WO2008102893A1

WO2008102893A1 - Long fiber-reinforced thermoplastic resin composition

Info

Publication number: WO2008102893A1
Application number: PCT/JP2008/053113
Authority: WO
Inventors: Masahiro Katayama; Yuichi Ohe; Hideaki Sakamoto
Original assignee: Daicel Polymer Ltd.
Priority date: 2007-02-23
Filing date: 2008-02-18
Publication date: 2008-08-28
Also published as: KR20090094467A; CN101622312B; CN101622312A; KR101122736B1; JP5226227B2; JP2008202012A

Abstract

Disclosed is a polycarbonate resin composition which is small in anisotropy of linear expansion coefficient, while being excellent in dimensional stability, fluidity and heat resistance. Specifically disclosed is a long fiber-reinforced thermoplastic resin composition obtained by blending 11-200 parts by weight of a reinforcing fiber per 100 parts by weight of a composition composed of a polycarbonate resin (PC) and a styrene resin (SR).

Description

Description Long fiber reinforced thermoplastic resin composition Technical Field

The present invention relates to a long fiber reinforced thermoplastic resin composition in which an alloy in a specified ratio of a polycarbonate resin (P C) and a styrene resin (S R) is reinforced as a resin. Background art

Polycarbonate is a thermoplastic resin with a carbonate ester bond in the main chain, and has excellent mechanical properties, heat resistance, and electrical properties, and is a typical engineering plastic. However, it has a decomposition temperature of about 320 ° C. When the number of processing steps by heating increases, decomposition begins and it becomes difficult to maintain its excellent mechanical strength.

JP-A 2 0 0 1— 2 9 4 7 4 1 includes a resin composition component composed of a polycarbonate resin and a silicon-containing inorganic filler such as talc, with ethylene (meth) acrylic acid copolymer. JP-A 2 0 0 3-2 7 7 5 9 7 includes a polycarbonate resin reinforced with chopped strands of glass fiber, and a blend of ethylene and ethylene (meth) acrylate ester copolymer. Methods of adding compounds and fluorine-containing polymers have been proposed. However, more robust performance is required. Disclosure of the invention

An object of the present invention is to provide a polycarbonate resin composition having a small linear expansion coefficient and excellent in dimensional stability, fluidity and heat resistance.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a polycarbonate resin and a polycarbonate resin and a resin composition are formed by a pultrusion method in which a roving fiber bundle is opened and impregnated with a molten resin. As a result, it has been found that a molded product having a remarkable mechanical strength can be obtained by specific blending of styrene resin and the present invention has been completed.

Therefore, the object of the present invention is to calculate the weight ratio of polycarbonate resin (PC) and styrene resin (SR). Jinno 31 = 95 5-30 30 70 Long fiber reinforced thermoplastic resin composition comprising 100 to 100 parts by weight of reinforcing fiber 1 1 to 200 parts by weight, and the reinforcing fiber is pelleted. The long fiber reinforced thermoplastic resin composition, which is arranged substantially parallel to the length direction, is shaped into a columnar shape, a prismatic shape, or a tape shape, and is cut into any length of 4 to 50 mm. provide.

The thermoplastic resin composition in which the polycarbonate resin (PC) and styrenic resin (SR) alloy of the present invention is fiber reinforced by a drawing method has excellent fluidity, mechanical strength, heat resistance, impact resistance, and dimensional accuracy. The present invention provides a long fiber reinforced resin composition for excellent molded products, and such pellets are particularly excellent in balance between heat resistance and fluidity. Detailed Description of the Invention

The fiber used in the present invention is not particularly limited. For example, inorganic fibers such as glass, carbon, basalt, silicon carbide, basalt, and boron; metal fibers such as stainless steel; aramid, rayon, Examples thereof include at least one selected from the group consisting of nylon and polyester organic fibers; cellulose fibers and the like. As the reinforcing fiber, at least one having higher elasticity than the matrix resin is selected, and a fiber having a large function of reinforcing the rigidity of the matrix resin is preferable. Glass, carbon and basalt fibers are particularly preferred. These fibers can be used in combination.

In the present invention, the reinforcing fiber has a diameter of 0.1 to 50 / zm, preferably 3 to 30 μπι, more preferably 4 to 20 μπι depending on the material. In the present invention, the reinforcing fiber contained in the pellet for molding does not become longer than the pellet length, although it depends on the pellet length, the average length is 4 to 5 Omm, preferably 5 to 40 mm, more preferably 6 to 3 Omm. Examples of the glass fiber include commercially available products such as E-glass, S-glass, C-glass, AR-glass, T-glass, D-glass and R-glass. When manufacturing pellets of fiber reinforced thermoplastic resin, glass fibers can be used in the form of a so-called glass roving in which a bundle of a plurality of filaments is usually wound into a coil. . A glass fiber diameter of 3 to 40 / im is suitable. If it is less than 3 μπι, impregnation with resin becomes difficult because the number of glass fibers is relatively increased when the glass content is high, and if it exceeds 40 μπι, the surface appearance of the molded product is significantly deteriorated. The optimum glass fiber diameter is 9 to 20 / m.

The glass fiber may be surface-treated with a binder (surface treatment agent) containing a force pulling agent. As the coupling agent, silane coupling agents such as aminosilane, epoxy silane, amide silane, azido silane, and acrylic silane, titanate coupling agents, and mixtures thereof can be used. Of these, aminosilanes and epoxysilanes are preferred, and epoxysilane coupling agents are particularly preferred. The type of film former used for collecting and bundling a plurality of filaments is not particularly limited, and any suitable one including those conventionally known can be used.

