JP4951848B2 - Fiber-reinforced crystalline thermoplastic resin composition and pellets thereof - Google Patents

Description

  The present invention relates to a fiber-reinforced crystalline thermoplastic resin composition and pellets thereof. More specifically, the present invention relates to a fiber reinforced thermoplastic resin composition and a pellet thereof that can provide a molded article having a small mechanical strength and an excellent appearance.

Conventionally, it has been known that fillers, glass fibers, and the like are blended as means for improving mechanical strength such as rigidity and impact strength of a crystalline thermoplastic resin.
For example, Chapters 6, 7 and 8 of “Interface Control and Composite Material Design” (Fumio Ide, Sigma Publishing (1995)) use glass fiber, carbon fiber or organic fiber, A crystalline thermoplastic resin composition with enhanced mechanical strength is described.

  JP-A-3-121146 contains a resin component composed of a polyolefin and a modified olefin polymer as a molding polyolefin resin composition with improved mechanical strength and the like, and reinforcing fibers, A polyolefin resin composition for long fiber reinforced molding is described in which the fibers have a length of at least 2 mm in the resin.

  However, from the fiber reinforced crystalline thermoplastic resin composition described in the above-mentioned publication ("Interface control and composite material design") or patent publication (Japanese Patent Laid-Open No. 3-121146), or the resin composition. Further improvement has been desired for the appearance of the molded article made of the obtained pellets.

  JP 2002-47381 A describes a fiber reinforced polyolefin resin composition containing polyolefin, reinforcing fibers and petroleum resin as a fiber reinforced polyolefin resin composition excellent in mechanical properties and appearance of a molded product. Yes. However, with respect to a molded article made of the fiber-reinforced polyolefin resin composition described in the above-mentioned patent publication (Japanese Patent Laid-Open No. 2002-47381) or pellets obtained from the resin composition, a decrease in mechanical strength is suppressed. Further improvements in appearance have been desired.

Japanese Patent Laid-Open No. 3-121146 JP 2002-47381 A Chapter 6, Chapter 7 and Chapter 8 of “Interface Control and Composite Material Design” (Fumio Ide, Sigma Publishing (1995))

  An object of the present invention is to provide a fiber-reinforced crystalline thermoplastic resin composition and a pellet thereof, which have a small decrease in mechanical strength and an excellent appearance of a molded product.

As a result of intensive studies in view of the actual situation, the present inventors have found that the present invention can solve the above problems, and have completed the present invention.
That is, the present invention relates to a crystalline thermoplastic resin (component (A)) of 10 to 99% by weight and a crystalline thermoplastic resin (component (B)) 90 having a crystallization temperature lower by 10 ° C. or more than that of the component (A). It is related with the composition containing 5-400 weight part of fibers (component (C)) with respect to 100 weight part of resin (I) and resin (I) containing -1 weight%. (However, the total amount of the resin (I) is 100% by weight.)

  The present invention also relates to a crystalline thermoplastic resin (component (A)), a crystalline thermoplastic resin (component (B)) having a crystallization temperature lower than that of the component (A) by 10 ° C. or more, and an unsaturated carboxylic acid or The fiber (component (C)) 5 to 400 per 100 parts by weight of the resin (II) containing a modified polyolefin resin (component (D)) partially or entirely modified with the derivative and 100 parts by weight of the resin (II) In the resin (II), the component (A) and the component (B) have a weight ratio of 10 to 99% by weight, and the component (B) 90 1% by weight (provided that the total amount of component (A) and component (B) is 100% by weight), and component (D) relative to the sum of the weight of component (A) and component (B) ) Weight ratio (component (D) / [component (A) + component (B)]) is 0. It relates the composition is 1 / 99.9 to 20/80.

  Furthermore, this invention relates to the molded article obtained from the pellet obtained from said composition, said composition, or said pellet.

  According to the present invention, it is possible to obtain a fiber-reinforced crystalline thermoplastic resin composition and pellets thereof that can provide a molded article with a low mechanical strength and an excellent appearance.

The crystalline thermoplastic resin (component (A)) used in the present invention is usually a thermoplastic resin having a crystallinity of 10% or more, and preferably a thermoplastic resin having a crystallinity of 20% or more. .
The crystallinity is measured by “Introduction to Polymer Chemistry” (Seizo Okamura et al., Chemical Doujin (published in 1970)) “New Edition Polymer Analysis Handbook” (Japan Analytical Chemistry Society / Polymer Analysis Research Party, As described in Kinokuniya (1995), etc., any known method such as an X-ray method, a density method, an infrared absorption method, an NMR method, or a calorimetric method may be used.

Examples of the component (A) used in the present invention include polyolefin resins such as polypropylene resins and polyethylene resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, and polyphenylene sulfide resins. Further, these resins may be used alone or at least two kinds may be blended.
The component (A) used in the present invention is preferably a polyolefin resin, and more preferably a polypropylene resin.

  In the present invention, examples of the polyamide resin used as the component (A) include nylon 6, nylon 46, nylon 66, nylon 11, nylon 12, nylon 6 · 10, nylon 6 · 12, and the like. Further, these polyamide resins may be used alone or at least two kinds may be blended.

