditions here were Shodex KG, Shodex K-806M×2, Shodex K-802, set to a flow rate of 0.8 mL/min, temperature of 23 ° C, and the detector was set using a differential refractometer (RI). For multi-angle light scattering (MALS).

Furthermore, the melt viscosity of the dendritic polyester of the present invention is preferably 0.01 to 30 Pa‧ s, better system 1~10Pa‧s. Further, the melt viscosity is a value measured by a high-flow type flow tester under conditions of a shear rate of 100/s at a liquid crystal starting temperature of the dendritic polyester + 10 °C.

The blending amount of the (C) dendritic polyester of the present invention is relative to (A) semi-aromatic polyamine 100 parts by weight of the resin is 0.01 to 10 parts by weight. When the blending amount of the (C) dendritic polyester is less than 0.01 part by weight, the fluidity, sheet formability, and thermal stability of the resin composition are lowered. Moreover, the warpage of the molded article becomes large. It is preferably 0.05 parts by weight or more, more preferably 0.5 parts by weight or more. On the other hand, when the blending amount of the (C) dendritic polyester exceeds 10 parts by weight, the rigidity of the molded article is lowered. It is preferably 8 parts by weight or less, more preferably 5 parts by weight or less.

The carbon fiber reinforced resin composition of the present invention can be further blended (D) Anhydride. By blending the acid anhydride, the fluidity of the resin composition, the sheet formability, and the rigidity at the time of sheet metal formation can be obtained while maintaining the mechanical properties of the molded article, and the effect of warpage of the molded article can be further reduced.

The (D) acid anhydride may be, for example, benzoic anhydride, isobutyric anhydride, itaconic anhydride, octane Anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethyl maleic anhydride, phthalic anhydride, trimellitic anhydride, 1,8-naphthalic anhydride, phthalic anhydride, maleic anhydride, and the like. These may also be used in two or more types. Among them, succinic anhydride, 1,8-naphthalic anhydride, phthalic anhydride and the like are preferred, and succinic anhydride and phthalic anhydride are more preferred.

The blending amount of the (D) acid anhydride of the present invention is relative to (A) semi-aromatic polyamide resin 100 parts by weight, preferably 0.01 to 5 parts by weight. By setting the blending amount of the (D) acid anhydride to the above preferred range, the fluidity of the resin composition can be improved while maintaining the mechanical properties of the molded article, the rigidity during sheet forming can be improved, and the molded article can be further reduced. song. More preferably, it is 0.05 part by weight or more, and particularly preferably 0.1 part by weight or more. Further, it is more preferably 2.5 parts by weight or less, and particularly preferably 2 parts by weight or less.

The resin composition of the present invention, (A) semi-aromatic polyfluorene in the resin composition The amine group concentration per 1 kg of the amine is preferably 0.1 to 30 meq/kg. Wherein the concentration of the terminal amine group per 1 kg of the semi-aromatic polyamine of the present invention is obtained by dissolving 0.2 g of the resin composition in 10 mL of hexafluoroisopropanol, and then applying a potential difference to the sample solution using a 0.02 N hydrochloric acid aqueous solution. The measurement was carried out by titration.

Thermal stability can be obtained by setting the terminal amine group concentration to the preferred range A resin composition which is excellent in both water and water absorption characteristics and has a markedly improved retention stability. More preferably, it is 0.2 meq/kg or more, and particularly preferably 0.3 meq/kg or more. More preferably, it is 15 meq/kg or less, and particularly preferably 10 meq/kg or less.

(A) semi-aromatic polyamine in the resin composition per 1 kg of terminal amine The base concentration can be, for example, a method of appropriately adjusting the polymerization conditions such as pressure, temperature, and polymerization time in the production of the semi-aromatic polyamide resin; adjusting the dicarboxylic acid, the diamine, and the terminal blocking agent. a method of forming a raw material; adding the above amount in any amount during melt-kneading (D) A method of an acid anhydride or the like.

