WO2012132764A1 - 炭素繊維強化ポリプロピレン樹脂組成物、成形材料、および成形品 - Google Patents
炭素繊維強化ポリプロピレン樹脂組成物、成形材料、および成形品 Download PDFInfo
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- WO2012132764A1 WO2012132764A1 PCT/JP2012/055419 JP2012055419W WO2012132764A1 WO 2012132764 A1 WO2012132764 A1 WO 2012132764A1 JP 2012055419 W JP2012055419 W JP 2012055419W WO 2012132764 A1 WO2012132764 A1 WO 2012132764A1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Definitions
- the present invention relates to a carbon fiber reinforced polypropylene resin material, and more specifically, a carbon fiber reinforced polypropylene resin composition and a molding material having particularly good flame retardancy and weather resistance and having excellent mechanical properties, And its molded product.
- a composition comprising a reinforcing fiber and a thermoplastic resin is lightweight and has excellent mechanical properties, it is widely used in sports equipment applications, aerospace applications, and general industrial applications.
- the reinforcing fibers used in these fiber-reinforced thermoplastic resin compositions include metal fibers such as aluminum fibers and stainless fibers, organic fibers such as aramid fibers, inorganic fibers such as silicon carbide fibers, and carbon fibers.
- metal fibers such as aluminum fibers and stainless fibers
- organic fibers such as aramid fibers
- inorganic fibers such as silicon carbide fibers
- carbon fibers is preferable from the viewpoint of the balance between specific strength, specific rigidity, and lightness, and among them, polyacrylonitrile-based carbon fiber is preferably used.
- exterior materials such as car body structural parts are required to have light weight, high strength and high rigidity, and at the same time have high flame resistance and weather resistance.
- polypropylene resin is vulnerable to heat and is a flammable resin.
- this action causes deterioration, that is, discoloration or deterioration of mechanical properties, and molded products using polypropylene resin as a matrix cannot withstand long-term use under significant light irradiation conditions. It is known.
- studies on imparting flame retardancy and weather resistance to carbon fiber reinforced polypropylene resin compositions have been insufficient.
- Patent Document 1 discloses a resin composition comprising a polyester resin, a polypropylene resin, and a graft-modified polypropylene resin for the purpose of increasing the strength and rigidity of the matrix resin.
- Patent Document 2 as a method for imparting flame retardancy and weather resistance to a polypropylene resin, a specific amount of a benzophenone ultraviolet absorber and a hydroxybenzoate light stabilizer is blended in a composition in which a halogen flame retardant is blended with polyolefin. Flame retardant polyolefin compositions are described.
- Patent Document 3 discloses a flame retardant polyolefin composition in which an acid adsorbent and an ultraviolet absorber are used in combination with a polyolefin resin flame retardant with a halogen compound.
- Patent Document 4 contains a polypropylene resin and at least one compound selected from the group consisting of a glitter material made of aluminum particles, a hindered amine light stabilizer, a benzoate compound, and a benzophenone compound.
- a glittering material-containing resin composition capable of obtaining a molded article having a silver metallic appearance and excellent light stability.
- Patent Document 5 discloses that a high degree of flame retardancy is maintained over a long period of time by incorporating a phosphate ester flame retardant and an amino ether type hindered amine stabilizer in a specific range in a polyolefin resin.
- Flame retardant polyolefin composite sheet that can be used and has sufficient sheet strength for practical use, and improved flame retardancy by synergistic effect of phosphate ester flame retardant and amino ether type hindered amine stabilizer Is disclosed.
- JP-A-8-157700 JP-A-6-128423 Japanese Patent Laid-Open No. 5-117451 JP 2006-137877 A JP 2002-337284 A
- Patent Document 1 Although there is a description in Patent Document 1 that carbon fiber is added as a filler to the above resin composition or a flame retardant is blended, the effect of improving the mechanical properties by carbon fiber and the expression of flame retardancy are actually It has not been clarified and no mention is made of weather resistance.
- Patent Document 2 mentions improvement of mechanical properties by carbon fiber.
- Patent Document 4 does not specifically examine the addition of carbon fiber.
- Patent Document 5 does not describe a combination with a brominated flame retardant, and what is disclosed in this document is limited to a thin film material having a thickness of micro order, There is no mention of improving mechanical properties by adding carbon fibers.
- the present invention provides a carbon fiber reinforced polypropylene resin composition and a molding material capable of providing a molded product having good flame retardancy and weather resistance, and excellent mechanical properties, and these
- the object is to provide a molded product.
- the carbon fiber reinforced polypropylene resin composition of the present invention has the following constitution. That is, A carbon fiber reinforced polypropylene resin composition obtained by blending the following components (C) to (F) with respect to a total of 100 parts by weight of (A) polypropylene resin and (B) modified polypropylene resin. (C) Carbon fiber 8 to 70 parts by weight (D) Bromine flame retardant 0.4 to 25 parts by weight (E) Antimony oxide compound 0.2 to 12.5 parts by weight (F) Amino ether type hindered amine light stabilizer 0.05-2 parts by weight.
- the molding material of the present invention has the following constitution.
- the molded article of the present invention has the following constitution. That is, A molded product obtained by molding the molding material.
- the weight ratio (A) / (B) of the component (A) to the component (B) is preferably 95/5 to 75/25.
- the carbon fiber reinforced polypropylene resin composition of the present invention further comprises (G) an ultraviolet absorber in an amount of 0.05 to 2 parts by weight with respect to a total of 100 parts by weight of the components (A) and (B). Is preferred.
- the molding material of the present invention comprises the above components (A), (B), (D), (E) and (F) melt-kneaded, and further (G) a pellet containing an ultraviolet absorber, and the above component (A ), (B) and a long fiber pellet containing (C), and the content of component (G) in the molding material after dry blending is such that the components (A) and (B) ) In the range of 0.05 to 2 parts by weight.
- the molding material of the present invention was obtained by melt-kneading (A) polypropylene resin, (B) modified polypropylene resin, (D) bromine-based flame retardant, (E) antimony oxide compound, and (F) amino ether type hindered amine light stabilizer.
- the components (C) to (F) are preferably in the following ranges with respect to a total of 100 parts by weight.