The carbon fiber used in the present invention is preferably treated with a sizing agent. Examples of the carbon fiber material that has been surface-treated with a sizing agent include polyacrylonitrile (P AN), pitch, and rayon carbon fibers, with PAN being preferred. Carbon fibers are commercially available in the form of rovings in which a large number of single yarns are bundled, and there are no particular restrictions on the thickness, number, and length, but generally the single yarn diameter is 3 to 10 μιη, Preferably, 4 to 8 μπι, more preferably 5 to 7 m can be used. Carbon fiber is generally used as a composite strengthening material with various matrix resins, and surface activation treatment such as electrolysis treatment and gas phase surface treatment with active gas to improve adhesion to matrix resin. Are preferably introduced with a functional group such as a hydroxyl group, a carboxyl group or an amino group on the surface.

The carbon fiber surface-treated with the sizing agent used in the present invention includes Land strength of preferably 35 Okgf / discussions ² (343 OMP a) above, more preferably rather is ^{400kgf / mm 2 (392 OMP a} ) above, more preferably 450 kgf / mra ²

(441 OMP a) or more, and the elastic modulus is 22 tf / ram ² (21 6000 MP a) or more, preferably 24 / image ² (235000 MP a) or more, more preferably 28 / 匪² ( 275000MP a) More than that can be used.

As the carbon fiber sizing agent according to the present invention, an aliphatic compound having a plurality of epoxy groups can be used. The above aliphatic compounds are acyclic linear saturated hydrocarbons, branched saturated hydrocarbons, acyclic linear unsaturated hydrocarbons, branched unsaturated hydrocarbons, or carbon atoms (CH ₃ , CH ₂ , CH, C) is a chain structure compound in which oxygen atoms (O), nitrogen atoms (NH, N), sulfur atoms (S0 ₃ H, SH), and carbon atom groups (CO) are replaced. Say. In the present invention, in an aliphatic compound having a plurality of epoxy groups, the largest atom among the total number of carbon atoms and heteroatoms (oxygen atoms, nitrogen atoms, etc.) constituting a chain structure connecting two epoxy groups The chain is called the longest atomic chain, and the total number of atoms constituting the longest atomic chain is called the number of atoms in the longest atomic chain. The number of atoms such as hydrogen bonded to the atoms constituting the longest atomic chain is not included in the total number. The structure of the side chain is not particularly limited, but a structure that does not easily become a crosslinking point is preferable in order to suppress the density of intermolecular crosslinking of the sizing agent compound from becoming too large. If the sizing agent compound has less than two epoxy groups, it is not possible to effectively bridge the carbon fiber and the matrix resin. Accordingly, the number of epoxy groups is preferably 2 or more in order to effectively bridge the carbon fiber and the matrix resin. On the other hand, if the number of epoxy groups is too large, the density of intermolecular crosslinking of the sizing agent compound increases, resulting in a brittle sizing layer, resulting in a decrease in the tensile strength of the composite. In the following, 4 or less is more preferable, and 2 is more preferable. More preferably, the two epoxy groups are at both ends of the longest atomic chain. That is, the presence of epoxy groups at both ends of the longest atomic chain prevents the local crosslink density from increasing, which is preferable for the composite tensile strength. As the structure of the epoxy group, a highly reactive daricidyl group is preferable. The molecular weight of the aliphatic compound is preferably 80 or more and 3200 or less, from the viewpoint of preventing deterioration of handleability as a bundling agent due to the resin viscosity being too low or too high. More preferably, it is more preferably 1500 or less, and further preferably 2200 or more and 10:00 or less.

Specific examples of the aliphatic compound having a plurality of epoxy groups in the present invention include, for example, diglycidyl ether compounds, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ethers, propylene diol diglycidyl ether, and polypropylene diamine. Examples include recall diglycidyl ethers, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and polyalkylene glycol diglycidyl ether. Polyglycidyl ether compounds include glyceryl polyglycidyl ether, diglyceryl polyglycidyl ether, polyglycidyl polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, triglyceryl ether Examples include methylolpropane polyglycidyl ethers, pentaerythritol polyglycidyl ethers, and polyglycidyl ethers of aliphatic polyhydric alcohols.

An aliphatic polydaricidyl ether compound having a highly reactive daricidyl group is preferable. More preferred are polyethylene glycol diglycidyl ethers, polypropylene dallicol diglycidyl ethers, alkanediol diglycidyl ethers and the like. In the aliphatic compound having a plurality of epoxy groups, the number of atoms of the longest atomic chain is preferably 20 or more. In other words, when the number of atoms is less than 20, the crosslink density in the sizing layer is high, so that a structure with low toughness is likely to be formed, and as a result, composite tensile strength may be difficult to develop. On the other hand, the number of atoms in the longest atomic chain is large, and the sizing layer tends to have a flexible and high toughness structure, so that the composite tensile strength is easily improved, and the tensile strength of brittle resin is particularly high. So more preferred Alternatively, the number of atoms in the longest atomic chain is 25 or more, more preferably 30 or more. However, the larger the number of atoms in the longest atomic chain, the more flexible the structure will be, but if it is too long it will bend and block the functional group, resulting in a decrease in the adhesion between the carbon fiber and the resin. Therefore, the number of atoms is preferably 200 or less, more preferably 100 or less. In the case where the aliphatic compound contains a cycloaliphatic skeleton, it can be used as long as the epoxy group is sufficiently away from the cyclic skeleton, specifically, if the number of atoms is 6 or more. In the present invention, an aromatic compound having a plurality of epoxy groups having 6 or more atoms between the epoxy group and the aromatic ring can also be used as a sizing agent. The number of atoms between the epoxy group and the aromatic ring refers to the total number of carbon atoms, heteroatoms (oxygen atoms, nitrogen atoms, etc.), and carbonyl groups constituting the chain structure connecting the epoxy group and the aromatic ring. . In this case, the linear structure is the same as the chain structure described above.