The carbon fiber reinforced resin composition of the present invention does not impair the present invention Within the scope of the purpose and effect, (E) a flame retardant may also be blended. (E) The flame retardant is not particularly limited as long as it can improve the flame retardancy of the composition, and may be, for example, a bromine compound, a chlorine compound, a fluorine compound, a phosphorus compound, a red phosphorus, a nitrogen compound, a ruthenium compound, Boron compound, hydrazine compound, and the like.

The resin composition of the present invention does not impair the effects of the present invention. In addition, it can also be blended, for example, stabilizer, mold release agent, ultraviolet absorber, colorant, flame retardant, anti-drip agent, slip agent, fluorescent whitening agent, phosphorescent pigment, fluorescent dye Additives such as flow modifiers, impact modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalyst antifouling agents, infrared absorbing agents, photochromic agents, fillers other than carbon fibers, or the present invention (A) a semi-aromatic polyamide resin and (C) a thermoplastic resin other than a dendritic polyester, a thermosetting resin, or the like.

The method for producing the resin composition of the present invention satisfies the requirements of the present invention In the premise of the requirements, the rest is not particularly limited, and it is preferred to use, for example, polyamine resin, carbon fiber, dendritic polyester, and other components as needed, by uniform smelting and kneading using a uniaxial or biaxial extruder. And a method of removing the solvent after mixing in a solution. From the viewpoint of productivity, a method of uniformly melting and kneading by a uniaxial or biaxial extruder is preferred, and from the viewpoint of obtaining a resin composition which is easily dispersed in carbon fibers and has excellent mechanical properties and surface appearance of the molded article, The system uses a twin-screw extruder for uniform melt-kneading. However, when the screw length is L and the screw diameter is D, a method of melt-mixing the wire using a twin-screw extruder of L/D>30 is particularly preferable. The term "screw length" as used herein refers to the length from the position where the raw material is supplied from the root of the screw to the tip end portion of the screw. Further, the melt-kneaded yarn is generally cut and granulated.

In the present invention, a method of injecting each component when performing melt kneading For example, an (A) semi-aromatic polyamide resin, (B) carbon fiber, (C) tree may be supplied from a main inlet provided at the root side of the screw using an extruder provided with two inlets. Polyester, and other ingredients as needed; supply (A) semi-aromatic polyamide resin, (C) dendritic polyester and other ingredients from the main input port, and from the main inlet and extruder front end a secondary input port, a method of supplying (B) carbon fiber and other components as needed; supplying (A) semi-aromatic polyamide resin and other components from the main input port, and from the main input port and the auxiliary input port Two methods of supplying (B) carbon fiber and other components as needed. From the viewpoint of production stability and excellent mechanical properties of the molded article, it is preferred to supply (A) a semi-aromatic polyamide resin, (C) dendritic polyester, and other components from the main inlet, and from the main inlet. A method of supplying (B) carbon fibers to a secondary input port provided between the front end of the extruder.

The carbon fiber weight in the granule obtained by the resin composition of the present invention is flat The average fiber length is not particularly limited, and is preferably in the range of 0.1 to 0.5 mm. When the weight average fiber length of the carbon fiber is in the above preferred range, sufficient impact strength and flexural modulus can be obtained, and there is no possibility that fluidity, surface appearance, and sheet formability are lowered.

In addition, the carbon fiber weight average fiber length in the granular material is obtained by calcining the granular material at 500 ° C for 1 hour, and the obtained ash is subjected to water dispersion, followed by filtration, and the residue is observed by an optical microscope, and the result of measuring 1,000 lengths is converted. It can be obtained for the weight average fiber length. Specifically, the granules of the resin composition were placed in a crucible of about 10 g, and smoldering was performed in an electric heating furnace until no flammable gas was generated, and then calcination was further performed in an electric furnace set at 500 ° C for 1 hour. A residue of only carbon fiber is obtained. The image was magnified 50 to 100 times by an optical microscope, and the length of 1,000 randomly selected samples was measured, and the measured value (mm) (effective number to the second decimal place) was used, according to the following formula (1) or formula (1) 2) can be calculated.