- the carbon fiber reinforced polypropylene resin composition and molding material of the present invention have good flame retardancy and weather resistance, and good interfacial adhesion between the carbon fiber and the polypropylene resin, so that bending characteristics, impact resistance characteristics, etc. Molded products with excellent mechanical properties can be obtained. Moreover, since the polypropylene resin is used, it also has light weight.
- the carbon fiber reinforced propylene resin composition, molding material, and molded product of the present invention are extremely useful for various parts and members such as electric / electronic equipment, OA equipment, home appliances, or automobile parts, internal members, and casings. It is.
- the resin composition of the present invention comprises at least (A) polypropylene resin, (B) modified polypropylene resin, (C) carbon fiber, (D) bromine flame retardant, (E) antimony oxide compound, (F) amino ether type hindered amine It is composed of a system light stabilizer.
- the (A) polypropylene resin means an unmodified polypropylene resin, specifically, a homopolymer of propylene or a copolymer of propylene and at least one ⁇ -olefin, conjugated diene, non-conjugated diene or the like. It is.
- Examples of the monomer repeating unit constituting the ⁇ -olefin include ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, etc.
- Examples of monomer repeating units constituting 12 ⁇ -olefins, conjugated dienes, and nonconjugated dienes include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and the like. Can select one type or two or more types.
- (A) As a skeleton structure of polypropylene resin a homopolymer of propylene, one or two or more random or block copolymers of propylene and the above-mentioned other monomers, or other thermoplastic monomers And a copolymer thereof.
- polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, and the like are preferable.
- unmodified polypropylene resins are structurally stable and have a good balance between flame retardancy and mechanical properties.
- One or two or more random or block polypropylenes of propylene and the other monomers are used.
- the (B) modified polypropylene resin is preferably an acid-modified polypropylene resin, and is a polypropylene resin having a carboxylic acid and / or salt group bonded to a polymer chain.
- the acid-modified polypropylene resin can be obtained by various methods.
- (A) a polypropylene resin has a neutralized or non-neutralized monomer having a carboxylic acid group, and / or saponified.
- a monomer having a carboxylic acid ester which is saponified or not saponified can be obtained by graft polymerization.
- a monomer having a neutralized or non-neutralized carboxylic acid group and a monomer having a saponified or unsaponified carboxylic acid ester group, for example, ethylene System unsaturated carboxylic acids and anhydrides thereof, and esters thereof, and compounds having unsaturated vinyl groups other than olefins.
- Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and the like. Examples thereof include (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, and the like.
- Examples of monomers having an unsaturated vinyl group other than olefin include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert -Butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (Meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohex
- Acid esters hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate Hydroxyl group-containing vinyls such as glycidyl (meth) acrylate, epoxy group-containing vinyls such as methyl glycidyl (meth) acrylate, vinyl isocyanate, isoprop Isocyanate group-containing vinyls such as ruisocyanate, aromatic vinyls such as styrene, ⁇ -methylstyrene, vinyltoluene and t-butylstyrene, acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, di Amides such as acetone acrylamide and maleic acid amide, vinyl esters such as vinyl acetate and vinyl
- the (B) modified polypropylene resin in order to improve the mechanical properties of the molded article, it is preferable to use the (B) modified polypropylene resin together with the (A) polypropylene resin, particularly from the viewpoint of the balance between flame retardancy and mechanical properties.
- the polypropylene resin and the (B) modified polypropylene resin are preferably used so that the weight ratio (A) / (B) is 95/5 to 75/25. More preferably, it is 95/5 to 80/20, and still more preferably 90/10 to 80/20.
- Carbon fibers used in the present invention include carbon fibers such as PAN, pitch and rayon. From the viewpoint of the balance between the strength and elastic modulus of the obtained molded product, PAN-based carbon fibers are preferable. For the purpose of imparting conductivity, reinforcing fibers coated with a metal such as nickel, copper, or ytterbium can also be used.
- the surface oxygen concentration ratio [O / C] which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy, is 0.05-0. 5 is preferable, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.3.
- the surface oxygen concentration ratio is 0.05 or more, the amount of functional groups on the surface of the carbon fiber can be secured, and stronger adhesiveness can be obtained.
- limiting in particular in the upper limit of surface oxygen concentration ratio Generally it can be illustrated to 0.5 or less from the balance of the handleability of carbon fiber, and productivity.
- the surface oxygen concentration ratio of carbon fiber is determined according to the following procedure by X-ray photoelectron spectroscopy. First, after cutting the carbon fiber bundle from which the sizing agent and the like adhering to the carbon fiber surface with a solvent was cut to 20 mm and spreading on a copper sample support table, using AlK ⁇ 1 and 2 as the X-ray source, The sample chamber is kept at 1 ⁇ 10 8 Torr. The kinetic energy value (K.E.) of the main peak of C1s is adjusted to 1202 eV as a peak correction value associated with charging during measurement. The C1s peak area is determined as K.E. by drawing a straight base line in the range of 1191 to 1205 eV. The O1s peak area is determined as K.E. by drawing a straight base line in the range of 947 to 959 eV.
- the surface oxygen concentration ratio is calculated as an atomic number ratio from the ratio of the O1s peak area to the C1s peak area using a sensitivity correction value unique to the apparatus.
- a sensitivity correction value unique to the apparatus.
- model ES-200 manufactured by Kokusai Electric Inc. is used, and the sensitivity correction value is set to 1.74.
- the means for controlling the surface oxygen concentration ratio [O / C] to 0.05 to 0.5 is not particularly limited.
- techniques such as electrolytic oxidation, chemical oxidation, and vapor phase oxidation Among these, electrolytic oxidation treatment is preferable.
- the average fiber diameter of the carbon fibers is not particularly limited, but is preferably in the range of 1 to 20 ⁇ m, preferably in the range of 3 to 15 ⁇ m, from the viewpoint of mechanical properties and surface appearance of the obtained molded product. More preferred.
- the number of single yarns in the case of reinforcing fiber bundles is not particularly limited and can be used in the range of 100 to 350,000, and in particular, in the range of 1,000 to 250,000. preferable. Further, from the viewpoint of productivity of reinforcing fibers, those having a large number of single yarns are preferable, and it is preferable to use them within the range of 20,000 to 100,000.