In the present invention, an aromatic polyamide can also be used as the polyamide resin used as the component (A). A thermoplastic copolyamide containing an aromatic component is preferable, and a polyamide capable of melt polymerization containing an aromatic amino acid and / or an aromatic dicarboxylic acid as a main constituent component is exemplified. Examples of the aromatic dicarboxylic acid include paraaminomethyl benzoic acid, paraaminoethyl benzoic acid, terephthalic acid, isophthalic acid and the like, and other diamines as constituent components include hexamethylene diamine, undecamethylene diamine, Dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, metaxylylenediamine, paraxylylenediamine, bis (p-aminocyclohexyl) methane, bis (p-aminocyclohexyl) propane, Examples thereof include bis (3-methyl, 4-aminocyclohexyl) methane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like.
Specific examples of the thermoplastic copolyamide containing an aromatic component include polyhexamethylene isophthalamide (nylon 6I).

  In the present invention, the polyester resin used as the component (A) is preferably an aromatic polyester resin, more preferably an aromatic dicarboxylic acid as a main acid component and an aliphatic as a main glycol component. Polyester resin which is glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid, naphthalenedicarboxylic acid, isophthalic acid, diphenyl ketone dicarboxylic acid, anthracene dicarboxylic acid, and the like. Examples of the aliphatic glycol include polymethylene glycol having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, and cyclohexanedimethanol. Aliphatic diols are mentioned.

  In the present invention, examples of the polyolefin resin used as the component (A) include a polypropylene resin, a polyethylene resin, and an α-olefin resin mainly containing an α-olefin having 4 or more carbon atoms. The polyolefin resin is preferably a polypropylene resin. These polyolefin resins may be used alone or at least two of them may be blended.

  Examples of the polypropylene resin include a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer, a propylene block copolymer obtained by homopolymerizing propylene and then copolymerizing ethylene and propylene. Can be mentioned.

Examples of the polyethylene resin include an ethylene homopolymer, an ethylene-propylene random copolymer, an ethylene-α-olefin random copolymer, and the like.
Examples of the α-olefin resin mainly containing an α-olefin having 4 or more carbon atoms include an α-olefin-propylene random copolymer and an α-olefin-ethylene random copolymer.

  Examples of the α-olefin having 4 or more carbon atoms used when the component (A) is a polyolefin resin include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl- 1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl -1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1- Pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like. 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

The crystalline thermoplastic resin (component (B)) used in the present invention is a crystalline thermoplastic resin having a crystallization temperature (Tc) of 10 ° C. or lower than that of the component (A).
And as a component (B), it is a thermoplastic resin with a crystallinity degree of 10% or more normally. As with component (A), the degree of crystallinity is measured by “Introduction to Polymer Chemistry” (Seizo Okamura et al., Kagaku Dojin (1970)), “New Edition Polymer Analysis Handbook” (Japan Analytical Chemistry Society / Polymer) Performed by known methods such as X-ray method, density method, infrared absorption method, NMR method, calorimetric method, etc., as described in Analytical Research Party, Kinokuniya (1995)) Can do.

Examples of the component (B) used in the present invention include a polyolefin resin, a polyester resin, a polyamide resin, a polyphenylene sulfide resin and the like, as in the component (A). These resins may be used alone, and at least 2 Seeds may be blended.
The component (B) is preferably a polyolefin resin, and examples of the polyolefin resin include a polypropylene resin and a polyethylene resin, and a polypropylene resin is more preferable.

  The crystallization temperature (Tc) of the component (B) used in the present invention is a crystallization temperature that is 10 ° C. or more lower than the crystallization temperature (Tc) of the component (A). From the viewpoint of ease of production, the crystallization temperature is preferably lower by 15 ° C. or more, more preferably by 20 ° C. to 110 ° C., and particularly preferably by 30 ° C. to 100 ° C.

The crystallization temperature (Tc) is the peak temperature of the peak where the calorific value is maximum in the crystallization exotherm curve measured according to the following method.
Using a differential scanning calorimeter (DSC-7 type rapid quenching type manufactured by PerkinElmer Co., Ltd.), 10 mg of a specimen was previously melted at 220 ° C. for 5 minutes in a nitrogen atmosphere. When the specimen did not melt at 220 ° C., the temperature was further raised and melted at 300 ° C. for 5 minutes. After the specimen is melted, the temperature is lowered to 40 ° C. at a rate of 5 ° C./min, and the crystallization exothermic curve is measured. In the crystallization exotherm curve obtained by the measurement, the peak temperature of the peak with the maximum calorific value was defined as the crystallization temperature (Tc). Thereafter, the temperature was raised at 5 ° C./min, and the peak temperature at which the endotherm was maximum in the obtained melting endothermic curve was defined as the melting point (Tm). In addition, the point at which melting of indium (In) measured at a rate of temperature increase of 5 ° C./min using this measuring machine was 156.6 ° C.

  The crystallization temperature (Tc) of the component (B) used in the present invention is preferably 100 ° C. or less, more preferably 0 to 95, from the viewpoint of the appearance of the obtained molded article and ease of molding and production. ° C, particularly preferably 30 to 90 ° C.

  When the component (B) used in the present invention is a polypropylene resin, the melt flow rate (MFR) of the polypropylene resin used is easy to manufacture and mold, from the viewpoint of mechanical strength such as rigidity and impact strength. Preferably it is 1-300 g / 10min, More preferably, it is 2-250g / 10min, Especially preferably, it is 4-200g / 10min. The melt flow rate (MFR) is A. S. T.A. M.M. It is a value measured at 230 ° C. and 21.2 N load according to D1238.

  When the component (B) used in the present invention is a polypropylene resin, the structure of the polypropylene resin used is described in “Polypropylene Handbook” (edited by Edward P. Moore, Jr, published by the Industrial Research Council (1998)). The structure may be any of an isotactic structure, a syndiotactic structure, an attack tic structure, or a mixture of these structures. Among these structures, a syndiotactic structure is preferable from the viewpoint of the appearance of a molded product.