Weight average fiber length (Lw) = Σ (Wi × Li) / Σ Wi = Σ (π × ri ² × Li × ρ × ni × Li) / Σ (π × ri ² × Li × ρ × ni) ‧ ‧ Formula 1)

Here, Li represents the fiber length of the carbon fiber, ni represents the carbon fiber count of the fiber length Li, Wi represents the carbon fiber weight of the fiber length Li, ri represents the fiber diameter of the carbon fiber of the fiber length Li, and ρ represents the density of the carbon fiber. The π system represents a pi, and the cross-sectional shape of the carbon fiber is approximated to a perfect circle of the fiber diameter ri. When the fiber diameter ri and the density ρ are constant, the above formula (1) approximates the following, and the weight average fiber length can be obtained by the formula (2).

Weight average fiber length (Lw) = Σ (Li ² × ni) / Σ (Li × ni) ‧ ‧ (2)

(B) A method of adjusting the weight average fiber length of the carbon fiber to the above range, for example, a method of blending a carbon fiber having an arbitrary fiber length distribution with a target fiber length; and adjusting a melt viscosity of the thermoplastic resin used Further, a method of imparting shear to the carbon fibers is adjusted, and a method of adjusting the number of screw rotations, the temperature of the barrel, and the amount of discharge when the resin composition described later is melt-kneaded is adjusted.

The carbon fiber reinforced resin composition of the present invention can be generally known. Any method such as injection molding, compression molding, extrusion molding, blow molding, press molding, or spinning can be processed into various molded articles. The molded article may be, for example, various types of films such as injection molded articles, extrusion molded articles, blow molded articles, uniaxially stretched, and biaxially stretched, such as various films, sheets, undrawn yarns, extended yarns, and super high-stretch yarns.

The resin composition of the present invention is preferably obtained by granules manufactured as described above The article is subjected to injection molding to produce various molded articles. The injection molding method can be, for example, injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the case of using supercritical fluid injection), insert molding, in-mold coating molding, heat-insulation molding, Rapid heating and cooling mold forming, two-color molding, sandwich molding, ultra-high-speed injection molding, etc., can be appropriately selected in accordance with the purpose. The advantages of these various forming methods are well known. also, The forming system may be any of a cold runner method and a hot runner method.

In the molded article obtained by molding the resin composition of the present invention, carbon fiber The weight average fiber length of the dimension is not particularly limited, and is preferably in the range of 0.01 to 0.5 mm. When the weight average fiber length of the carbon fiber is in the preferred range, sufficient impact strength, bending elastic modulus, and the possibility that the surface appearance is lowered are not obtained. In addition, the weight of the carbon fibers in the molded article is as long as the average fiber length is obtained by cutting a sample of a predetermined amount from the molded article at 500 ° C for 1 hour, and then the obtained ash is subjected to water dispersion, followed by filtration, and the residue is observed by an optical microscope to measure 1,000. The result of the length of the branch is converted into a weight average fiber length and can be obtained. Specifically, a sample in which a resin composition molded product was cut out was placed in a crucible of about 10 g, and smoldering was performed in an electric heating furnace until no combustible gas was generated, and then calcination was further performed in an electric furnace set at 500 ° C for 1 hour. And obtain a residue of only carbon fiber. The image was magnified 50 to 100 times by an optical microscope, and the length of 1,000 randomly selected samples was measured, and the measured value (mm) (effective number to the second decimal place) was used, according to the former formula (1) or formula (1) 2) can be calculated.

Adjusting the weight average fiber length of the (B) carbon fiber in the molded article to the above The means of the range is, for example, a method of using a granular material having an arbitrary fiber length distribution in accordance with the target fiber length; and appropriately adjusting the number of screw rotations, the barrel temperature, the injection pressure, and the back pressure during melt processing such as injection molding. Method, etc.

A molded article obtained by molding the resin composition of the present invention, a molded article The ratio of the weight average fiber length to the number average fiber length (Lw/Ln) of the carbon fiber in the medium is preferably 1.0 or more and less than 1.3. When Lw/Ln is in the preferable range, a molded article excellent in surface appearance and warpage can be obtained.

Average the average fiber length and number of (B) carbon fibers in the molded article The ratio of the fiber length (Lw/Ln) to the above range is, for example, a method of using a granule having an arbitrary fiber length distribution in accordance with the target fiber length; and appropriately adjusting a screw for performing melt processing such as injection molding. Method of number of rotations, barrel temperature, injection pressure, and back pressure.

