WO2011030544A1 - 炭素繊維強化樹脂組成物 - Google Patents
炭素繊維強化樹脂組成物 Download PDFInfo
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- WO2011030544A1 WO2011030544A1 PCT/JP2010/005503 JP2010005503W WO2011030544A1 WO 2011030544 A1 WO2011030544 A1 WO 2011030544A1 JP 2010005503 W JP2010005503 W JP 2010005503W WO 2011030544 A1 WO2011030544 A1 WO 2011030544A1
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- 0 CC(*)(C(C=O)N1*N)C(C)(*)C1=O Chemical compound CC(*)(C(C=O)N1*N)C(C)(*)C1=O 0.000 description 1
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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
- 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
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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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 resin composition and a molded product obtained using the same.
- Methods for improving the interfacial adhesion between polyolefin resin and carbon fiber include adding acid-modified polyolefin resin to matrix resin, sizing treatment of carbon fiber with sizing agent composed of polyolefin resin and silane coupling agent, patent As disclosed in Literature 1-3, a method of sizing carbon fibers with a sizing agent containing acid-modified polypropylene as an essential component is known.
- JP-A-6-107442 Japanese Patent Laid-Open No. 2-84566 JP 2006-124847 A
- An object of the present invention is to provide a carbon fiber reinforced resin composition having improved strength characteristics such as tensile fracture stress and bending strength.
- the following carbon fiber reinforced resin composition, resin composition, and molded article comprising these are provided.
- A a polyolefin resin, (B) an acid-modified polyolefin resin, and (C) a modified carbon fiber having an adhesion amount of 0.2 to 5.0% by mass of an amino group-containing modified polyolefin resin.
- 2. The carbon fiber reinforced resin composition according to 1, wherein the mass ratio of (A) :( B) is 80 to 99:20 to 1. 3.
- the modified carbon fiber (C) is obtained by attaching the amino group-containing modified polyolefin resin to the surface of the carbon fiber and then heat-treating at 200 to 300 ° C. for 5 seconds to 3 minutes. Or a carbon fiber reinforced resin composition. 5.
- the modified carbon fiber (C) is obtained by attaching the amino group-containing modified polyolefin resin to the surface of the carbon fiber and then heat-treating at 220 to 240 ° C. for 20 seconds to 40 seconds. Or a carbon fiber reinforced resin composition. 6). 6.
- the amino group-containing modified polyolefin resin is one compound selected from the group consisting of ethylene-ethyl acrylate-maleic anhydride copolymer, maleic anhydride grafted polyethylene resin, and maleic anhydride grafted polypropylene resin; 7.
- the amino group-containing modified polyolefin resin has an amino group and 70 to 99.98 mol% of repeating units represented by the following formula (I) in the molecule, and a repeating unit represented by the following formula (II): 8.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- R 5 represents an alkyl group, and R 5 represents an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 5 to 17 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aryl alkylene group having 7 to 12 carbon atoms, or 4 to 4 carbon atoms.
- R 1 to R 5 may be the same or different for each repeating unit.
- a resin composition comprising 3 to 60% by mass of the modified carbon fiber (C), comprising the carbon fiber reinforced resin composition according to any one of 9.1 to 8 and a thermoplastic resin. 10.
- the interfacial adhesion of the carbon fiber to the polyolefin resin is improved, and the carbon fiber reinforced resin
- the strength characteristics (tensile fracture stress, bending strength) of the composition can be improved.
- the carbon fiber reinforced resin composition of the present invention has a modified amount in which the adhesion amount of (A) polyolefin resin, (B) acid-modified polyolefin resin, and (C) amino group-containing modified polyolefin resin is 0.2 to 5.0% by mass. Contains carbon fiber.
- polyolefin resin (A) examples include homopolymers of ⁇ -olefins such as ethylene, propylene, butene-1,3-methylbutene-1,4-methylbutene-1, octene-1, copolymers thereof, and others
- copolymer examples include a block copolymer, a random copolymer, and a graft copolymer.