The polypropylene resin having a syndiotactic structure is observed at 20.2 ppm on the basis of tetramethylsilane in a ¹³ C-NMR spectrum measured with a 1,2,4-trichlorobenzene solution at 135 ° C. A polypropylene resin having a value (syndiotactic pentad fraction [rrrr]) divided by the sum of peak intensities attributed to methyl groups of propylene units usually 0.3 to 0.9. Yes, preferably a polypropylene resin of 0.5 to 0.9, more preferably 0.7 to 0.9. The necessary peaks were assigned according to A. Zambelli et al, Macromolecules, 6, 925 (1973).

  Either or both of the component (A) and the component (B) used in the present invention are partially or completely unsaturated carboxylic acid or a derivative thereof from the viewpoint of mechanical strength such as impact strength and rigidity. It may be denatured. In addition, as unsaturated carboxylic acid or its derivative used for modification | denaturation of a component (A) and a component (B), it is the same as that of unsaturated carboxylic acid or its derivative used for the modified polyolefin resin (component (D)) mentioned later. Things.

  As a method for producing the crystalline thermoplastic resin (component (A)) and the crystalline thermoplastic resin (component (B)) used in the present invention, “new polymer production process” (edited by Koji Saeki, Industrial Research Committee (1994) Issue)), “Polyester resin” (Eiichiro Takiyama, Nikkan Kogyo Shimbun (published in 1970)), “Polyamide resin” (Edited by Osamu Fukumoto, Nikkan Kogyo Shimbun (published in 1970)), etc. Examples thereof include a method of production by a combination method, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like. And the method of using these polymerization methods independently may be sufficient, and the method of combining at least 2 types may be sufficient.

When the component (A) and the component (B) are polyolefin resins, as a method for producing the polyolefin resin, “New polymer production process” (edited by Koji Saeki, Industrial Research Committee (1994)), JP-A-4-323207 Examples thereof include a solution polymerization method, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like described in JP-A-61-287917. And the method of using these polymerization methods independently may be sufficient, and the method of combining at least 2 types may be sufficient.
The catalyst used for the production of the polyolefin resin is preferably a multi-site catalyst obtained using a solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom, or a single site catalyst obtained using a metallocene complex or the like. It is done.

And when a component (A) and a component (B) are polypropylene resins, as a manufacturing method of a polypropylene resin, "new polymer manufacturing process" (edited by Koji Saeki, industrial research group (1994 issue)), Unexamined-Japanese-Patent No. 4- Examples thereof include a solution polymerization method, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like described in JP-A No. 323207 and JP-A-61-287917. And the method of using these polymerization methods independently may be sufficient, and the method of combining at least 2 types may be sufficient.
The catalyst used for the production of the polypropylene resin is preferably a multisite catalyst obtained using a solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom, or a single site catalyst obtained using a metallocene complex or the like. It is done.
Moreover, the manufacturing method of the polypropylene resin which is a syndiotactic structure is described in Unexamined-Japanese-Patent No. 5-17589, Unexamined-Japanese-Patent No. 5-131558, etc.

  Examples of the fibers (component (C)) used in the present invention include inorganic fibers, organic fibers, natural fibers, and the like, such as glass fibers, carbon fibers, metal fibers, aromatic polyamide fibers, kenaf fibers, bamboo fibers, and polyester fibers. , Nylon fiber, jute fiber, ramie fiber, cellulose fiber and the like. Among these, glass fiber is preferable.

  The weight average fiber length of the fiber (component (C)) is preferably 2 to 100 mm from the viewpoint of improving mechanical strength such as rigidity and impact strength, and from the viewpoint of ease of production and molding, Especially preferably, it is 2-50 mm. In addition, the weight average fiber length of a fiber (component (C)) is the length in the composition of this invention, and is the weight average fiber length measured by the method described in Unexamined-Japanese-Patent No. 2002-5924. is there.

  In order to converge the fiber (component (C)) used in the present invention, a sizing agent may be used. Examples of the sizing agent include polyolefin resins, polyurethane resins, polyester resins, acrylic resins, epoxy resins, starches. And vegetable oils. Furthermore, you may mix | blend lubricants, such as acid-modified polyolefin resin, a surface treating agent, and paraffin wax.

  In order to improve the wettability and adhesion between the fiber (component (C)) used in the present invention and the crystalline thermoplastic resin (component (A) and / or component (B)), the fiber (component ( C)) may be pretreated with a surface treating agent. Examples of the surface treatment agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a chromium coupling agent, a zirconium coupling agent, and a borane coupling agent. Of these, silane coupling agents and titanate coupling agents are preferred, and silane coupling agents are particularly preferred.

  Examples of the silane coupling agent include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4). -Epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, aminosilanes are preferable, and γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are more preferable.

  Examples of the method for treating the fiber (component (C)) used in the present invention with the surface treatment agent include conventionally used methods such as an aqueous solution method, an organic solvent method, and a spray method.

The modified polyolefin resin (component (D)) used in the present invention is
(1) A modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to an olefin homopolymer,
(2) a modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to a copolymer of at least two olefins,
(3) A modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to a block copolymer obtained by homopolymerizing an olefin and then copolymerizing at least two olefins, or
(4) A modified polyolefin resin obtained by copolymerizing at least one olefin and an unsaturated carboxylic acid and / or a derivative thereof.
The modified polyolefin resin (component (D)) may be used alone or in combination of at least two kinds.