The molded article obtained by molding the resin composition of the present invention can be widely used The range is used for various purposes such as automobile parts, electric appliances, electronic components, building components, various containers, daily necessities, household groceries, and sanitary articles. The molded article obtained by using the resin composition of the present invention is particularly suitable for a housing of an electric/electronic part because it is particularly high in rigidity and excellent in surface appearance and water absorption characteristics. Moreover, since it is excellent in fluidity and sheet formability and can reduce warpage, it is suitable for a thin-plate electronic machine frame having an average wall thickness of 0.5 to 1.0 mm or less. In addition, the average wall thickness of the thin-plate electronic machine frame refers to the average value of the number of wall thicknesses randomly selected in the electronic machine frame. The wall thickness can be measured using a micrometer. The thin electronic device frame can be, for example, a frame of a notebook personal computer, an electronic organizer, a mobile phone, a PDA, a digital camera, a projector, and the like. It is more suitable for the frame of a notebook PC with a large area and needs fluidity.

[Examples]

In order to further clarify the present invention, the following examples and comparative examples are described, but the present invention is not limited to the examples. In addition, various characteristics in the examples were evaluated in accordance with the following methods.

(1) The ultimate viscosity of polyamide resin

0.1 g of polyamine resin was dissolved in 50 mL of a 98% sulfuric acid solution, and the number of seconds of the sample solution was measured at 30 ° C ± 0.05 ° C using an Ubbel-type viscometer, and the ultimate viscosity was calculated according to the following formula.

[η]=η _sp /[C(1+0.205η _sp )], η _sp =(tt ₀ )/t ₀

In the above formula, [η] represents the ultimate viscosity (dL/g), η _sp represents the specific viscosity, C represents the sample concentration (g/dL), and t represents the number of seconds of the sample solution (seconds), t ₀ It is the number of seconds of flow of sulfuric acid (seconds).

(2) Melting point of polyamide resin

Using a precision scanning calorimeter EXSTAR DSC6000 manufactured by Seiko Instruments Co., Ltd., temporarily hold the polyamide resin at 330 ° C for 5 minutes, then cool down to 23 ° C at a rate of 10 ° C / min, and measure the temperature at 10 ° C / min. Melt the endothermic spike and set it to the melting point.

(3) Flexural modulus and bending strength of the molded article

The pellets of the resin composition obtained in each of the examples and the comparative examples were subjected to injection molding into a bending test under the conditions of a barrel temperature of 300 ° C and a mold temperature of 80 ° C using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. Sheets were evaluated for bending strength and flexural modulus at 23 ° C according to ISO178.

(4) Impact resistance of molded articles

The pellets of the resin composition obtained in each of the examples and the comparative examples were subjected to injection molding into a summer at a barrel temperature of 300 ° C and a mold temperature of 80 ° C using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. The Charpy impact strength (with a notch) was evaluated at 23 ° C according to ISO 179.

(5) Liquidity of resin composition

The pellets of the resin composition obtained in each of the examples and the comparative examples were subjected to a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a barrel temperature of 320 ° C and a mold temperature of 130 ° C. Injection molding was carried out under the conditions of an injection pressure of 55 MPa, an injection time of 5 seconds, and a molded article thickness of 0.7 mm. After the first 20 shots were formed, the flow length of the molded article that was formed 10 times was averaged, and the value was set to a bar flow length. The larger the value, the more excellent the fluidity.

(6) Water absorption of molded articles

The pellets of the resin composition obtained in each of the examples and the comparative examples were subjected to injection molding into dumbbells under the conditions of a barrel temperature of 300 ° C and a mold temperature of 80 ° C using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. Test piece. Using the obtained dumbbell test piece, it was allowed to stand at 80 ° C and 95% RH, and a water absorption test for measuring the change in weight with time was measured, and the weight at the time of drying (before the water absorption test) and after 1,000 hours was measured, and the following formula was used. Take the water absorption rate. In addition, the "weight during drying" in the following formula means the initial weight of the dumbbell test piece before the water absorption test is performed.