- polyethylene resins such as high density, medium density, low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polypropylene, ethylene-propylene
- polyethylene resins such as high density, medium density, low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polypropylene, ethylene-propylene
- polystyrene resins may be used alone or in a mixture, but polypropylene resins are particularly suitable.
- a commercially available polypropylene-based resin can be used, and one whose fluidity is adjusted with an organic peroxide can also be used.
- the melt flow rate is preferably 10 to 500 g / 10 minutes, more preferably 60 to 300 g / 10 minutes, and further preferably 100 to 200 g / 10 minutes (according to JIS K7210, temperature 230 ° C., load 2.16 kg). Measured under the following conditions). If the MFR is less than 10 g / 10 min, the dispersibility of the reinforcing fibers in the molded product may be reduced, and the appearance of the molded product may be poor. If the MFR is greater than 500 g / 10 min, the impact strength may be reduced, which is preferable. Absent.
- the polyolefin resin includes ethylene- ⁇ -olefin copolymer rubber, ethylene- ⁇ -olefin-nonconjugated diene copolymer rubber (for example, EPDM), ethylene-aromatic monovinyl compound-nonconjugated diene. Rubbers such as system copolymer rubbers and hydrogenated products thereof may be contained.
- the modified polyolefin resin (B) modified with an acid such as an unsaturated carboxylic acid or a derivative thereof improves the interfacial strength between the modified carbon fiber or between the modified carbon fiber and the polyolefin resin, such as breaking stress and bending strength. Significantly improve strength characteristics.
- the polyolefin resin to be modified may be the same as or different from the polyolefin resin (A), but the same resin is preferable.
- a polyethylene resin and a polypropylene resin are preferable, and polypropylene is particularly preferable.
- Examples of the acid used for modification include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid.
- unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid.
- derivatives of these unsaturated carboxylic acids can also be used, and examples of the derivatives include acid anhydrides, esters, amides, imides, metal salts, and the like.
- maleic anhydride For example, maleic anhydride, itaconic anhydride, methyl acrylate And methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethyl maleate, acrylamide, maleic amide, sodium acrylate, sodium methacrylate and the like.
- unsaturated dicarboxylic acids or derivatives thereof are preferred, and maleic anhydride is more preferred.
- unsaturated carboxylic acids or derivatives thereof may be used alone or in combination of two or more.
- a well-known method is employ
- the acid content in the acid-modified polyolefin resin such as unsaturated carboxylic acid or derivative thereof is preferably 0.1 to 10% by mass, more preferably 0.8 to 8% by mass. Acid content amount and IR spectrum of the resin, determined from the peak area of 1670cm -1 ⁇ 1810cm -1.
- the intrinsic viscosity [ ⁇ ] of the acid-modified polyolefin resin measured in tetralin at 135 ° C. is preferably 0.1 to 3.0 dL / g. If it is less than 0.1 dL / g, the physical properties such as strength characteristics of the molded product may be deteriorated. If it exceeds 3.0 dL / g, the fluidity of the composition may be lowered, and molding may be difficult.
- a modified carbon fiber (C) in which the adhesion amount of the amino group-containing modified polyolefin resin is 0.2 to 5.0% by mass is used.
- the method for attaching the amino group-containing modified polyolefin resin will be described in detail later, but a method of attaching an aqueous dispersion of a sizing agent containing an amino group-containing modified polyolefin resin as a sizing agent and attaching the aqueous dispersion of the sizing agent to a carbon fiber bundle. (Hereinafter, this method is referred to as “sizing treatment”).
- the adhesion amount of the amino group-containing modified polyolefin resin is 0.2 to 5.0% by mass, preferably 0.4 to 4.0% by mass, and more preferably 0.5 to 4.0% by mass.
- the molecular layer covering the surface of the single fiber of the carbon fiber is preferably about 1 to 3 layers. If the adhesion amount is less than 0.2% by mass, the effect of attaching the amino group-containing modified polyolefin resin may be insufficient, and the process passability, handleability, and affinity with the sizing agent may decrease. is there.