  Examples of the method for producing the modified polyolefin resin (component (D)) used in the present invention include “Practical Polymer Alloy Design” (Fumio Ide, Industrial Research Group (1996)), Prog. Polym. Sci. 24, 81-142 (1999), Japanese Patent Application Laid-Open No. 2002-308947, and the like, and any of a solution method, a bulk method, and a melt-kneading method may be used. Moreover, the manufacturing method which combined these methods may be sufficient.

Examples of the unsaturated carboxylic acid used in the modified polyolefin resin (component (D)) include maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid.
Further, examples of the unsaturated carboxylic acid derivative include acid anhydrides, ester compounds, amide compounds, imide compounds, metal salts, and the like of the above unsaturated carboxylic acids. Specific examples thereof include maleic anhydride, itaconic anhydride. Acid, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, Examples include dimethyl fumarate, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, and sodium methacrylate.
Moreover, you may use what dehydrates and produces | generates unsaturated carboxylic acid by the process grafted to a polypropylene like citric acid and malic acid.

  The unsaturated carboxylic acid and / or derivative thereof is preferably acrylic acid, glycidyl ester of methacrylic acid, or maleic anhydride.

As the modified polyolefin resin (component (D)) used in the present invention, preferably,
(5) A modified polyolefin resin obtained by graft polymerization of maleic anhydride to a polyolefin resin having a unit derived from ethylene and / or propylene as a main constituent unit of the polymer, or
(6) A modified polyolefin resin obtained by copolymerizing an olefin mainly composed of ethylene and / or propylene and glycidyl methacrylate or maleic anhydride.

The content of the unit derived from the unsaturated carboxylic acid and / or derivative thereof, which is a structural unit of the modified polyolefin resin (component (D)) used in the present invention, is a mechanical strength such as impact strength, fatigue characteristics, and rigidity. From this point of view, it is preferably 0.1 to 10% by weight.
The modified polyolefin resin (component (D)) is a modified polyolefin resin obtained by random copolymerization or block copolymerization of (4) at least one olefin and an unsaturated carboxylic acid and / or derivative thereof. In some cases, the content of units derived from the unsaturated carboxylic acid and / or derivative thereof is preferably 3 to 10% by weight.

Modified polyolefin resin (component (D))
(1) When it is a modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to an olefin homopolymer,
(2) a modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to a copolymer of at least two olefins, or
(3) In the case of a modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to a block copolymer obtained by copolymerizing at least two olefins after homopolymerizing the olefin,
The content of units derived from the unsaturated carboxylic acid and / or derivative thereof is preferably 0.1 to 10% by weight.

The composition of the present invention contains a crystalline thermoplastic resin (component (A)) and a crystalline thermoplastic resin (component (B)) whose crystallization temperature (Tc) is 10 ° C. or lower than that of the component (A). In the case of a composition containing resin (I) and fiber (component (C)), the weight ratio of component (A) and component (B) in resin (I) is 99 to 10 wt. %, And component (B) is 1 to 90% by weight. (However, the total amount of the resin (I) is 100% by weight.)
From the viewpoint of improving mechanical strength such as rigidity and impact strength and from the viewpoint of the appearance of the molded product, the component (A) is preferably 98 to 10% by weight and the component (B) is 2 to 90% by weight. More preferably, the component (A) is 96 to 15% by weight and the component (B) is 4 to 85% by weight.

  And content of a fiber (component (C)) is 5-400 weight part with respect to 100 weight part of resin (I), and the viewpoint of improving mechanical strength, such as rigidity and impact strength, or manufacture From the viewpoint of ease of molding, it is preferably 10 to 300 parts by weight, and particularly preferably 10 to 240 parts by weight.

  The composition of the present invention comprises a crystalline thermoplastic resin (component (A)), a crystalline thermoplastic resin (component (B)) having a crystallization temperature lower than that of the component (A) by 10 ° C. or higher, and an unsaturated carboxylic acid. Or a resin (II) containing a resin (II) containing a modified polyolefin resin (component (D)) partially or entirely modified with a derivative thereof and a fiber (component (C)) In regard to the weight ratio of the component (A) and the component (B), the component (A) is 10 to 99% by weight and the component (B) is 90 to 1% by weight. (However, the total amount of the component (A) and the component (B) is 100% by weight.) And, regarding the weight ratio of the component (A) and the component (B), the mechanical strength such as rigidity and impact strength is improved. From the viewpoint of controlling the appearance and appearance of the molded product, the component (A) is preferably 98 to 10% by weight, the component (B) is 2 to 90% by weight, and more preferably the component (A). Is 96 to 15% by weight, and component (B) is 4 to 85% by weight.

  The ratio of the weight of the component (D) to the total weight of the component (A) and the component (B) (component (D) / [component (A) + component (B)]) is 0.1 / 99. .9-20 / 80. From the viewpoint of improving mechanical strength such as rigidity and impact strength and fatigue characteristics, and from the viewpoint of ease of molding and production, it is preferably 0.1 / 99.9 to 20/80, more preferably 0. 3 / 99.7 to 20/80, particularly preferably 0.5 / 99.5 to 20/80.

  Furthermore, content of a fiber (component (C)) is 5-400 weight part with respect to 100 weight part of resin (II) containing a component (A), a component (B), and a component (D), From the viewpoint of improving mechanical strength such as rigidity and impact strength, and from the viewpoint of ease of production and molding, it is preferably 10 to 300 parts by weight, particularly preferably 10 to 240 parts by weight.