If the number of atoms between the epoxy group and the aromatic ring is less than 6 as a sizing agent, a rigid and sterically large compound will be interposed at the interface between the carbon fiber and the matrix resin. The reactivity with the surface functional groups present on the surface cannot be improved, and as a result, improvement in the lateral characteristics of the composite cannot be expected.

Two phenol rings connected by an alkylidene group, that is, bisphenol A part or F part, have the effect of improving the compatibility with the matrix resin and the effect of improving the fluff resistance. The skeleton of the aromatic compound having a plurality of epoxy groups having 6 or more atoms between the epoxy group and the aromatic ring may be a condensed polycyclic aromatic compound. Examples of the skeleton of the condensed polycyclic aromatic compound include naphthalene, anthracene, phenanthrene, chrysene, pyrene, naphthacene, triphenylene, 1,2-benzanthracene, and benzopyrene. Naphthalene, anthracene, phenanthrene, and pyrene having a small skeleton are preferable. The epoxy equivalent of the condensed polycyclic aromatic compound having a plurality of epoxy groups is preferably from 150 to 35, more preferably from 200 to 300, from the viewpoint of obtaining a sufficient effect of improving adhesiveness. The molecular weight of the condensed polycyclic aromatic compound having a plurality of epoxy groups is from 400 to 80, from the viewpoint of preventing the handling property as a sizing agent from deteriorating due to a high resin viscosity. Furthermore, 400-600 is preferred.

In the present invention, sizing agents include bisphenol type epoxy compounds having a low molecular weight such as Epicoat 828 and Epicoat 834, linear low molecular weight epoxy compounds, polyethylene glycol, polyurethane, polyester emulsifiers, surfactants, etc. These components may be added for the purpose of adjusting viscosity, improving scratch resistance, improving fuzz resistance, improving bundling properties, and improving higher-order processability. Further, there is no problem even if a rubber such as butadiene nitrile rubber or a linear epoxy-modified compound having elastomer properties such as epoxy-terminated butadiene nitrile rubber is added. Carbon fiber surface-treated with such a sizing agent (s) is a commercial product, such as Tre force T 700 SC— 2.4000— 50 C (registered trademark, manufactured by Toray Industries, Inc.), etc. Is mentioned.

Moreover, the basalt fiber used in the present invention is preferably treated with various surface treatment agents in order to improve adhesion with a thermoplastic resin.

As the surface treatment agent, a silane coupling agent is preferable, and as the silane coupling agent, one of an epoxy group, a vinyl group, an amino group, a methacryl group, an acryl group, and a linear alkyl group is included in the molecule. The silane coupling agent that you have can be used. One silane coupling agent may be used, or two or more silane coupling agents may be used in combination. Among the silane coupling agents, epoxy silanes, amino silanes, and linear alkyl silanes having an epoxy group, an amino group, and a linear alkyl group in the molecule are particularly preferable. As the epoxy group of the epoxy silane coupling agent, glycidyl group, alicyclic epoxy group, etc. are suitable, and as a powerful silane coupling agent, Nippon Tunica A-1186, A-187 AZ-6137, AZ-6165 (trade name) and the like. Examples of aminosilane-based silane coupling agents include primary amines, secondary amines, or both. A— 1 1 00, A— 1 1 10, A— 1 120, manufactured by Nippon Tunica Co., Ltd. Specific examples include Y-9669, A-1 1 60 (name of product). Examples of linear alkylsilanes include those having a hexyl group, an octyl group, and a decyl group. Nippon Tunica Co., Ltd. Specific examples include AZ _ 6 1 7 1 manufactured by AZ -6 1 7 7 (named above, trade name), KBM-3 1 0 3 C (trade name) manufactured by Shin-Etsu Silicone Co., Ltd., and the like. Of these, epoxy silane is preferred.

The long fiber reinforced resin pellet of the present invention is obtained by a pultrusion method in which a fiber is impregnated with a thermoplastic resin while pulling continuous reinforcing fibers. For example, a resin additive may be added to the thermoplastic resin as necessary, and the thermoplastic resin may be supplied in a molten state from the extruder to the crosshead die while pulling the continuous fiber through the crosshead die. It is obtained by impregnating a continuous fiber for reinforcement with a thermoplastic resin, heating the melt-impregnated material, cooling, and cutting it at right angles to the drawing direction, so that the reinforcing fiber has the same length in the longitudinal direction of the pellet. Are arranged in parallel. In pultrusion, the resin is impregnated basically while drawing a continuous reinforcing fiber bundle. The resin is fed from an extruder or the like to the cross head while passing the fiber bundle through the cloth head. In addition to the method of supplying and impregnating, a method of impregnating resin emulsion, suspension, or impregnation bath containing solution through fiber bundles, spraying resin powder onto fiber bundles or inside powder tanks A method is known in which a resin bundle is passed through a fiber bundle and a resin powder is adhered to the fiber, and then the resin is melted and impregnated. Particularly preferred is the crosshead method. In addition, the resin impregnation operation in these pultrusion moldings is generally carried out in one stage, but this may be divided into two or more stages, and the impregnation method may be different. .

The polycarbonate resin (PC) used in the present invention includes a polyester carbonate resin in addition to the polycarbonate resin. Polycarbonate resins are usually obtained by the reaction of dihydroxy compounds with phosgene (phosgene method), or the reaction of dihydroxy compounds with carbonates such as diphenyl carbonate (ester exchange method). The dihydroxy compound may be an alicyclic compound or the like, but is preferably a bisphenol compound.