- the carbon fiber used in the present invention is preferably a carbon fiber sized by a polyfunctional compound.
- a polyfunctional compound The compound which has 2 or more functional groups, such as an epoxy group, a urethane group, an amino group, and a carboxyl group, can be used, and these are used together 1 type or 2 types or more. May be. Adhesiveness between the reinforcing fiber and the matrix resin can be sufficiently exhibited when the number of functional groups is 2 or more. Therefore, the number of functional groups is preferably 2 or more, more preferably 3 or more.
- the compound include polyfunctional epoxy resins, acid-modified polypropylene, and neutralized products of acid-modified polypropylene.
- polyfunctional epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolac type epoxy resin and the like.
- an aliphatic epoxy resin that easily exhibits adhesiveness with the matrix resin is preferable.
- the crosslinking density after the crosslinking reaction becomes high, and therefore it tends to be a structure with low toughness, and even if it exists between the reinforcing fiber and the matrix resin, it is fragile. It is easy to peel off and the strength of the fiber reinforced composite material may not be expressed.
- the aliphatic epoxy resin since it has a flexible skeleton, it tends to have a high toughness structure even if the crosslinking density is high.
- strength of a fiber reinforced composite material when it exists between a reinforced fiber and matrix resin, in order to make it soft and it is hard to peel, it is easy to improve the intensity
- the aliphatic epoxy resin include, for example, diglycidyl ether compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4- Examples include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and polyalkylene glycol diglycidyl ether.
- diglycidyl ether compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4- Examples include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl
- polyglycidyl ether compound glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane
- examples thereof include glycidyl ethers, pentaerythritol polyglycidyl ethers, polyglycidyl ethers of aliphatic polyhydric alcohols, and the like.
- an aliphatic polyglycidyl ether compound having a large number of highly reactive glycidyl groups is preferable.
- glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, and polypropylene glycol glycidyl ether are more preferable.
- Aliphatic polyglycidyl ether compounds are preferred because they have a good balance of flexibility, crosslink density, and compatibility with the matrix resin and effectively improve adhesion.
- Acid-modified polypropylene, neutralized product of acid-modified polypropylene for example, a polymer main chain mainly composed of hydrocarbon such as propylene, a carboxyl group formed by unsaturated carboxylic acid, or a metal salt or ammonium salt thereof And having a side chain containing.
- the polymer main chain may be a random copolymer obtained by copolymerizing propylene and an unsaturated carboxylic acid, or may be a graft copolymer obtained by grafting an unsaturated carboxylic acid on propylene.
- Acid-modified polypropylene and neutralized product of acid-modified polypropylene are flexible while having many functional groups in one molecule, and since the skeleton is the same polypropylene as the matrix resin, compatibility with the matrix resin is high. It is preferable because it is easy to improve adhesiveness.
- Unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, isocrotonic acid, citraconic acid, allyl succinic acid, mesaconic acid, glutaconic acid, nadic acid, methyl nadic acid, tetrahydrophthalic acid And methyltetrahydrophthalic acid.
- maleic acid, acrylic acid, and methacrylic acid are preferable because they are easily copolymerized.
- Only one type of unsaturated carboxylic acid may be used for copolymerization with propylene or graft copolymerization with propylene, or two or more types of unsaturated carboxylic acids may be used.
- the neutralized product of acid-modified polypropylene is at least partially neutralized with metal cations such as Na, K, Li, Mg, Zn, Ca, Cu, Fe, Ba, Al or ammonium ions. It is preferable.
- the total amount is 0.05 to 5 mmol in terms of a group represented by —C ( ⁇ O) —O— per 1 g of acid-modified polypropylene or neutralized product of acid-modified polypropylene. It is preferable that it is equivalent. More preferably, it is 0.1 to 4 mmol equivalent, and still more preferably 0.3 to 3 mmol equivalent.
- a method for analyzing the content of the carboxylate as described above a method of quantitatively detecting a metal species forming a salt by ICP emission analysis, or a method using IR, NMR, elemental analysis, etc. A method for quantifying the carbonyl carbon of the acid salt is mentioned.
- the polyfunctional compound By applying the polyfunctional compound to the reinforcing fiber as a sizing agent, even if the addition amount is small, it effectively adapts to the surface properties such as functional groups on the surface of the reinforcing fiber and improves the adhesive properties and composite overall properties. Can be made. In addition, it improves bundling, bending resistance, and abrasion resistance, and suppresses the occurrence of fluff and yarn breakage in the high-order processing step. It can also improve the high-order workability as a so-called paste and bundling agent. it can.
- the sizing agent adhesion amount is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 2% by mass with respect to the mass of the reinforcing fiber alone. % Or less is more preferable. If the sizing agent adhesion amount is in the above preferred range, the effect of improving the adhesiveness is sufficient, while the physical properties of the matrix resin are not deteriorated.
- the sizing agent also includes other components such as bisphenol-type epoxy compounds, linear low molecular weight epoxy compounds, polyethylene glycol, polyurethane, polyester, emulsifiers and surfactants, viscosity adjustment, improved scratch resistance, improved fuzz resistance, It may be added for the purpose of improving the focusing property and improving the high-order workability.
- the means for applying the sizing agent there are no particular restrictions on the means for applying the sizing agent, but there are, for example, a method of immersing in a sizing liquid through a roller, a method of contacting a roller to which the sizing liquid is adhered, and a method of spraying the sizing liquid in a mist form. .
- a batch type or a continuous type may be sufficient, the continuous type which has good productivity and small variations is preferable.
- it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active ingredient attached to the reinforcing fiber is uniformly attached within an appropriate range.
- the drying temperature and drying time should be adjusted according to the amount of the compound attached, but the time required for complete removal of the solvent used to apply the sizing agent and drying is shortened, while the thermal deterioration of the sizing agent is prevented and sizing is performed.
- the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower, preferably 180 ° C. More preferably, it is 250 degrees C or less.