- the adhesion amount exceeds 5% by mass
- the amino group-containing modified polyolefin resin is interposed between the single fibers, bridging occurs, and the movement between the single fibers is restricted by the pseudo-bonding between the single fibers, and the carbon fibers
- the spreadability of the bundle tends to decrease.
- the uniformity of the carbon fiber bundle may be impaired.
- the permeability of the sizing agent is hindered, making it difficult to obtain a uniform modified carbon fiber bundle, and there is a concern that the characteristics as the carbon fiber bundle may be deteriorated.
- the adhesion amount of the amino group-containing modified polyolefin resin can be adjusted, for example, by adjusting the solid content concentration of the sizing agent aqueous dispersion containing the amino group-containing modified polyolefin resin. Specifically, when the solid content concentration of the sizing agent aqueous dispersion is increased, the adhesion amount tends to increase.
- the adhesion amount of the amino group-containing modified polyolefin resin was measured according to the SACMA method SRM14-90, and the total amount of the sizing agent adhering to the carbon fiber bundle was measured from the mass difference before and after the pyrolysis treatment by the pyrolysis method. Calculated as the adhesion rate to the carbon fiber bundle before the pyrolysis treatment. Specifically, it can be obtained by the following formula (1). However, when an amino group-containing modified polyolefin resin and other components are used in combination as a sizing agent, the adhesion amount of the amino group-containing modified polyolefin resin is based on the solid component in the sizing agent aqueous dispersion as a whole.
- Adhesion amount (%) 100 ⁇ (W1-W2) / W1 (1)
- the amino group-containing modified polyolefin resin (hereinafter sometimes abbreviated as “compound (a)”) is a modified carbon fiber bundle, a polyolefin resin and an acid-modified polyolefin resin (hereinafter collectively referred to as “polyolefin resin”). And the like, the amino group in the molecule enhances the interaction with the surface of the carbon fiber bundle. On the other hand, it is a component that acts as a useful coupling agent that causes strong interaction between the compound (a) and the acid-modified polyolefin resin and the polyolefin chain of these skeletons causes a strong bond with the polyolefin resin due to molecular entanglement.
- the main chain is formed of a carbon-carbon bond, and has an amino group at least at a part of the side chain or the terminal of the main chain.
- Such a compound (a) include (i) a reaction product of an acid-modified polyolefin resin (hereinafter sometimes abbreviated as “compound (b)”) and a compound having an amino group, (Ii) A reaction product of an epoxidized polyolefin resin (hereinafter sometimes abbreviated as “compound (c)”) and a compound having an amino group.
- compound (b) a reaction product of an acid-modified polyolefin resin
- compound (c) A reaction product of an epoxidized polyolefin resin
- a reaction product of the compound (b) or the compound (c) and a compound having two or more amino groups has a primary amino group, it is suitable as the compound (a). If it has a primary amino group, the interaction on the surface of the polyolefin resin or carbon fiber will be good, and a stronger bond will be produced.
- the compound (b) is not particularly limited as long as it is acid-modified so as to have a functional group that reacts with an amino group.
- the polyolefin skeleton may be a single olefin such as ethylene, propylene, or butene, or may be a plurality of different olefins. Examples of olefins include olefins having 2 to 8 carbon atoms. Examples of such a compound (b) include those shown below.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 1 to 4 an alkoxy group, an alkoxycarbonyl group having 1 to 18 carbon atoms, or an alkylcarboxyl group having 1 to 17 carbon atoms.
- R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R 1 to R 4 may be the same or different for each repeating unit.
- the acid-modified polyolefin resin having a skeleton represented by the formula (I) and a skeleton represented by the formula (III) can be obtained, for example, by copolymerizing an olefin and maleic anhydride. Further, olefin and maleic acid may be copolymerized while dehydrating. In this case, it can be copolymerized with other unsaturated carboxylic acids.