Bisphenol compounds include bis (4-hydroxyphenyl) methane, 1, 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) 1_bis (4-hydroxyphenyl), propane, 2, 2 —Bis (4—Horoki Bis such as propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) hexane

(Hydroxyl reel) C 卜 8 Alkane; 1, 1-bis (4-Hydroxyphenyl) Bis (hydroxyl reel) such as cyclohexane C4-12 cycloalkane; 4, A'-hydroxydiphenyl ether; 4, 4 '— Dihydroxy diphenyl ^ / Hong; 4, 4' — Dihydroxy dipheny ^ / snored. These bisphenol compounds may be used alone or in combination of two or more.

A preferred polycarbonate resin is an aromatic polycarbonate, and bisphenol type aromatic polycarbonate (bisphenol type aromatic polycarbonate) is particularly preferable.

The viscosity average molecular weight of the polycarbonate resin (PC) used in the present invention is from 1300 to 20000, preferably from 14000 to: 19000, more preferably from 15,000 to 18000. In addition, the viscosity average molecular weight referred to in the present application is a value measured by the method of Examples described later.

Examples of the styrene resin (SR) include a resin (or polymer) containing at least an aromatic vinyl monomer (or styrene monomer) as a polymerization component.

Aromatic vinyl monomers include, for example, styrene, alkyl-substituted styrene (for example, vinylol toluene, vinylol xylene, p-ethynole styrene, p-isopropino styrene, butynole styrene, p-t-butino styrene. ), Halogen-substituted styrene (eg, chlorostyrene, promostyrene, etc.), monoalkyl-substituted styrene substituted with an alkyl group at the α-position (eg, α-methylstyrene, etc.), and the like. These aromatic vinyl monomers can be used alone or in combination of two or more. Of these aromatic butyl monomers, styrene monomers such as styrene, vinyltoluene and α-methylstyrene (especially styrene) are usually used.

The styrene resin may be a copolymer with a monomer (copolymerizable monomer) copolymerizable with an aromatic vinyl monomer. To copolymerizable monomer (vinyl monomer) Includes vinyl cyanide monomers, acrylic monomers, butyl ester monomers, unsaturated polycarboxylic acids or acid anhydrides, imide monomers, and the like. In addition, the bull monomer may be a vinyl halide monomer such as bull chloride.

Examples of the vinyl cyanide monomer include (meth) acrylonitrile, nitrogenated (meth) acrylonitrile and the like. These vinyl cyanide monomers can be used alone or in combination of two or more. Of these vinyl cyanide monomers, (meth) atarylonitrile such as acrylonitrile is usually used.

In the present invention, the weight ratio of the aromatic vinyl monomer to the vinyl cyanide monomer is 90 10 to 60/40, preferably 85Z1 5 to 65Z35, more preferably 85/1 5 to 70 / Preferably 30 copolymers are used.

In particular, a graft copolymer obtained by polymerizing a monomer component containing an aromatic vinyl monomer and a vinyl cyanide monomer as main components in the presence of a rubbery polymer is preferred.

The weight average molecular weight of the styrene resin (in the rubber-containing styrene resin described later, the styrene resin as a matrix resin excluding rubber) is, for example, 1,00 0 to: 1,000,000, preferably 30,000 ~ 500,000, more preferably about 50,000-500,000.

The styrene resin may be a resin (rubber-containing styrene resin) containing a rubber component from the viewpoint of imparting excellent properties such as impact resistance to the resin composition. A rubber-containing styrene resin is a matrix composed of a styrene resin by mixing (or blending) or copolymerization (grafting polymerization, block polymerization, etc.) of a styrene resin and a rubber component (or rubber-like polymer). A polymer in which a rubbery polymer (rubber component) is dispersed may be used. A rubber-containing styrene-based resin is usually obtained by polymerizing at least an aromatic vinyl monomer in the presence of a rubber-like polymer by a conventional method (bulk polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, etc.). And a graft copolymer (rubber-grafted styrene-based polymer). As will be described later, in the present invention, as the rubber-containing styrene resin, a resin obtained by a block polymerization method can be suitably used.

Examples of rubber-like polymers include Gen rubber [polybutadiene (low cis type or high cis type polybutadiene), polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-acrylonitrile copolymer, isobutylene. one isoprene copolymer, styrene one isobutylene one Butaje down copolymer rubber, ethylene one醉酸Bulle copolymer, acrylic rubber (poly Akuriru acid c ₂ _ ₈ alkyl esters principal component and copolymerizing elastomeric one such ), Ethylene-α-olefin-based copolymers (ethylene-propylene rubber (EPR), etc.), ethylene-α-olefin-polyene copolymers (ethylene-propylene rubber (EP DM), etc.), urethane rubber, silicone rubber, Ptyl rubber, hydrogenated gen rubber (hydrogenation Styrene one butadiene copolymer, and hydrogenated butadiene polymer) and the like. In these rubber-like polymers, the copolymer may be a random or block copolymer, and the block copolymer has a Α type, ABA type, taper type, radial teleblock type structure. Copolymers having These rubbery polymers can be used alone or in combination of two or more.

A preferable rubber component is a polymer of conjugated 1,3-gen or a derivative thereof, particularly a gen-based rubber such as polybutadiene (butadiene rubber), isoprene rubber, styrene-butadiene copolymer.

In the rubber-containing styrenic resin, the content of the rubber component is about 0 to 30% by weight, preferably about 5 to 30% by weight, and more preferably about 10 to 30% by weight with respect to the entire styrenic resin. is there.