- the solvent used for the sizing agent examples include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone and the like, but water is preferable from the viewpoint of easy handling and disaster prevention. Accordingly, when a compound insoluble or hardly soluble in water is used as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse in water.
- styrene-maleic anhydride copolymer styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, anionic emulsifier such as sodium polyacrylate
- anionic emulsifier such as sodium polyacrylate
- Nonionic emulsifiers such as cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, sorbitan ester ethyl oxide adducts, etc.
- a nonionic emulsifier having a small size is preferable because it hardly inhibits the adhesive effect of the polyfunctional compound.
- the blending amount of carbon fiber is 8 to 70 parts by weight with respect to 100 parts by weight in total of (A) polypropylene resin and (B) modified polypropylene resin.
- the amount is preferably 10 to 60 parts by weight, more preferably 15 to 50 parts by weight.
- the carbon fiber is less than 8 parts by weight, the mechanical properties of the molded product may be insufficient. If it exceeds 70 parts by weight, the fluidity may decrease during molding such as injection molding, The surface quality may deteriorate.
- (D) brominated flame retardant used in the present invention known ones can be used. Typical examples include decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, 1,2-bis (2 ′, 3 ′, 4 ′, 5 ′, 6′-pentabromophenyl) ethane, 1, 2-bis (2,4,6-tribromophenoxy) ethane, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, 2,6-dibromophenol, 2,4-dibromophenol, brominated polystyrene, ethylenebistetrabromophthalimide, hexabromocyclododecane, hexabromobenzene, pentabromobenzyl acrylate, 2,2-bis [4 ′ (2 ′′, 3 ′′ -dibromopropoxy )-, 3 ',
- the amount of the brominated flame retardant is 0.4 to 25 parts by weight with respect to 100 parts by weight in total of (A) polypropylene resin and (B) modified polypropylene resin. The amount is preferably 5 to 15 parts by weight. (D) If the brominated flame retardant is less than 0.4 part by weight, a sufficient flame retardant effect may not be obtained. If it exceeds 25 parts by weight, the mechanical properties are deteriorated, the specific gravity of the molded product is increased or the molded product is increased. The flame retardant may bleed out from the surface.
- (E) antimony oxide compound used in the present invention known compounds can be used. Typical examples include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, antimony trichloride, antimony trisulfide, antimony oxychloride, antimony perchloropentane dichloride, and potassium antimonate. Antimony trioxide and antimony pentoxide are particularly preferable. These may be used alone or in combination of two or more.
- the compounding amount of the antimony oxide compound is 0.2 to 12.5 parts by weight with respect to 100 parts by weight in total of (A) polypropylene resin and (B) modified polypropylene resin.
- the amount is preferably 2.5 to 7.5 parts by weight.
- the antimony oxide compound is less than 0.2 parts by weight, a sufficient flame retardant effect may not be obtained, and when it exceeds 12.5 parts by weight, the mechanical properties decrease or the specific gravity of the molded article increases. There is.
- the (F) amino ether type hindered amine light stabilizer used in the present invention refers to a hindered amine light stabilizer having a structure represented by the following structural formula (1) in the compound.
- Examples include Tinuvin 123, Tinuvin 152, Tinuvin NOR 371 FF, Tinuvin XT850 FF, Tinuvin XT855 FF, Flamestab NOR 116 FF manufactured by BASF Japan, and ADEKA KAAdeka Stub LA-81. These may be used alone or in combination of two or more.
- R 1 is an arbitrary structure other than hydrogen
- R 2 includes at least one of an alkyl group, a cycloalkyl group, an alkylcarbonyl group, and a cycloalkylcarbonyl group.
- Preferred carbon number of R 2 is from 5 to 12
- Aminoether-type hindered amine light stabilizers are oxidized by oxygen, ultraviolet rays, etc., to generate nitrooxide radicals, capture the alkyl radicals generated in polypropylene resin, take the structure of aminoether (-NOR), and further alkyl Weather resistance is maintained by capturing radicals and peroxide radicals.
- thermal decomposition that generates flammable gas is a chain reaction involving active radicals.
- the nitrooxide radical as described above is generated during combustion from the amino ether type hindered amine light stabilizer, and this captures and lowers the active radical, and exhibits flame retardancy.
- the flame retardancy is synergistically improved by the combined use with a brominated flame retardant.
- the cause of this mechanism is not always clear, but nitrooxide radicals derived from aminoether-type hindered amine light stabilizers promote the radical trapping effect of brominated flame retardants, so-called flame retardants such as antimony oxide compounds. Presumed to work equivalent to an auxiliary agent.
- a non-amino ether type hindered amine light stabilizer having an NH or NR (R: alkyl group) structure is an amine compound, so that when it is attacked by an acid, it causes a neutralization reaction and has an effect as a weathering agent. descend. Therefore, when a halogen-based flame retardant is used in combination as in the present invention, the effect of improving weather resistance is lost, which is not preferable. At the same time, some nitrooxide radicals take time due to the structure, which is not preferable because the peroxide radicals may not be captured in the polypropylene resin.
- the compounding amount of the amino ether type hindered amine light stabilizer is 0.05 to 2 parts by weight with respect to 100 parts by weight in total of (A) polypropylene resin and (B) modified polypropylene resin.
- (G) UV absorber is added in combination with an amino ether type hindered amine light stabilizer to improve the weather resistance and flame retardancy. Since an effect is expectable, it is preferable.
- a well-known thing can be used for a ultraviolet absorber, For example, a benzotriazole type
- UV absorber When (G) UV absorber is added in addition to the above components (A) to (F), 0.05 to 2 parts by weight per 100 parts by weight in total of (A) polypropylene resin and (B) modified polypropylene resin Is preferred. (G) When the ultraviolet absorber is within this preferred range, the mechanical properties are not lowered and the flame retardancy is not lowered.
- the carbon fiber reinforced polypropylene resin composition in the present invention may contain other fillers and additives as long as the object of the present invention is not impaired.
- these include inorganic fillers, conductivity imparting agents, crystal nucleating agents, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers, mold release agents, antistatic agents Agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents.
- pellets, stampable sheets, prepregs, SMC, BMC, etc. can be used as the molding material of the carbon fiber reinforced polypropylene resin composition, but the most desirable molding material is used for injection molding. It is a pellet.