Water absorption rate (%) = [(95% RH weight after 1,000 hours - weight when dry) / weight when dry] × 100

(7) Water absorption characteristics of molded articles

Using the dumbbell test piece after the water absorption test of the above (6), the bending strength was evaluated in the same manner as in the above (3), and the strength retention ratio was obtained from the following formula.

Strength retention rate (%) = (bending strength after water absorption test) / (bending strength before water absorption test) × 100

(8) Warpage of the molded article

The pellets of the resin composition obtained in each of the examples and the comparative examples were subjected to a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries Co., Ltd. at a barrel temperature of 320 ° C, a mold temperature of 130 ° C, an ejection time of 10 seconds, and a cooling time. Fill the resin at 80mm × 80mm × under 20 seconds After the injection molding was carried out in a mold having a thickness of 1 mm, it was taken out in a state where the gate portion was not cut by cooling, and a test piece for warpage evaluation was used. After the test piece was allowed to stand at 25 ° C and a humidity of 65% for 24 hours, the height of the buckling (the amount of warpage) on the opposite end surface was measured based on the gate side, and the evaluation was performed in the following four stages. .

Excellent: The bounce height is below 0.5mm.

Good: The bounce height is more than 0.5mm and less than 1.0mm.

Poor: The bounce height is more than 1.0mm and less than 3.0mm.

Inferior: The bounce height exceeds 3.0mm.

(9) Surface appearance

The surface gloss and surface unevenness of the test piece of 80 mm × 80 mm × 1 mm thick prepared in the above (8) were visually observed and evaluated according to the following criteria.

Good: the surface gloss is high and almost no bumps are found.

Poor: Although the surface gloss is high, there are bumps.

Inferior: The surface is rough and dull.

(10) Sheet formability of resin composition

In order to verify the applicability to the thin-plate electronic machine frame, the 750-ton injection molding machine was used for the pellets of the resin composition obtained in each of the examples and the comparative examples, and the extrusion temperature was 320 ° C, and the mold temperature was 100 to 120 ° C. Next, in the case where the hot runner was not used, injection molding was performed using a 220 mm × 300 mm × 0.8 mm thick mold (11-point gate). The results were evaluated in the following three stages.

Excellent: The molded product can be obtained and the warpage is small.

Good: Although warpage occurs, a molded article can be obtained.

Inferior: The molded article cannot be obtained due to insufficient filling.

(11) Thermal stability of resin composition

The resin temperature at the time of melt-kneading by the twin-screw extruder in each of the examples and the comparative examples was measured, and the gas generation conditions were evaluated in accordance with the following three stages.

Excellent: almost no gas is generated.

Good: A small amount of gas is generated.

Inferior: a large amount of gas.

(12) Terminal amine concentration of polyamine resin and resin composition

0.2 g of a pellet of a polyamide resin or a resin composition was dissolved in 10 mL of hexafluoroisopropanol to form a sample solution, which was measured by performing potentiometric titration using a 0.02 N hydrochloric acid aqueous solution.

(13) Staying stability

Using the produced resin composition pellets, the MFR at the residence time of 5 minutes and 30 minutes was measured according to ASTM D-1238-82 under the conditions of a load of 2.16 kg and a temperature of 300 ° C, and the calculation was made to be MFR5. , MFR30 ratio: MFR30/MFR5.

The closer the value is to 1, the better the retention stability is. When the value is less than 1, the viscosity is increased due to the retention, and the formability is lowered. When the value is more than 1, the resin is decomposed due to the retention. If it is in the range of 0.8 to 1.2, the retention stability will be better, and it will be better in the range of 0.9 to 1.1.

(14) Average fiber length of carbon fiber of granules and molded articles

10 g of the sample was cut out from the granular material and the tensile test piece, and calcined in an electric furnace set at 500 ° C for 1 hour, and then dispersed in ion-exchanged water and filtered, and the residue was observed by an optical microscope at a magnification of 50 to 100 times. The length of 1,000 pieces was measured, and the weight average fiber length (Lw) and the number average fiber length (Ln) of the carbon fibers of the granular material and the molded article were respectively determined.