The form of the rubbery polymer dispersed in the matrix composed of the styrene resin is not particularly limited, and may be a salami structure, a core shell structure, an onion structure, or the like.

The particle diameter of the rubber-like polymer constituting the dispersed phase is, for example, a weight average particle diameter of 2300 to 300,000 nm, preferably 2400 to 2200 nm, and more preferably 2400. It can be selected from a range of about ˜1500 nm. The graft ratio of the rubbery polymer is about 5 to 1550%, preferably about 10 to about 1550%.

The styrenic resin can be obtained by a conventional method (bulk polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, etc.). For example, a non-rubber-containing styrene resin can be obtained by a conventional method using aromatic vinyl monomers (and copolymerizable monomers such as cyanide bur monomers and acrylic monomers as required). (Bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, etc.) can be obtained by polymerization. In addition, the rubber-containing styrenic resin is usually prepared by using at least an aromatic vinyl monomer in the presence of a rubber-like polymer by a conventional method (bulk polymerization, bulk suspension polymerization, suspension polymerization, solution polymerization, emulsion polymerization). Etc.). However, in methods such as solution polymerization and emulsion polymerization, impurities derived from other components in the reaction system tend to be mixed in the resin.

Therefore, in the present invention, a styrenic resin obtained by a polymerization method (suspension polymerization, bulk polymerization, bulk suspension polymerization, etc.) in which impurities such as an organic acid (or a salt thereof) described later are not easily mixed in the resin. Can be suitably used. In particular, the styrene resin obtained by bulk polymerization has a higher content of impurities such as organic acids or salts thereof, as well as sodium, chlorine, and sulfate ions, compared to resins obtained by emulsion polymerization. As a result, it is effective in reducing the content of these impurities in the resin composition.

The styrene resin (S R) used in the present invention preferably has a total content of sodium, chlorine, and sulfate of 10 ppm or less. The content ratio of sodium, chlorine and sulfate ions is a value measured by the method of Examples described later.

For this reason, a styrene-based resin is a resin obtained by bulk polymerization, that is, a resin obtained by bulk polymerization of at least an aromatic vinyl monomer [for example, an aromatic vinyl monomer and A copolymer obtained by bulk polymerization of a vinyl cyanide monomer and / or an acrylyl monomer, and obtained by bulk polymerization of at least an aromatic vinyl monomer in the presence of a rubbery polymer. Rubber-containing styrene resin, etc.] It can be used appropriately.

Typical styrenic resins include, for example, styrene resins that do not contain a rubber component (rubber-free styrene resins) {eg, polystyrene (GPPS), aromatic bullet monomers, and vinyl cyanide monomers. And / or a copolymer with an acryl-based monomer [for example, styrene-acrylonitrile copolymer (AS resin), styrene-methyl methacrylate copolymer (MS resin), acrylonitrile-styrene-methyl methacrylate copolymer Etc.] Copolymers of aromatic bule monomers and unsaturated carboxylic anhydrides [for example, styrene monomaleic anhydride copolymers

(SMA resin etc.), etc.], rubber-containing styrene resin (for example, impact-resistant polystyrene (HIPS), methyl methacrylate-modified HIPS (transparent HIPS), styrene-acrylonitrile-butadiene copolymer (ABS resin), Methyl methacrylate modified ABS resin (transparent ABS resin), α-methylstyrene modified ABS resin, imide modified ABS resin, styrene-methyl methacrylate-butadiene copolymer (MB S resin), AXS resin, methyl methacrylate Modified A XS resin, etc.}. The AXS resin refers to a resin obtained by graft-polymerizing talironitrile A and styrene S to rubber component X (acrylic rubber, chlorinated polyethylene, ethylene-propylene rubber, ethylene monoacetate copolymer, etc.). Specific examples include acrylonitrile / acrylic rubber / styrene resin (AAS resin), acrylonitrile / ethylene / propylene rubber / styrene resin (AES resin), and the like. These styrenic resins are particularly preferably resins obtained by bulk polymerization.

Among these styrenic resins, styrene resins with high-impact polystyrene, acrylic monomers and / or vinyl cyanide monomers as polymerization components (or copolymerization components) [acrylic monomer units and Styrenic resin having a vinyl or cyanide monomer unit as a structural unit, for example, co-polymerization of an aromatic vinyl monomer with a vinyl cyanide monomer and Z or acrylic monomer Styrenic resins that do not contain rubber components, such as copolymers (for example, copolymers of styrene monomers such as AS resins and vinyl cyanide monomers), acrylic monomers and / or vinyl cyanide Containing rubber containing rubber as a copolymer component (Rubber graft) Styrenic resin (Rubber component containing allylic monomer and / or cyanurized monomer and styrene monomer) Combined materials (for example, ABS resin, AAS resin, AES resin, MB S resin, methacrylic acid-modified ABS resin, etc.) are preferred. These styrenic resins can be used alone or in combination of two or more. The styrenic resin (SR) used in the present invention desirably has a melt flow rate of 20 g / 1 Omin or more, preferably 30 gZl Omin or more, more preferably 40 gZl Omin or more. The melt flow rate is a value measured by the method of an example described later.