  You may mix | blend at least 1 type of elastomer with the composition of this invention as needed. Examples of elastomers include ethylene / α-olefin random copolymers, ethylene / α-olefin / non-conjugated polyene random copolymers, hydrogenated block copolymers, other elastic polymers, and mixtures thereof. .

  Further, depending on the purpose, known substances generally added to crystalline thermoplastic resins, for example, antioxidants, heat stabilizers, neutralizers, stabilizers such as ultraviolet absorbers, anti-bubble agents, flame retardants, Flame retardant aids, dispersants, antistatic agents, lubricants, anti-blocking agents such as silica, colorants such as dyes and pigments, plasticizers, nucleating agents and crystallization accelerators may be blended.

  Further, glassy flakes, mica, glass powder, glass beads, talc, clay, alumina, carbon black, Wollastonite and other plate-like and powdery inorganic compounds, whiskers and the like may be blended.

  As a manufacturing method of the composition of this invention, well-known various methods are mentioned. For example, after mixing all the components to make a uniform mixture, or by combining several components separately and mixing to make a uniform mixture, the mixture is melt kneaded or pultrusion Examples include molding methods. Examples of a method for obtaining a uniform mixture include a method of mixing with a Henschel mixer, a ribbon blender, a blender or the like. Examples of the melt kneading method include a Banbury mixer, a plast mill, a Brabender plastograph, and a single screw or twin screw extruder.

Among these production methods, the pultrusion method is preferable from the viewpoint of ease of production, mechanical strength such as rigidity and impact strength. The pultrusion method is basically a method of impregnating a fiber bundle with a resin while drawing a continuous fiber bundle.
(1) A method in which a fiber bundle is passed through an impregnation tank containing a resin emulsion, suspension, or solution, and the fiber bundle is impregnated with resin.
(2) A method of impregnating a fiber bundle by blowing the resin powder onto the fiber bundle, or after passing the fiber bundle through a tank containing the powder and attaching the resin to the fiber,
(3) A method of supplying the resin to the crosshead from an extruder or the like while allowing the fiber bundle to pass through the crosshead, and impregnating the fiber bundle.
The method using the crosshead of the above (3) is preferable, and the method using the crosshead described in JP-A-3-272830 is particularly preferable.

  In the pultrusion method, the resin impregnation operation may be performed in one stage, or may be performed in at least two stages. Moreover, you may blend the pellet manufactured by the pultrusion method, and the pellet manufactured by the melt-kneading method.

The pellet of the present invention is a pellet obtained from the composition of the present invention. From the viewpoint of obtaining a molded product having excellent strength without impairing the injection moldability when applied to injection molding, the pellet Is preferably 2 to 50 mm, and the contained fiber (component (C)) and the pellet length are preferably equal.
In the pellet of the present invention, the contained fiber (component (C)) is equal in pellet length to the fiber (component) contained in the pellet measured by the method described in JP-A-2002-5924. (C)) means that the weight average fiber length is 90 to 110% of the pellet length.

  The molded product of the present invention is a molded product obtained from the composition of the present invention or a pellet thereof. Examples of the molding method include an injection molding method, an injection compression molding method, a gas assist molding method, and an extrusion molding method.

In particular, when the molded product of the present invention is a molded product obtained by injection molding from the composition or pellet of the present invention, from the viewpoint of mechanical strength and durability of the molded product, the fibers (components) The weight average fiber length of (C) is preferably 1 to 10 mm.
A molded article in which the weight average fiber length of the fiber (component (C)) in the molded article is 1 to 10 mm is produced by injection molding the composition or pellet of the present invention under normal processing conditions. Can do. Preferred processing conditions include a low back pressure during molding, a deep groove in the screw of the molding machine, a low injection speed during molding, a wide flow path in the mold, and a nozzle diameter of the molding machine. For example, enlarge it.

The molded product according to the present invention includes a fender, an over fender, a grill guard, a cowl louver, a wheel cap, a side protector, a side molding, a side lower skirt, a front grill, a side, which require mechanical strength, durability and a good appearance. Exterior parts such as steps, roof rails, rear spoilers and bumpers, interior parts such as instrument panel lowers and trims that require heat-resistant rigidity, bumper beams, cooling fans, fan shrouds, lamp housings, car heater cases, fuse boxes, air cleaners It can be used for plastic parts for automobiles such as parts in the engine such as cases.
Also, parts of various electrical products such as electric tools, cameras, video cameras, microwave ovens, electric kettles, pots, vacuum cleaners, personal computers, copiers, printers, FDD, CRT machine housings, and various machines such as pump casings It can be used for parts such as parts, tanks, pipes, structures such as building forms.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these examples.
The manufacturing method of the sample for evaluation used in the examples or comparative examples is shown below.
(1) Manufacturing method of long fiber reinforced pellets By the method described in JP-A-3-121146, the long fiber reinforced pellets (E-1) and the compositions shown in Table 3 are long in the composition shown in Table 1. A fiber reinforced pellet (E-2) was produced. The impregnation temperature was 270 ° C., the take-up speed was 13 m / min, and the fiber diameter of the glass fiber used was 16 μm.