- the pellet generally refers to a pellet obtained by kneading a desired amount of resin, a filler, a chopped yarn of fibers, or continuous fibers in an extruder, and extruding and pelletizing.
- the length of the pellet in the pellet is shorter than the length in the longitudinal direction of the pellet, but the pellet in the present invention includes a long fiber pellet and is preferably used. Can do.
- Such long fiber pellets are arranged such that fibers are arranged substantially parallel to the longitudinal direction of the pellet, and the fiber length in the pellet is equal to or longer than the pellet length. It points to something.
- the length of the long fiber pellet is preferably 1 to 50 mm, more preferably 3 to 20 mm in the longitudinal direction.
- the resin may be impregnated in the fiber bundle or may be coated on the fiber bundle.
- the fiber bundle may be impregnated in advance with a resin having the same viscosity as that of the coated fiber or a resin having a lower viscosity (or lower molecular weight) than the coated resin.
- the amount of resin impregnated or coated on the fiber bundle is preferably 50 to 1,900 parts by weight, more preferably 150 to 900 parts by weight with respect to 100 parts by weight of the fiber bundle.
- the amount of the low viscosity (or low molecular weight) resin is preferably 10 to 40 parts by weight with respect to 100 parts by weight of the carbon fiber.
- the fiber length in the molded product is longer than the pellet in which the fiber length in the pellet is shorter than the length in the longitudinal direction of the pellet. More preferably used.
- the component (G) is further added to pellets obtained by melt-kneading the components (A), (B), (D), (E) and (F), or pellets obtained by melt-kneading. It is preferable from the viewpoint of ease of handling and composition change that a pellet obtained by blending and a long fiber pellet containing the above components (A), (B) and (C) is dry blended.
- dry blending is different from melt-kneading and refers to stirring and mixing the melt-kneaded pellets and the long fiber pellets to form substantially uniform pellets.
- a molding material in which the component (C) is coated with a polypropylene resin composition obtained by melt-kneading the components (A), (B), (D), (E) and (F) is used.
- a polypropylene resin composition obtained by melting and kneading the above components (A), (B), (D), (E) and (F) with a resin covering carbon fibers or It is a polypropylene resin composition obtained by melt-kneading the component (G), and since it can be produced continuously, it is excellent in productivity and handleability, and the uniformity of the resin composition around the carbon fiber is high.
- a polypropylene resin composition obtained by melt-kneading the component (G) is excellent in productivity and handleability, and the uniformity of the resin composition around the carbon fiber is high.
- Examples of the molding method of the carbon fiber reinforced polypropylene resin composition and the molding material in the present invention include injection molding, press molding, transfer molding, and combinations thereof. Injection molding is preferable from the viewpoint of excellent molding efficiency. used.
- Molded products are suitable for automobile parts such as instrument panels, door beams, under covers, lamp housings, pedal housings, radiator supports, spare tire covers, front ends, and other modules.
- home / office electrical product parts such as telephones, facsimiles, VTRs, copiers, televisions, microwave ovens, audio equipment, toiletries, refrigerators, air conditioners, and the like are also included.
- a housing used for a personal computer, a mobile phone and the like and a member for electric / electronic equipment represented by a keyboard support which is a member for supporting a keyboard inside the personal computer. Since carbon fiber having conductivity is used as the reinforcing fiber, such a member for electrical / electronic equipment is more preferable because it imparts electromagnetic wave shielding properties.
- A Self-extinguishing within 30 seconds after flame contact.
- Judgment was made based on the following criteria, and a, b, and c were regarded as acceptable.
- F Innumerable cracks are generated on the entire surface of the test piece, and the carbon fibers on the surface are exposed.
- a sizing agent mother liquor in which polyglycerol polyglycidyl ether as a polyfunctional compound was dissolved or dispersed in water so as to be 2% by weight was prepared, and a sizing agent was imparted to the carbon fiber by a dipping method. And dried.
- the carbon fiber thus obtained had a sizing agent adhesion of 1.0% by weight.
- the extruder cylinder temperature was set to 220 ° C.
- the carbon fiber (C) obtained from the reference example was supplied to a die port (3 mm in diameter) for discharging the molten resin, the resin-coated strand was cooled, and the pelletizer The pellet length was cut to 10 mm to obtain a long fiber pellet.
- composition of (C), (D), (E), (F) with respect to the total of 100 parts by weight of the components (A) and (B) of the melt-kneaded pellets and the long fiber pellets thus obtained. was dry blended to obtain a molding material so that
- Example 3 When dry blending the melt-kneaded pellets and the long fiber pellets, dry blending was performed so that the composition of (C) carbon fiber was 60 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). Except for the above, molding evaluation was carried out in the same manner as in Example 1. The evaluation results are summarized in Table 1.
- Example 4 When dry blending the melt-kneaded pellets and the long fiber pellets, the composition of the (D) brominated flame retardant is 2 parts by weight with respect to the total of 100 parts by weight of the components (A) and (B), and (E) 3 Molding evaluation was performed in the same manner as in Example 1 except that dry blending was performed so that the amount of antimony oxide was 1 part by weight. The evaluation results are summarized in Table 1.
- Example 5 When dry blending the melt-kneaded pellet and the long fiber pellet, the composition of the brominated flame retardant (D) is 20 parts by weight, and (E) 3 parts per 100 parts by weight of the total of the components (A) and (B). Molding evaluation was performed in the same manner as in Example 1 except that dry blending was performed so that the amount of antimony oxide was 10 parts by weight. The evaluation results are summarized in Table 1.
- Example 6 When dry blending the melt-kneaded pellets and the long fiber pellets, the composition of the (F) amino ether type hindered amine light stabilizer is 0.05% with respect to 100 parts by weight of the total of the components (A) and (B). Molding evaluation was performed in the same manner as in Example 1 except that dry blending was performed so as to be part. The evaluation results are summarized in Table 1.