In the present invention, a thermoplastic resin other than the polycarbonate resin and the styrene resin may be included. Examples of such other thermoplastic resins include polyester resins (polybutylene terephthalate, polyethylene terephthalate, etc.), polyamide resins (polyamide 5, polyamide 6, polyamide 6 6, polyamide 6). 10, Polyamide 1 1, Polyamide 1 2, Polyamide 6 12, Polyamide 6 66, Polyamide 6 Z 11 Aliphatic polyamide resins such as Polyamide 6T, Polyamide 9, Polyamide MX D Aromatic polyamide resins such as alicyclic polyamide resins, etc.), polyurethane resins, olefin resins (including polyethylene (including low-density polyethylene and high-density polyethylene)), polypropylene, ethylene-propylene copolymer, ethylene Single or copolymer of olefins such as propylene rubber (also elastomers) ), Cyclic polyolefin resin, etc.}, acrylic resin, vinyl resin (vinyl chloride resin, vinyl acetate resin, ethylene-vinyl oxalate copolymer, polybutyl alcohol, ethylene-vinyl alcohol copolymer) And thermoplastic elastomers (polyester thermoplastic elastomers, etc.). These other thermoplastic resins may be crystalline resins or non-crystalline resins. These other thermoplastic resins may be used alone or in combination of two or more.

In the resin composition of the present invention, a conventional additive such as a compatibilizer, a plasticizer, a flame retardant aid (for example, polytetrafluoroethylene) is used unless the resin properties are deteriorated. Any fluorine-containing resin), colorants, stabilizers (antioxidants, light stabilizers, heat stabilizers, etc.), lubricants, dispersants, foaming agents, antibacterial agents, and the like. These additives can be used alone or in combination of two or more.

The long fiber reinforced thermoplastic resin composition of the present invention exhibits excellent heat resistance. Specifically, generally, the deflection temperature under load (1.8 M Pa) is 130 ° C. or higher.

The long fiber reinforced resin pellet of the present invention is the above long fiber reinforced thermoplastic resin composition, wherein the reinforcing fibers are arranged substantially parallel to the length direction of the pellet, and are cylindrical, prismatic, or tape. It is shaped into a shape and cut to any length of 4 to 50 mm. The preferred pellet length is 6 to 25 mm, more preferably 6 to 2 O mm.

Examples of a molding method for forming the long fiber reinforced resin pellet of the present invention into a molded product include an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, and a foam molding method.

In molding, it is preferable to maintain the fiber contained in the pellet with the longest possible fiber length. To that end, in general molding methods and molding equipment, the shear generated by the rotation of the screw when plasticizing the material is large, and there is a high probability that the fiber will break. Nare ,. Therefore, it is preferable to use a molding machine with a plasticizing system developed for each company's long fiber reinforced thermoplastic resin. Also, the molding conditions for protecting the fiber length are 10 to 30 ° from the general plasticization temperature when molding in a state in which reinforcing fibers are not added to the matrix resin (non-reinforced). It is desirable to reduce shear due to plasticization, such as setting a higher temperature. Furthermore, the design of the mold and / or die is not particularly limited, but the flow path of the resin is designed to be as wide as possible, and the shape of the resin flow path is examined, and then the pressure is determined. A design with reduced loss is desirable to protect the fiber length.

In this way, by taking the condition that the fiber length is increased at the time of molding, the weight average fiber length of the reinforcing fiber dispersed in the molded body formed from the long fiber reinforced resin pellet is 0.5 mn! A long fiber reinforced resin molded product of ˜5 mm can be achieved. Strengthen The ratio of the polycarbonate resin (PC) and styrene resin (SR) impregnated into the fiber is usually PC / SR = 95Z5 to 3◦70 in weight ratio, preferably PCZSR = 90Zl 0 to 50Z50 Particularly preferably, PC, SR = 80Z20 to 60Z40. If the PCZSR ratio is greater than 95 5, that is, if the polycarbonate resin is excessive, the fluidity will deteriorate, leading to a decrease in moldability. In addition, if the PC / SR ratio is smaller than 30Z70, that is, if the PC is small, the heat resistance is lowered and the strength peculiar to PC cannot be exhibited. The ratio of the reinforcing fibers contained in the long fiber reinforced resin pellet is usually 11 to 200 parts by weight, preferably 25 to 150 parts by weight, particularly preferably 100 parts by weight of the pellets. 30 to 100 parts by weight. If the reinforcing fiber is less than 11 parts by weight, the mechanical strength of the molded product decreases, and if the reinforcing fiber exceeds 200 parts by weight, the resin cannot be sufficiently impregnated by the drawing method, and the pellets have a lot of fluff. It becomes difficult to manufacture. Brief Description of Drawings

Fig. 1 shows a 15 Omm square plate (thickness = 3 mm, gate width = 15 Omm) for measuring the linear expansion coefficient, with its test piece in the flow direction (MD) and flow right angle direction (TD) at the center. Is cut out. In the figure, reference numeral 1 is an injection gate, 2 is an arrow indicating the injection flow direction, 3 is a specimen collection point in the flow direction (MD), and 4 is a test in the direction perpendicular to the flow (TD). It means each sampling point. Example

Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples. In addition, materials and physical property measuring methods and injection molding apparatuses used in Examples and Comparative Examples are shown below.

[Materials used]

P C: Viscosity average molecular weight (Mv) = 1 7800

ABS 1: ABS resin, polymer obtained by bulk polymerization method, rubber type: polyb Tagen, rubber content 20%, copolymerization ratio of monomer components constituting the matrix: Styrene acrylonitrile = 82 18 (weight ratio), rubber weight average particle size 1000 nm, menoleto flow rate 54 g / 10min

ABS 2: ABS resin, polymer obtained by bulk polymerization, the rubber species: polybutylene Tajen, rubber content 20 wt ^_0/0, the copolymerization ratio of the monomer components constituting the Matrigel box: styrene Noah methacrylonitrile Nitrile = 77 23 (Weight ratio), rubber weight average particle size 1 300 nm, melt flow rate 40 g / 10min

AS 1: AS resin, Copolymerization ratio of monomer components constituting the matrix: styrene acrylonitrile = 73/27 (weight ratio), solution viscosity sp Z c (4 mg m 1 concentration of black mouth form solution, 25 ° C): 0.85, Menore flow rate 2 8g / 10min

Glass fiber roving: Fiber diameter 17 / m, epoxy silane coupling agent treatment

P

Strike

Short glass fiber (chopped strand): Fiber diameter 13 μm, fiber length 3 mm, treated with epoxysilane coupling agent

[Physical property measurement]

Viscosity average molecular weight (Mv): Using an Ubbelohde viscometer, the viscosity of a methylene chloride solution at 20 ° C was measured. From this, the intrinsic viscosity [77] was obtained and calculated by the following formula.