(2) Manufacturing method of sample for evaluation (Examples 1, 3, 4, Comparative Examples 1, 3, 4)
The samples for glossiness (gloss) measurement, tensile strength measurement, and IZOD impact strength measurement were reinforced with the long fiber obtained in (1) above under the following conditions using the following Japan Steel Works molding machine. After the pellets (E-1) were blended with the composition shown in Table 2, a sample for evaluation was produced by injection molding. In addition, as a sample for gloss (gloss) measurement, a 150 mm × 150 mm, 3 mm thick flat plate was molded and evaluated. At the time of blending the raw materials, 1 part by weight of a pigment master batch (carbon black concentration: 14% by weight) was added to 100 parts by weight of the raw materials and colored black.
Molding machine: Japan Steel Works molding machine J150E
Clamping force: 150t
Screw: Deep groove screw for long fibers Screw diameter: 46mm
Screw L / D: 20.3
Molding conditions Cylinder temperature: 250 ° C
Mold temperature: 50 ℃
Back pressure: 0 MPa

(Example 2, comparative example 2)
Using the following Ube Machinery machine molding machine, the long fiber reinforced pellets (E-2) obtained in (1) above were blended with the composition shown in Table 4 under the following conditions, and then injection molded. Samples for evaluation of gloss (gloss) (flat plate, 130 mm × 120 mm, 3 mm thickness) were produced. At the time of blending the raw materials, 1 part by weight of a pigment master batch (carbon black concentration: 14% by weight) was added to 100 parts by weight of the raw materials and colored black.
Molding machine: Ube Machinery's molding machine MD350S-III
Clamping force: 170t
Screw: General purpose screw Screw diameter: 45mm
Screw L / D: 18
Molding conditions Cylinder temperature: 250 ° C
Mold temperature: 40 ℃
Back pressure: 20 MPa

The physical properties in Examples and Comparative Examples were measured according to the methods shown below.
(1) MFR (unit: g / 10 minutes)
A. S. T.A. In accordance with MD1238, the measurement was performed under the following conditions.
Measurement temperature: 230 ° C
Load: 21.2N

(2) Tensile strength (unit: MPa)
A. S. T.A. In accordance with MD638, the measurement was performed under the following conditions.
Measurement temperature: 23 ° C
Sample thickness: 3.2 mm
Tensile speed: 10 mm / min

(3) IZOD impact strength (unit: KJ / m ² )
A. S. T.A. The measurement was performed under the following conditions according to MD256.
Measurement temperature: 23 ° C
Sample thickness: 6.4 mm [with V notch]

(4) Glossiness (gross) (Unit:%)
A. S. T.A. M.M. According to D523, the measurement was performed under the following conditions.
Incident angle: 60 °

(5) Crystallization temperature (Tc, unit: ° C)
Using a differential scanning calorimeter (DSC-7 type rapid quenching type manufactured by PerkinElmer Co., Ltd.), 10 mg of a test piece was previously melted at 220 ° C. for 5 minutes in a nitrogen atmosphere, and then at a rate of temperature decrease of 5 ° C./min. The peak temperature of the peak where the calorific value is maximum in the obtained crystallization exothermic curve was defined as the crystallization temperature (Tc). Thereafter, the temperature was raised at 5 ° C./min, and the peak temperature at which the endotherm was maximum in the obtained melting endothermic curve was defined as the melting point (Tm). In addition, the point at which melting of indium (In) measured at a rate of temperature increase of 5 ° C./min using this measuring machine was 156.6 ° C.

(6) Syndiotactic pentad fraction [rrrr]
The sample was dissolved in 1,2,4-trichlorobenzene, and ¹³ C-NMR measurement was performed at 135 ° C. From the obtained spectrum, the peak intensity observed at 20.2 ppm based on tetramethylsilane is divided by the sum of the peak intensity attributed to the methyl group of the propylene unit to obtain a syndiotactic pentad fraction [rrrr]. Was calculated. The necessary peak assignments were in accordance with A. Zambelli et al, Macromolecules, 6, 925 (1973).

Example 1
According to the method described in JP-A-3-121146, a long fiber reinforced pellet (E-1) having the composition shown in Table 1 and a glass fiber content of 50% by weight and a pellet length of 9 mm is obtained. Created. The crystalline thermoplastic resin (A-1) used is a propylene homopolymer (MFR = 80 g / 10 min, crystallization temperature (Tc) = 127 ° C.), and the modified polyolefin resin (D-1) used is , Maleic anhydride-modified polypropylene resin (MFR = 60 g / 10 min, grafting amount of maleic anhydride = 0.6% by weight). The maleic anhydride-modified polypropylene resin used was prepared by the method described in JP-A-2002-308947.

  Further, the obtained long fiber reinforced pellet (E-1) was mixed with the composition described in Table 2 and then injection molded. Table 2 shows the tensile strength, IZOD impact strength, and gloss (gloss) of the obtained sample. In addition, the weight average fiber length of the glass fiber in the obtained sample was 4 mm. The crystalline thermoplastic resin (B-1) used for mixing with the long fiber reinforced pellets (E-1) and having a crystallization temperature (Tc) lower than that of the component (A) by 10 ° C. or more is FINAPLAS 1751 (manufactured by Atofina). MFR = 25 g / 10 min, crystallization temperature (Tc) = 79 ° C., [rrrr] = 0.77).

Comparative Example 1
In Example 1, the crystalline thermoplastic resin (B-1) having a crystallization temperature Tc lower by 10 ° C. or more than the component (A-1) used for mixing with the long fiber reinforced pellets (E-1) A sample was obtained in the same manner as in Example 1 except that the thermoplastic resin (A-3) was changed. In addition, the weight average fiber length of the glass fiber in the obtained sample was 4 mm. The crystalline thermoplastic resin (component (A-3)) used for mixing with the long fiber reinforced pellets was a propylene homopolymer (MFR = 25 g / 10 min, crystallization temperature (Tc) = 128 ° C.).