- Example 7 When dry blending the melt-kneaded pellets and the long fiber pellets, the composition of the (F) amino ether type hindered amine light stabilizer is 1.5 weights with respect to a total of 100 parts by weight of the components (A) and (B). Molding evaluation was performed in the same manner as in Example 1 except that dry blending was performed so as to be part. The evaluation results are summarized in Table 1.
- Example 8 Molding evaluation was performed in the same manner as in Example 1 except that the weight ratio (A) / (B) of the components (A) and (B) contained in the melt-kneaded pellets and the long fiber pellets was 95/5. .
- the evaluation results are summarized in Table 1.
- Example 9 Molding evaluation was performed in the same manner as in Example 1 except that the weight ratio (A) / (B) of the components (A) and (B) contained in the melt-kneaded pellets and the long fiber pellets was 75/25. .
- the evaluation results are summarized in Table 1.
- Example 10 When preparing the melt-kneaded pellet, (G) a benzotriazole ultraviolet absorber (Tinuvin 326 manufactured by BASF Japan Ltd.) is further blended, and the total amount of the above components (A) and (B) is 100 parts by weight. (G) Molding evaluation was performed in the same manner as in Example 1 except that dry blending was performed so that the composition of the benzotriazole-based ultraviolet absorber was 0.3 parts by weight. The evaluation results are summarized in Table 1.
- Example 11 When dry blending the melt-kneaded pellets and the long fiber pellets, the composition of the (D) brominated flame retardant is 0.5 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). ) Molding evaluation was performed in the same manner as in Example 1 except that dry blending was performed so that the amount of antimony trioxide was 0.25 parts by weight. The evaluation results are summarized in Table 1.
- Example 12 When preparing the melt-kneaded pellet, (G) a benzotriazole ultraviolet absorber (Tinuvin 326 manufactured by BASF Japan Ltd.) is further blended, and the total amount of the above components (A) and (B) is 100 parts by weight. (G) Molding evaluation was carried out in the same manner as in Example 1 except that dry blending was performed so that the composition of the benzotriazole ultraviolet absorber was 2 parts by weight. The evaluation results are summarized in Table 1.
- NOR type represents an amino ether type
- non-NOR type represents a non-amino ether type
- the carbon fiber reinforced polypropylene resin composition, molding material, and molded article of the present invention have good flame retardancy and weather resistance, as well as excellent mechanical properties such as bending properties and impact resistance properties. It is extremely useful for various parts and members such as equipment, OA equipment, home appliances, or automobile parts, internal members, and housings.
Abstract
Description
(A)ポリプロピレン樹脂と(B)変性ポリプロピレン樹脂の合計100重量部に対し、下記成分(C)~(F)を配合してなる炭素繊維強化ポリプロピレン樹脂組成物、である。
(C)炭素繊維 8~70重量部
(D)臭素系難燃剤 0.4~25重量部
(E)酸化アンチモン化合物 0.2~12.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.05~2重量部
上記課題を解決するため、本発明の成形材料は次の構成を有する。すなわち、
(A)ポリプロピレン樹脂、(B)変性ポリプロピレン樹脂、(D)臭素系難燃剤、(E)酸化アンチモン化合物および(F)アミノエーテル型ヒンダードアミン系光安定剤を溶融混練したペレットならびに、(A)ポリプロピレン樹脂、(B)変性ポリプロピレン樹脂および(C)炭素繊維を含む長繊維ペレットとをドライブレンドした成形材料であって、ドライブレンド後の成形材料中の成分(C)~(F)の含有量が、上記成分(A)と(B)の合計100重量部に対し、次の範囲である成形材料、である。
(D)臭素系難燃剤 0.4~25重量部
(E)酸化アンチモン化合物 0.2~12.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.05~2重量部
上記課題を解決するため、本発明の成形品は次の構成を有する。すなわち、
上記成形材料を成形してなる成形品、である。
(D)臭素系難燃剤 0.4~25重量部