(Production Example 1) Production of Polyamide Resin (A-1)

a mixture of 4,539.3 g (27.3 mol) of citric acid, (a) 1,9-nonanediamine and (b) 2-methyl-1,8-octanediamine [(a)/(b)=50 /50 (Morby)] 4,478.8 g (28.3 mol), benzoic acid 101.6 g (0.83 mol), sodium hypophosphite monohydrate 9.12 g (relative to the total mass of the raw material 0.1% by mass), and distilled water 2.5 The liter was placed in a hot press with an internal volume of 20 liters and replaced with nitrogen. The mixture was stirred at 100 ° C for 30 minutes, and the temperature inside the autoclave was raised to 220 ° C over 2 hours. At this time, the pressure inside the autoclave was raised to 2 MPa. After continuing the reaction for 2 hours in this state, the temperature was raised to 230 ° C, and then the temperature was maintained at 230 ° C for 2 hours, and the water vapor was gradually removed, and the reaction was carried out while maintaining the pressure at 2 MPa. Next, the pressure was lowered to 1 MPa over 30 minutes, and the reaction was further carried out for 1 hour to obtain a prepolymer having an ultimate viscosity [η] of 0.18 dL/g.

The obtained prepolymer was dried at 100 ° C under reduced pressure for 12 hours, and pulverized to a particle size of 2 mm or less, and solid phase polymerization was carried out at 230 ° C and 13 Pa (0.1 mmHg) for 8 hours to obtain a melting point of 262 ° C and an ultimate viscosity. 0.91 dL/g of white polyamide resin (A-1).

(Production Example 2) Production of Polyamide Resin (A-2)

In Production Example 1, only the solid phase polymerization time was changed to 2 hours, and a polyamide resin (A-2) having a melting point of 262 ° C and an ultimate viscosity of 0.52 dL/g was produced.

(Production Example 3) Production of Polyamine Resin (A-3)

In Production Example 1, a polyamide resin (A-3) was produced in the same manner except that the amount of benzoic acid added was changed to 1.02 g (0.008 mol). The melting point of (A-3) was 262 ° C, and the ultimate viscosity was 0.9 dL/g.

(Production Example 4) Production of Polyamine Resin (A'-3)

Except that the molar ratio of the mixture of (a) 1,9-nonanediamine and (b) 2-methyl-1,8-octanediamine is changed to (a)/(b)=80/20, The rest were produced in the same manner as in Production Example 1 to produce a polyamide resin. (A'-3). The melting point of (A'-3) was 302 ° C and the ultimate viscosity was 0.91 dL/g.

(Production Example 5) Production of dendritic polyester (C-1)

In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4'-dihydroxybiphenyl, and 7.28 of p-citric acid were charged. g (0.045 mol), polyethylene terephthalate having an intrinsic viscosity of about 0.6 dL/g, 14.41 g (0.075 mol), and acetic anhydride (62.48 g, 1.00 equivalent of total phenolic hydroxyl groups) under a nitrogen atmosphere The reaction was carried out at 145 ° C for 2 hours while stirring. Then, 31.52 g (0.15 mol) of trimellitic acid was added, and the temperature was raised to 260 ° C, and the mixture was stirred for 3 hours. When the theoretical amount of acetic acid was 91%, the heating and stirring were stopped, and the contents were spit out in cold water. A dendritic polyester (C-1) was obtained.

Knot of nuclear magnetic resonance spectroscopy for the obtained dendritic polyester (C-1) The p-oxybenzoate unit content p is 2.66, and the content q of the 4,4'-dioxybiphenyl unit and the ethylene oxide unit is 0.66, relative to the pyromellitic acid residue. The phthalate unit content r was 0.66, and p+q+r=4. The terminal is present in a ratio of carboxylic acid to ethyl sulfonate of 64:36.