Example 2
According to the method described in JP-A-3-121146, a long fiber reinforced pellet (E-2) having the composition described in Table 3 and a glass fiber content of 60% by weight and a pellet length of 9 mm is obtained. Created. The crystalline thermoplastic resin (A-3) used is a propylene homopolymer (MFR = 120 g / 10 min, crystallization temperature (Tc) = 122 ° C.), and the modified polyolefin resin (D-2) used is , Maleic anhydride-modified polypropylene resin (MFR = 40 g / 10 min, maleic anhydride graft amount = 0.2 wt%). Furthermore, the obtained long fiber reinforced pellets (E-2) and the crystalline thermoplastic resin (B-1) having a crystallization temperature Tc lower by 10 ° C. or more than the component (A-3) are mixed in the composition described in Table 4. Then, injection molding was performed. The gloss (gloss) of the obtained sample is shown in Table 4. In addition, the weight average fiber length of the glass fiber in the obtained sample was 1.7 mm.

Comparative Example 2
In Example 2, the crystalline thermoplastic resin (B-1) having a crystallization temperature (Tc) lower by 10 ° C. or more than the component (A-3) used for mixing with the long fiber reinforced pellets (E-2). A sample was obtained in the same manner as in Example 2 except that the crystalline thermoplastic resin (A-2) was changed. In addition, the weight average fiber length of the glass fiber in the obtained sample was 1.7 mm.

Example 3
According to the method described in JP-A-3-121146, a long fiber reinforced pellet (E-3) having a composition shown in Table 1 and a glass fiber content of 40% by weight and a pellet length of 9 mm is obtained. Created. The crystalline thermoplastic resin (A-3) used is a propylene homopolymer (MFR = 120 g / 10 min, crystallization temperature (Tc) = 127 ° C.), and the crystallization temperature Tc from the component (A-3). The crystalline thermoplastic resin (B-1) having a temperature of 10 ° C. or lower is FINAPLAS 1751 (MFR = 25 g / 10 min, crystallization temperature (Tc) = 79 ° C., [rrrr] = 0.77) manufactured by Atofina. It was.
Further, the obtained long fiber reinforced pellet (E-3) was injection molded. Table 2 shows the tensile strength, IZOD impact strength, and gloss (gloss) of the obtained sample. In addition, the weight average fiber length of the glass fiber in the obtained sample was 4 mm.

Comparative Example 3
In Example 3, except that the crystalline thermoplastic resin (B-1) having a crystallization temperature Tc lower by 10 ° C. or more than the component (A-1) was changed to the crystalline thermoplastic resin (A-2). A sample was obtained in the same manner as in Example 2. In addition, the weight average fiber length of the glass fiber in the obtained sample was 4 mm. The crystalline thermoplastic resin (component (A-2)) used was a propylene homopolymer (MFR = 25 g / 10 min, crystallization temperature (Tc) = 128 ° C.).

Example 4
According to the method described in JP-A-3-121146, a long fiber reinforced pellet (E-4) having the composition shown in Table 1 and a glass fiber content of 40% by weight and a pellet length of 9 mm is obtained. Created. Further, after mixing the obtained long fiber reinforced pellet (E-4) and the crystalline thermoplastic resin (B-1) having a crystallization temperature Tc lower by 10 ° C. or more than the component (A) with the composition described in Table 5. , Injection molded. The gloss (gloss) of the obtained sample is shown in Table 5. In addition, the weight average fiber length of the glass fiber in the obtained sample was 4 mm.

Comparative Example 4
In Example 4, the crystalline thermoplastic resin (B-1) used for mixing with the long fiber reinforced pellets (E-4) and having a crystallization temperature (Tc) lower by 10 ° C. or more than the component (A) is crystallized. A sample was obtained in the same manner as in Example 4 except that the thermoplastic resin (A-2) was changed. In addition, the weight average fiber length of the glass fiber in the obtained sample was 4 mm.

Ａ−１：プロピレン単独重合体（ＭＦＲ＝８０ｇ／１０分、結晶化温度（Ｔｃ）＝１２７℃）
Ａ−２：プロピレン単独重合体（ＭＦＲ＝２５ｇ／１０分、結晶化温度（Ｔｃ）＝１２８℃）
Ａ−３：プロピレン単独重合体（ＭＦＲ＝１２０ｇ／１０分、結晶化温度（Ｔｃ）＝１２２℃）
Ｃ−１：ガラス繊維（繊維径：１６μｍ）
Ｄ−１：無水マレイン酸変性ポリプロピレン樹脂（ＭＦＲ＝６０ｇ／１０分、無水マレイン酸グラフト量＝０．６重量％）

A-1: Propylene homopolymer (MFR = 80 g / 10 min, crystallization temperature (Tc) = 127 ° C.)
A-2: Propylene homopolymer (MFR = 25 g / 10 min, crystallization temperature (Tc) = 128 ° C.)
A-3: Propylene homopolymer (MFR = 120 g / 10 min, crystallization temperature (Tc) = 122 ° C.)
C-1: Glass fiber (fiber diameter: 16 μm)
D-1: Maleic anhydride-modified polypropylene resin (MFR = 60 g / 10 min, maleic anhydride graft amount = 0.6% by weight)

Ａ−２：プロピレン単独重合体（ＭＦＲ＝２５ｇ／１０分、結晶化温度（Ｔｃ）＝１２８℃）
Ｂ−１：アトフィナ社製ＦＩＮＡＰＬＡＳ １７５１（ＭＦＲ＝２５ｇ／１０分、結晶化温度（Ｔｃ）＝７９℃）
Ｅ−１：長繊維強化ペレット（表１に記載した長繊維強化ペレット（Ｅ−１）を用いた。）

A-2: Propylene homopolymer (MFR = 25 g / 10 min, crystallization temperature (Tc) = 128 ° C.)
B-1: FINAPLAS 1751 (MFR = 25 g / 10 min, crystallization temperature (Tc) = 79 ° C.) manufactured by Atofina
E-1: Long fiber reinforced pellets (The long fiber reinforced pellets (E-1) described in Table 1 were used.)