(E)酸化アンチモン化合物 0.2~12.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.05~2重量部
本発明の成形材料は、上記成分(A)、(B)、(D)、(E)および(F)を溶融混練し、さらに(G)紫外線吸収剤を配合したポリプロピレン樹脂組成物にて(C)炭素繊維を被覆した成形材料であって、被覆後の成形材料中の成分(G)の含有量が、上記成分(A)と(B)の合計100重量部に対し、0.05~2重量部の範囲であることが好ましい。
アミノエーテル型ヒンダードアミン系光安定剤は、酸素、紫外線などにより酸化され、ニトロオキサイドラジカルを生成し、ポリプロピレン樹脂中に生成したアルキルラジカルを捕獲し、アミノエーテル(-NOR)の構造をとり、さらにアルキルラジカルおよび過酸化物ラジカルを捕獲することで耐候性を保持する。
また前記長繊維ペレットにおいて、樹脂は繊維束中に含浸されていても、繊維束に被覆されていてもよい。特に樹脂が被覆された長繊維ペレットの場合、繊維束には被覆されたものと同じか、あるいは被覆された樹脂よりも低粘度(または低分子量)の樹脂が、予め含浸されていてもよい。
ISO 178に準拠し、3点曲げ試験冶具(圧子半径5mm)を用いて支点距離を64mmに設定し、試験速度2mm/minの試験条件にて曲げ強度を測定した。試験機として、“インストロン(登録商標)”万能試験機5566型(インストロン社製)を用いた。
ISO 179に準拠し、ノッチ加工付きシャルピー衝撃試験を試験温度23℃の条件下で行った。シャルピー試験機はCEAST社製 RESIL25を用いた。試験片寸法は、厚み4mm、幅10mm、長さ80mmの試験片を用いた。温度調整はタバイ製 PU-1K型恒温器を用いて、恒温器内で40min以上静置して温度一定にした後、試験を行った。
FMVSS No.302延焼試験に準拠し、寸法100mm×150mm×3mmtの角板を用いて、高さ38mmのガスバーナー炎を角板の端部に着火するまで接炎し、端部から標線に至るまでの間の自己消火性を測定した。
以下の基準に基づき判定を行い、a、b、cを合格とした。
紫外線ロングライフフェードメーター(スガ試験機械(株)製)を用いて、83℃、水スプレーサイクルなしの条件下、寸法100mm×100mm×3mmtの角板に光照射した。光照射時間が500時間を経過した際の試験片表面をデジタルマイクロスコープ(キーエンス(株)製、型式VHX-900)で観察し、表面の状態で耐候性を測定した。
ポリアクリロニトリルを主成分とする共重合体から紡糸、焼成処理、表面酸化処理を行い、総単糸数24,000本、単繊維径7μm、単位長さ当たりの質量1.6g/m、比重1.8g/cm3、表面酸素濃度[O/C]0.06の連続炭素繊維を得た。この連続炭素繊維のストランド引張強度は4,880MPa、ストランド引張弾性率は225GPaであった。続いて、多官能性化合物としてポリグリセロールポリグリシジルエーテルを2重量%になるように水に溶解、または分散させたサイジング剤母液を調整し、浸漬法により炭素繊維にサイジング剤を付与し、230℃で乾燥を行った。こうして得られた炭素繊維のサイジング剤付着量は1.0重量%であった。
JSW製TEX-30α型2軸押出機(スクリュー直径30mm、ダイス直径5mm、バレル温度220℃、スクリュー回転数150rpm)を使用し、(A)ポリプロピレン樹脂(プライムポリマー(株)製プライムポリプロJ105G樹脂)と(B)マレイン酸変性ポリプロピレン樹脂(三井化学(株)製アドマーQE840)を重量比(A)/(B)=85/15でペレットブレンドしたもの、(D)臭素系難燃剤(丸菱油化工業(株)製ノンネンPR-2)、(E)三酸化アンチモン(昭和化学(株)製)、(F)アミノエーテル型ヒンダードアミン系光安定剤(BASFジャパン(株)製Tinuvin 123)をメインホッパーから供給し、下流の真空ベントより脱気を行いながら、溶融樹脂をダイス口から吐出し、得られたストランドを冷却後、カッターで切断して溶融混練ペレットを得た。
(D)臭素系難燃剤 5重量部
(E)酸化アンチモン化合物 2.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.3重量部
次に得られたドライブレンドした成形材料を、住友重機械工業社製SE75DUZ-C250型射出成形機を用いて、射出時間:10秒、保圧力:成形下限圧+10MPa、保圧時間:10秒、シリンダー温度:230℃、金型温度:60℃で特性評価用試験片(成形品)を成形した。得られた試験片は、温度23℃、50%RHに調整された恒温恒湿室に24時間放置後に特性評価試験に供した。次に、得られた特性評価用試験片(成形品)を上記(1)~(4)に示した射出成形品評価方法に従い評価した。評価結果をまとめて表1に示した。
単軸押出機の吐出先端部に溶融樹脂の被覆ダイス口を設置した長繊維強化樹脂ペレット製造装置を使用し、押出機シリンダー温度を220℃に設定し、(A)ポリプロピレン樹脂(プライムポリマー(株)製プライムポリプロJ105G樹脂)と(B)マレイン酸変性ポリプロピレン樹脂(三井化学(株)製アドマーQE840)を重量比(A)/(B)=85/15でペレットブレンドしたもの、(D)臭素系難燃剤(丸菱油化工業(株)製ノンネンPR-2)、(E)三酸化アンチモン(昭和化学(株)製)、(F)アミノエーテル型ヒンダードアミン系光安定剤(BASFジャパン(株)製Tinuvin 123)をメインホッパーから供給し、スクリュー回転数200rpmで溶融させ、参考例から得られた(C)炭素繊維を、溶融樹脂を吐出するダイス口(直径3mm)へ供給して、樹脂を被覆したストランドを冷却後、ペレタイザーでペレット長10mm長さに切断して長繊維ペレットとして成形材料を得た。この際、下記成形材料について、上記成分(A)と(B)の合計100重量部に対して、(C)、(D)、(E)、(F)の組成が下記の通りになるよう、各成分の供給量を調整した。
(D)臭素系難燃剤 5重量部
(E)酸化アンチモン化合物 2.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.3重量部
次に得られた長繊維ペレット状の成形材料を、住友重機械工業社製SE75DUZ-C250型射出成形機を用いて、射出時間:10秒、保圧力:成形下限圧+10MPa、保圧時間:10秒、シリンダー温度:230℃、金型温度:60℃で特性評価用試験片(成形品)を成形した。得られた試験片は、温度23℃、50%RHに調整された恒温恒湿室に24時間放置後に特性評価試験に供した。次に、得られた特性評価用試験片(成形品)を上記(1)~(4)に示した射出成形品評価方法に従い評価した。評価結果をまとめて表1に示した。
溶融混練ペレットと長繊維ペレットをドライブレンドする際に、上記成分(A)と(B)の合計100重量部に対して、(C)炭素繊維の組成が60重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットと長繊維ペレットをドライブレンドする際に、上記成分(A)と(B)の合計100重量部に対して、(D)臭素系難燃剤の組成が2重量部、(E)三酸化アンチモンが1重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットと長繊維ペレットをドライブレンドする際に、上記成分(A)と(B)の合計100重量部に対して、(D)臭素系難燃剤の組成が20重量部、(E)三酸化アンチモンが10重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットと長繊維ペレットをドライブレンドする際に、上記成分(A)と(B)の合計100重量部に対して、(F)アミノエーテル型ヒンダードアミン系光安定剤の組成が0.05重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットと長繊維ペレットをドライブレンドする際に、上記成分(A)と(B)の合計100重量部に対して、(F)アミノエーテル型ヒンダードアミン系光安定剤の組成が1.5重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレット、および長繊維ペレットに含まれる成分(A)と(B)の重量比(A)/(B)が95/5であること以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレット、および長繊維ペレットに含まれる成分(A)と(B)の重量比(A)/(B)が75/25であること以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットを作製する際に、さらに(G)ベンゾトリアゾール系紫外線吸収剤(BASFジャパン(株)製Tinuvin 