[] = 1. 23 X 10-5Mv 0. 83

Menoleto flow rate: Conforms to I S01 1 33 (220 ° C. 10 kg) Sodium concentration: 2 g of sample is precisely weighed in a platinum crucible, carbonized with an electric heater and burner, and then electric furnace (400 ° C 1.5 hours and 500 ° C, 2 hours) ashing was completed. A small amount of ultrapure water and 0.5 ml of nitric acid were added to this ashed product and heated on a sand bath to dissolve the ash. After evaporation to dryness, 0.1 N nitric acid aqueous solution was added to make up to 2 Om 1 to prepare a test solution for atomic absorption analysis. Using an atomic absorption analyzer (manufactured by Shimadzu Corporation, 8-680), the total amount of sodium in this test solution was measured (unit: p pm (μg / g)). Note that a blank using a crucible without filling the sample. The blank test was subtracted to obtain the total amount of sodium in the sample. For the calibration curve standard solution, dilute commercially available standard solution for atomic absorption analysis with 0.1 N nitric acid aqueous solution as appropriate, and sodium concentration 0, 0.02, 0.05, 0.1, 0.5, 1. The one adjusted to 0 μg / m 1 was used.

Chlorine concentration: Sample 20-3 Omg was precisely weighed and the total chlorine content in the sample was measured by coulometric titration using a chlorine analyzer (TOX-100 manufactured by Mitsubishi Chemical Corporation).

(Unit: p p m μg / g)).

Sulfate ion concentration: 6 g of sample was purified and filled in a polytetrafluoroethylene (Teflon: registered trademark) container previously washed with ultrapure water, and after adding 15 g of ultrapure water, set to 1 10 ° C It was left in the dryer for 20 hours and extracted with steam. The solution was diluted as appropriate, and the filtrate filtered through a 0.2 μπι membrane filter was used as a measurement solution and measured with the following anion analyzer (unit: p pm (μg / g)).

Equipment used: D I ONEX DX-320

Precolumn: AG— 1 5

Column: AS— 1 5

Eluent: 5-7 OmM KOH gradient

Flow rate: 0.5ml / min

Detector: Electric conduction detector

Column temperature: 30 ° C

Injection volume: 200 μ 1

Tensile test: according to I SO 527-1

Deflection temperature under load: Conforms to I S O 75—1 (1.8 OMP a: flatwise) Charpy impact test: Conforms to I S01 79 l eA (edgewise)

Linear expansion coefficient: 1 Approximate central part of a 50 square plate (thickness = 3, gate width = 150) was cut in the flow direction (MD) and flow right angle direction (TD), and the linear expansion coefficient in the longitudinal direction of the test piece Was measured.

Test piece: 20 X 10 X 3 (mm), Measurement range: 40 ° C to 80 ° C, Unit: X 1 GT ⁵ (1 / K) (See Fig. 1 for test piece) Fiber length measurement method (weight average fiber length): A sample of about 5 g is cut out from the molded product, and ashed at 650 ° C to take out the fiber. The weight average fiber length was determined from the force of some of the extracted fibers (approximately 500).

Fluidity: Flow length of spiral flow (cross section: thickness 2 mm, width 20 mm) measured at cylinder temperature 280 ° C, mold temperature 1 20 ° C, injection pressure 98MPa, measured value is L / T .

[injection molding]

Equipment: JC 150EII, manufactured by Nippon Copper Works

Screw: Screw for exclusive use of long fibers

Molding temperature (cylinder temperature): 280 ° C

Mold temperature: 100 ° C

Molded product: I SO multipurpose test piece, 150 square flat plate molded product

Example 1

Extruded with a mixture of 70 parts by weight of PC and 30 parts by weight of ABS 1 connected to the crosshead as a thermoplastic resin while pulling glass fiber roving through a crosshead that has been processed into a corrugated continuous fiber passage. supplied in a molten state (280 ° C) from the machine, was impregnated into a glass fiber, taking as a strand through a shaping die, cooled, and cut, the glass fiber content 40 wt ^_0/0, length 1 A 1 mm pellet was obtained. Test pieces for measuring the physical properties of the obtained pellets were prepared by injection molding.

Example 2

A glass fiber roving was drawn through a corrugated crosshead in the continuous fiber passage, and a mixture of 60 parts by weight of PC and 40 parts by weight of ABS 1 was connected to the crosshead as a thermoplastic resin. After being fed from the extruder in a molten state (280 ° C) and impregnating the glass fiber, it is taken out as a strand through a shaping die, cooled and then cut, glass fiber content 40% by weight, length 1 lmm The pellet was obtained. Test pieces for measuring the physical properties of the obtained pellets were prepared by injection molding. Example 3

A glass fiber roving is drawn through a crosshead formed by corrugated continuous fiber passages, and a mixture of 70 parts by weight of PC and 30 parts by weight of ABS 2 is connected to the crosshead as a thermoplastic resin. After being fed from an extruder in a molten state (280 ° C.) and impregnating into glass fiber, it is taken out as a strand through a shaping die, cooled, and cut to have a glass fiber content of 40 weight. / ₀ to give Perez bets length 1 1 mm. Test pieces for measuring the physical properties of the obtained pellets were prepared by injection molding.