Nuclear magnetic resonance spectroscopy is used to dissolve dendritic polyester (C-1) in pentafluorophenol 50%: a solution of a heavy chloroform 50% mixed solvent, and a nuclear magnetic resonance spectrum analysis of the proton nucleus was carried out at 40 °C. 7.44 ppm and 8.16 ppm spikes derived from p-oxybenzoate units, 7.04 ppm, 7.70 ppm spikes derived from 4,4'-dioxybiphenyl units, and 8.31 ppm derived from phthalate units were detected. A spike, a 4.75 ppm spike derived from an ethylene oxide unit, and a 9.25 ppm spike derived from trimesic acid. From the area intensity ratio of each peak, the content ratio of each structural unit was calculated, and the third decimal place was rounded off. From the ratio of the peak area intensity derived from the branched structure portions P, Q, and R to the peak area intensity derived from the organic residue S, the contents of the contents p, q, r and the branch point S were calculated. Further, the peak shift of the three protons of the trimesic acid was used to determine the presence or absence of the carboxylic acid reaction, and the branching degree was calculated. 0.68 (the third decimal place is rounded off). Further, the degree of branching was calculated by calculating the ratio of the three functional groups of the three functional groups of trimesic acid.

The melting point Tm of the obtained dendritic polyester (C-1) is 185 ° C, and the initial temperature of the liquid crystal The degree is 159 ° C and the number average molecular weight is 2,300. In addition, the melting point (Tm) is an endothermic peak temperature (Tm1) observed when the dendritic polyester (C-1) is measured at a temperature rise of 20 ° C / min from room temperature. After the observation, the temperature was maintained at Tm1 + 20 ° C for 5 minutes, and then temporarily cooled to room temperature according to the temperature drop condition of 20 ° C / minute, and the endothermic peak temperature (Tm observed) was measured according to the temperature rise condition of 20 ° C / min. ). The liquid crystal onset temperature is set to a temperature at which the entire field of view starts to flow at a shear rate of 100 (1/sec), a temperature increase rate of 5.0 ° C/min, and an objective lens of 60 times by a shear stress heating device (CSS-450). .

Furthermore, the number average molecular weight of the dendritic polyester (C-1) will be based on pentafluorophenol.

/Chloroform = 35/65 wt% mixed solvent, adjusted to a dendritic polyester solution having a concentration of 0.08% (wt/vol), and the absolute molecular weight was measured by GPC-LS (gel permeation chromatography-light scattering) method. The measurement conditions here were set as follows: the column was Shodex KG, Shodex K-806M×2, Shodex K-802, flow rate 0.8 mL/min, temperature 23 ° C, and the detector was a differential refractometer (RI). Multi-angle light scattering (MALS).

The other raw materials used in the examples and comparative examples are as follows.

(A'-4) Polyamide MXD6 resin "Reny" (registered trademark) #6002 (Mitsubishi Engineering Plastics Co., Ltd.) (melting point: 238 ° C)

(A'-5) Polyamine 10T resin "Vestamid" (registered trademark) HT Plus M3000 (manufactured by Daicel-Evonik Co., Ltd.) (melting point: 285 ° C)

(A'-6) Polyamine 6 resin "Amilan" (registered trademark) CM1001 (manufactured by Toray Industries, Inc.) (melting point: 222 ° C)

(B-1) PAN carbon fiber "Torayca" (registered trademark) short fiber TV14-006 (Toray) System, original yarn T700SC-12K: strand yarn strength 4.9GPa, yarn elastic modulus 230GPa)

(D-1) succinic anhydride (manufactured by Sigma-Aldrich Japan Co., Ltd.), SAJ1 grade

(E-1) phosphinate compound "EXOLIT" (registered trademark) OP1230 (manufactured by Clariant Japan Co., Ltd.)

(E-2) Acrylic acid modified tetrafluoroethylene "METABLEN" (registered trademark) A3800 (manufactured by Mitsubishi Rayon Co., Ltd.).

[Examples 1 to 8 and Comparative Examples 1 to 8]

A twin-screw extruder (TEX30 α manufactured by Nippon Steel Works Co., Ltd.) having a barrel temperature set to the temperature shown in Table 1 and a screw rotation number of 200 rpm was used. Polyamine resin, dendritic polyester, acid anhydride and flame retardant were supplied from the main funnel according to the formulations shown in Tables 1 and 2, and carbon fibers were supplied from the side feeder to the molten resin and melt-kneaded. The strands spun from the mold were cooled in water, cut into a length of 3.0 mm by a strand cutter, and pelletized to obtain a pellet of a carbon fiber reinforced resin composition. Using the produced pellets, various characteristics were evaluated by the above method. The results are shown in Tables 1-2.