326)を配合し、上記成分(A)と(B)の合計100重量部に対して、(G)ベンゾトリアゾール系紫外線吸収剤の組成が0.3重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットと長繊維ペレットをドライブレンドする際に、上記成分(A)と(B)の合計100重量部に対して、(D)臭素系難燃剤の組成が0.5重量部、(E)三酸化アンチモンが0.25重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットを作製する際に、さらに(G)ベンゾトリアゾール系紫外線吸収剤(BASFジャパン(株)製Tinuvin 326)を配合し、上記成分(A)と(B)の合計100重量部に対して、(G)ベンゾトリアゾール系紫外線吸収剤の組成が2重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表1に示した。
溶融混練ペレットを作製する際に、(F)アミノエーテル型ヒンダードアミン系光安定剤を配合しない以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
溶融混練ペレットと長繊維ペレットをドライブレンドする際に、上記成分(A)と(B)の合計100重量部に対して、(F)アミノエーテル型ヒンダードアミン系光安定剤の組成が3重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
溶融混練ペレットを作製する際に、(F)アミノエーテル型ヒンダードアミン系光安定剤に代わって非アミノエーテル型ヒンダードアミン系光安定剤(BASFジャパン(株)製Chimassorb 2020 FDL)を配合し、上記成分(A)と(B)の合計100重量部に対して、非アミノエーテル型ヒンダードアミン系光安定剤の組成が0.3重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
溶融混練ペレットを作製する際に、(F)アミノエーテル型ヒンダードアミン系光安定剤
に代わってベンゾエート系光安定剤(BASFジャパン(株)製Tinuvin 120)を配合し、上記成分(A)と(B)の合計100重量部に対して、非アミノエーテル型ヒンダードアミン系光安定剤の組成が0.3重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
溶融混練ペレット、および長繊維ペレットに含まれる成分(A)と(B)の重量比(A)/(B)が100/0であること以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
溶融混練ペレット、および長繊維ペレットに含まれる成分(A)と(B)の重量比(A)/(B)が0/100であること以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
溶融混練ペレットを作製する際に、(D)臭素系難燃剤と(E)酸化アンチモン化合物に代わってリン系難燃剤(ADEKA(株)製FP-600)を配合し、上記成分(A)と(B)の合計100重量部に対して、リン系難燃剤の組成が5重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
溶融混練ペレットを作製する際に、(D)臭素系難燃剤と(E)酸化アンチモン化合物に代わってリン系難燃剤(ADEKA(株)製FP-600)を配合し、上記成分(A)と(B)の合計100重量部に対して、リン系難燃剤の組成が30重量部となるようにドライブレンドした以外は実施例1と同様にして成形評価を行った。評価結果をまとめて表2に示した。
Claims (8)
- (A)ポリプロピレン樹脂と(B)変性ポリプロピレン樹脂の合計100重量部に対し、下記成分(C)~(F)を配合してなる炭素繊維強化ポリプロピレン樹脂組成物。
(C)炭素繊維 8~70重量部
(D)臭素系難燃剤 0.4~25重量部
(E)酸化アンチモン化合物 0.2~12.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.05~2重量部 - 上記成分(A)と上記成分(B)の重量比(A)/(B)が95/5~75/25である請求項1に記載の炭素繊維強化ポリプロピレン樹脂組成物。
- さらに(G)紫外線吸収剤を、上記成分(A)と(B)の合計100重量部に対し、0.05~2重量部配合してなる請求項1または2に記載の炭素繊維強化ポリプロピレン樹脂組成物。
- (A)ポリプロピレン樹脂、(B)変性ポリプロピレン樹脂、(D)臭素系難燃剤、(E)酸化アンチモン化合物および(F)アミノエーテル型ヒンダードアミン系光安定剤を溶融混練したペレットならびに、(A)ポリプロピレン樹脂、(B)変性ポリプロピレン樹脂および(C)炭素繊維を含む長繊維ペレットをドライブレンドした成形材料であって、ドライブレンド後の成形材料中の成分(C)~(F)の含有量が、上記成分(A)と(B)の合計100重量部に対し、次の範囲である成形材料。
(C)炭素繊維 8~70重量部
(D)臭素系難燃剤 0.4~25重量部
(E)酸化アンチモン化合物 0.2~12.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.05~2重量部 - 上記成分(A)、(B)、(D)、(E)および(F)を溶融混練し、さらに(G)紫外線吸収剤を配合したペレットならびに、上記成分(A)、(B)および(C)を含む長繊維ペレットとをドライブレンドした成形材料であって、ドライブレンド後の成形材料中の成分(G)の含有量が、上記成分(A)と(B)の合計100重量部に対し、0.05~2重量部の範囲である請求項4に記載の成形材料。
- (A)ポリプロピレン樹脂、(B)変性ポリプロピレン樹脂、(D)臭素系難燃剤、(E)酸化アンチモン化合物および(F)アミノエーテル型ヒンダードアミン系光安定剤を溶融混練したポリプロピレン樹脂組成物にて(C)炭素繊維を被覆した成形材料であって、被覆後の成形材料中の成分(C)~(F)の含有量が、上記成分(A)と(B)の合計100重量部に対し、上記成分(C)~(F)が次の範囲である成形材料。
(C)炭素繊維 8~70重量部
(D)臭素系難燃剤 0.4~25重量部
(E)酸化アンチモン化合物 0.2~12.5重量部
(F)アミノエーテル型ヒンダードアミン系光安定剤 0.05~2重量部 - 上記成分(A)、(B)、(D)、(E)および(F)を溶融混練し、さらに(G)紫外線吸収剤を配合したポリプロピレン樹脂組成物にて(C)炭素繊維を被覆した成形材料であって、被覆後の成形材料中の成分(G)の含有量が、上記成分(A)と(B)の合計100重量部に対し、0.05~2重量部の範囲である請求項6に記載の成形材料。
- 請求項4~7のいずれかに記載の成形材料を成形してなる成形品。
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EP2692794B1 (en) | 2019-12-25 |
CN103443193A (zh) | 2013-12-11 |
EP2692794A1 (en) | 2014-02-05 |
CN103443193B (zh) | 2016-03-23 |
EP2692794A4 (en) | 2014-10-22 |
JP5857957B2 (ja) | 2016-02-10 |
JPWO2012132764A1 (ja) | 2014-07-28 |
KR20140018292A (ko) | 2014-02-12 |
KR101843220B1 (ko) | 2018-03-28 |
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