Example 4

Connect the mixture of 70 parts by weight of PC and 70 parts by weight of ABS as a thermoplastic resin to the crosshead while drawing the glass fiber roving through the crosshead with the corrugated continuous fiber passage. Supplied in a molten state (280 ° C) from the extruded extruder, impregnated into glass fiber, taken out as a strand through a shaping die, cooled, cut, and glass fiber content 30% by weight A pellet with a length of 11 mm was obtained. Test pieces for measuring the physical properties of the obtained pellets were prepared by injection molding.

Example 5

As a thermoplastic resin, 70 parts by weight of PC, 20 parts by weight of ABS 1, and 10 parts by weight of AS 1 are drawn as glass fiber roving through a crosshead formed by corrugated continuous fiber passages. After being fed in a molten state (280 ° C) from an extruder connected to a cloth head and impregnating the glass fiber, the mixture is taken out as a strand through a shaping die and cooled. The pellet was cut to obtain a pellet having a glass fiber content of 30% by weight and a length of 11 mm. Test pieces for measuring the physical properties of the obtained pellets were prepared by injection molding.

Example 6

A glass fiber roving was drawn through a corrugated crosshead in the continuous fiber passage, and a mixture of 70 parts by weight of PC and 30 parts by weight of AS1 was connected to the crosshead as a thermoplastic resin. Served from the extruder in the molten state (280 ° C) Feeding and, after impregnating a glass fiber, take-up as a strand through a shaping die, cooled, and cut, the glass fiber content 3 0 wt ^_0/0, to obtain a pellet of length 1 1 mm. Test pieces for measuring physical properties of the obtained pellets were prepared by injection molding.

Comparative Example 1

Without the method of impregnating the fibers with the cloth in the crosshead, a mixture of 70 parts by weight of PC and 30 parts by weight of ABS 1 as thermoplastic resin 70 parts by weight and short glass fibers (chopped strands) After mixing 30 parts by weight with a tumbler and a renderer, the mixture was melt kneaded with an extruder to obtain a pellet-like resin composition. The same test piece as in the example was prepared by injection molding of the obtained pellets.

Comparative Example 2

The same operation as in Example 1 was carried out except that a resin containing PC alone was used instead of a mixture of 70 parts by weight of PC and 30 parts by weight of ABS 1 as the thermoplastic resin.

Comparative Example 3

The same operation as in Example 1 was performed except that the glass fiber content was changed to 5% by weight.

Claims

The scope of the claims

1. A long fiber reinforced thermoplastic resin composition comprising 11 to 200 parts by weight of reinforcing fibers per 100 parts by weight of a composition comprising a polycarbonate resin (PC) and a styrene resin (SR).

2. Claim in which polycarbonate resin (PC) and styrenic resin (SR) are blended with 1 to 200 parts by weight of reinforcing fiber per 100 parts by weight of composition with PCZSR = 95 5 to 30Z70 as weight ratio Item 10. A long fiber reinforced thermoplastic resin composition according to Item 1.

3. Styrene resin (SR) 1 Long fiber reinforced thermoplastic resin according to any one of claims 1 to 2, which is a copolymer of an aromatic bur monomer and a vinyl cyanide monomer. Composition.

4. Styrenic resin (SR), graft copolymer obtained by polymerizing monomer component containing aromatic vinyl monomer and vinyl cyanide monomer as main components in the presence of rubber polymer The long fiber reinforced thermoplastic resin composition according to any one of claims 1 and 2.

5. proportion of rubbery polymer is from 1 to 30 weight ^_0/0 for styrenic resin (SR), the weight ratio of the aromatic Bulle based monomer and vinyl cyanide-based monomer is 90 10 The long fiber reinforced thermoplastic resin composition according to any one of claims 1 to 2 and 4, wherein the composition is -60 to 40.

6. The long fiber reinforced thermoplastic resin composition according to any one of claims 1 to 5, wherein the styrene resin (SR) is a styrene resin obtained by bulk polymerization.

7. Styrenic resin (SR) 長 Long fiber reinforced thermoplastic resin according to any one of claims 1 to 6, which is a styrene resin having a total content of sodium, chlorine and sulfate ions of 10 ppm or less. Composition.

8. Styrenic resin (SR) force The long fiber reinforced thermoplastic resin composition according to any one of claims 1 to 7, wherein the melt flow rate is 20 gZl 0 min or more.

9. The long fiber reinforced thermoplastic resin composition according to any one of claims 1 to 8, wherein the polycarbonate resin (PC) has a viscosity average molecular weight of 13000 to 200000.

10. The long fiber reinforced thermoplastic resin composition according to any one of claims 1 to 9, wherein a deflection temperature under load (1.8 MPa) is 130 ° C or higher.

1 1. Reinforcing fiber consists of glass, carbon, silicon carbide, basalt, boron inorganic fiber; stainless steel metal fiber; aramid, rayon, nylon, polynaphthalate, polyester organic fiber; cellulose fiber The long fiber reinforced thermoplastic resin composition according to any one of claims 1 to 10, comprising at least one fiber selected from the group.

1 2. The long fiber reinforced thermoplastic resin composition according to any one of claims 1-11, wherein the reinforcing fiber is surface-treated with an epoxy binder.

13. Claims in which the reinforcing fibers are arranged substantially parallel to the longitudinal direction of the pellet, are shaped like a cylinder, prism, or tape and cut to a length of 4-5 Omm Item 11. A long fiber reinforced thermoplastic resin composition according to any one of Items 1 to 12;