Ａ−３：プロピレン単独重合体（ＭＦＲ＝１２０ｇ／１０分、結晶化温度（Ｔｃ）＝１２２℃）
Ｃ−１：ガラス繊維（繊維径：１６μｍ）
Ｄ−２：無水マレイン酸変性ポリプロピレン樹脂（ＭＦＲ＝４０ｇ／１０分、無水マレイン酸グラフト量＝０．２重量％）

A-3: Propylene homopolymer (MFR = 120 g / 10 min, crystallization temperature (Tc) = 122 ° C.)
C-1: Glass fiber (fiber diameter: 16 μm)
D-2: Maleic anhydride-modified polypropylene resin (MFR = 40 g / 10 min, maleic anhydride graft amount = 0.2% by weight)

Ｂ−１：アトフィナ社製ＦＩＮＡＰＬＡＳ １７５１（ＭＦＲ＝２５ｇ／１０分、結晶化温度（Ｔｃ）＝７９℃）
Ａ−２：プロピレン単独重合体（ＭＦＲ＝２５ｇ／１０分、結晶化温度（Ｔｃ）＝１２８℃）
Ｅ−４：長繊維強化ペレット（表１に記載した長繊維強化ペレット（Ｅ−４）を用いた。）

B-1: FINAPLAS 1751 (MFR = 25 g / 10 min, crystallization temperature (Tc) = 79 ° C.) manufactured by Atofina
A-2: Propylene homopolymer (MFR = 25 g / 10 min, crystallization temperature (Tc) = 128 ° C.)
E-4: Long fiber reinforced pellet (The long fiber reinforced pellet (E-4) described in Table 1 was used.)

Each of Example 1 and Example 3 satisfying the requirements of the present invention is Comparative Example 1 and Comparative Example which do not contain the component (B) having a crystallization temperature Tc of 10 ° C. or more lower than the component (A) which is a requirement of the present invention. Compared with each of Example 3, it can be seen that there is little decrease in tensile strength and IZOD impact strength, glossiness (gloss) is improved, and the appearance is greatly improved.
In addition, each of Example 2 and Example 4 satisfying the requirements of the present invention does not contain the component (B) having a crystallization temperature Tc of 10 ° C. or lower than the component (A) which is a requirement of the present invention. It can be seen that the glossiness (gloss) is improved and the appearance is greatly improved as compared with each of Comparative Example 4 and Comparative Example 4.

Claims (8)

10 to 99% by weight of a crystalline polyolefin resin (component (A)),
90 to 1% by weight of a crystalline polypropylene resin (component (B)) having a syndiotactic structure having a crystallization temperature lower than that of the component (A) by 10 ° C. or more and a crystallization temperature of 0 to 95 ° C. Containing resin (I);
The composition containing 5-400 weight part of fibers (component (C)) with respect to 100 weight part of resin (I). (However, the total amount of the resin (I) is 100% by weight.)   The composition according to claim 1, wherein the component (A) is a crystalline polyolefin resin partly or entirely modified with an unsaturated carboxylic acid or a derivative thereof.   The composition according to claim 1 or 2, wherein the component (B) is a crystalline polypropylene resin partially or entirely modified with an unsaturated carboxylic acid or a derivative thereof.   A crystalline polyolefin resin (component (A)), a crystalline polypropylene resin (component (B)) having a crystallization temperature lower than that of the component (A) by 10 ° C. or more and a crystallization temperature of 0 to 95 ° C .; Resin (II) containing a modified polyolefin resin (component (D)) partially or wholly modified with an unsaturated carboxylic acid or derivative thereof and 100 parts by weight of resin (II), fibers (component (C )) A composition containing 5 to 400 parts by weight, wherein in resin (II), the weight ratio of component (A) and component (B) is 10 to 99% by weight of component (A), Component (B) is 90 to 1% by weight (provided that the total amount of component (A) and component (B) is 100% by weight), and the weight of component (A) and the weight of component (B) Ratio of weight of component (D) to total (component (D) / Component (A) + component (B)]) is the composition is 0.1 / 99.9 to 20/80.   The composition according to any one of claims 1 to 4, wherein the melt flow rate (230 ° C, 21.2N) of the component (B) is 1 to 300 g / 10 minutes. The composition according to any one of claims 1 to 5 , wherein the fiber (component (C)) has a weight average fiber length of 2 to 100 mm. It is a pellet obtained from the composition described in any one of claims 1 to 6 , the pellet length is 2 to 50 mm, and the weight average fiber length and pellet length of the contained fiber (component (C)) are Pellets characterized by being equal. A molded article obtained from the composition according to any one of claims 1 to 6 or the pellet according to claim 7 , wherein the weight average fiber length of fibers (component (C)) in the molded article is 1 mm or more. .