The carbon fiber reinforced resin composition shown in Examples 1 to 8 can obtain heat stability. Excellent in properties, retention stability, fluidity and sheet formability, with very high rigidity (bending elastic modulus), and excellent strength, impact resistance, water absorption characteristics (low water absorption), and surface appearance. Reduced molded articles. On the other hand, the carbon fiber-reinforced resin compositions shown in Comparative Examples 1 and 7 did not contain (C) dendritic polyester, and thus had poor fluidity, sheet formability, and thermal stability (gas generation), and molded articles. The warpage is also insufficient. In the carbon fiber-reinforced resin composition shown in Comparative Examples 2 to 5, fluidity, water absorption, water absorption characteristics, warpage, sheet formability, and thermal stability were not used because the semi-aromatic polyamide resin specified in (A) was not used. Any of the characteristics (gas generation conditions) is poor. In the carbon fiber reinforced resin composition shown in Comparative Example 6, since the blending amount of the (B) carbon fiber is 44 parts by weight with respect to 100 parts by weight of the (A) semi-aromatic polyamide resin, the bending elastic modulus is obtained. difference. In the carbon fiber reinforced resin composition shown in Comparative Example 8, since the blending amount of the (B) carbon fiber is in a state of excess of 212 parts by weight based on 100 parts by weight of the (A) semi-aromatic polyamide resin, it is apparent during melt kneading. The heat causes a large amount of gas to be generated, and the granulation is difficult.

(industrial availability)

The carbon fiber-reinforced resin composition of the present invention can obtain a molded article which is excellent in thermal stability, retention stability, fluidity, and sheet formability, and has rigidity equivalent to metal, excellent surface appearance and water absorption characteristics, and warpage. Therefore, it is suitable for an electronic machine housing such as a personal computer, a mobile phone, or the like that requires light weight, high rigidity, sheet formability, and good surface appearance.

Claims (10)

A carbon fiber reinforced resin composition comprising, by weight of 100 parts by weight of (A) a semi-aromatic polyamide resin, 68 to 200 parts by weight of (B) carbon fibers, and 0.01 to 10 parts by weight of (C) dendritic polyester. And the obtained (A) semi-aromatic polyamine resin is a dicarboxylic acid containing 60 to 100 mol% of p-citric acid in the total amount of dicarboxylic acid, and 1,9-壬 in the total amount of diamine. A diamine and a 2-methyl-1,8-octanediamine total of 60 to 100 mol% of a diamine are obtained by polycondensation, and have a melting point of 220 to 300 °C. The carbon fiber reinforced resin composition according to the first aspect of the invention, wherein the (A) acid anhydride is further blended in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the (A) semi-aromatic polyamide resin. The carbon fiber reinforced resin composition according to claim 1 or 2, wherein the (A) semi-aromatic polyamide resin has a limit viscosity of 0.5 to 1.3 dL measured at 30 ° C in 0.2 g/dL concentrated sulfuric acid. /g range. The carbon fiber reinforced resin composition according to claim 1 or 2, wherein the carbon fiber reinforced resin composition (A) semi-aromatic polyamide resin has a terminal amine group concentration of 0.1 to 30 meq/kg per 1 kg. . A granular material obtained by molding a carbon fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 4, wherein the carbon fiber has a weight average fiber length of 0.1 to 0.5 mm. A molded article obtained by subjecting a granular material of the fifth aspect of the patent application to injection molding. The molded article of claim 6, wherein the carbon fiber in the molded article has a weight average fiber length of 0.01 to 0.5 mm. Such as the molded article of claim 6 or 7, wherein among the molded articles, carbon fiber The ratio of the weight average fiber length to the number average fiber length (Lw/Ln) is 1.0 or more and less than 1.3. An electronic machine frame obtained by subjecting a granular material of the fifth application of the patent application to injection molding. For example, the electronic machine frame of claim 9 wherein the average wall thickness is 0.5 to 1.0 mm.