- unsaturated carboxylic acids examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid and itaconic acid, acrylic acid esters such as methyl acrylate, ethyl acrylate and propyl acrylate, and methacrylic acid such as methyl methacrylate, ethyl methacrylate and propyl methacrylate.
- unsaturated carboxylic acid esters such as acid esters and unsaturated carboxylic acids such as vinyl acetate can be used.
- acid-modified polyolefin resin having a skeleton represented by formula (I) and a skeleton represented by formula (III) include ethylene-maleic anhydride copolymers, propylene-maleic anhydride copolymers, ethylene -Propylene-maleic anhydride copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-vinyl acetate-maleic anhydride copolymer, and the like.
- Examples of the acid-modified polyolefin resin having a skeleton represented by formula (I) in the main chain and a group represented by formula (IV) in the side chain include, for example, maleic acid, maleic anhydride, and polyolefin resin. And an acid-modified polyolefin resin obtained by reacting with a radical initiator by melt kneading or the like.
- examples of the polyolefin resin include polyolefin resins obtained by polymerizing olefins such as ethylene, propylene, and butene alone or in the presence of a polymerization catalyst such as a so-called Ziegler-Natta catalyst.
- it is a polypropylene homopolymer.
- radical initiator For example, a butyl peroxide, a dicumyl peroxide, a benzoyl peroxide etc. are mentioned.
- the amount of the radical initiator used may be about 0.01 to 1 part by mass with respect to 100 parts by mass of the polyolefin resin.
- the melt kneading temperature is generally about 160 to 270 ° C.
- Examples of the acid-modified polyolefin resin having a skeleton represented by the formula (I) in the main chain and a group represented by the formula (V) in the side chain include copolymerization of an olefin and an unsaturated carboxylic acid, It can be obtained by copolymerizing an olefin and an unsaturated carboxylic acid ester and then hydrolyzing it.
- Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, and fumaric acid.
- examples of unsaturated carboxylic acid esters include acrylic acid esters such as methyl acrylate, ethyl acrylate, and propyl acrylate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and propyl methacrylate, and vinyl acetate.
- acrylic acid esters such as methyl acrylate, ethyl acrylate, and propyl acrylate
- methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and propyl methacrylate
- vinyl acetate vinyl acetate
- the olefin illustrated previously is mentioned as an olefin which can be used here.
- Polymerization conditions and hydrolysis conditions are not particularly limited and may be carried out by known methods.
- the structural unit represented by the formula (I) is 70 to 99.98 mol%, and the formulas (III) and (V It is preferable to contain 0.02 to 30 mol% of structural units derived from the compound for introducing the group (ii).
- the compound (b-2) preferably contains 0.5 to 20% by mass of the group of the above formula (IV).
- the content of the structural unit or group is less than the above lower limit value, the adhesion to the carbon fiber becomes insufficient, and if it exceeds the above upper limit value, the affinity with the polyolefin is insufficient. It becomes.
- other than the repeating units other than the above formulas (I) and (III) and the side chains represented by the above formulas (IV) and (V) as long as the effects of the present invention are not impaired. It may contain side chains.
- the compound (b) is, for example, one compound selected from the group consisting of ethylene-ethyl acrylate-maleic anhydride copolymer, maleic anhydride grafted polyethylene resin, and maleic anhydride grafted polypropylene resin. is there.
- a commercially available compound can be used as the compound (b).
- Yumex series (trade name, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene) manufactured by Sanyo Chemical Industries, Ltd.
- Bondine series (trade name, ethylene-ethyl acrylate-maleic anhydride copolymer) manufactured by Atofina
- Lexpearl ET series (trade name, ethylene-ethyl acrylate-maleic anhydride copolymer) manufactured by Nippon Polyolefin Co., Ltd.
- Hostamont AR503, AR504 (trade name, maleic anhydride grafted polypropylene) manufactured by Clariant.
- the compound (c) those obtained by copolymerizing an olefin with an epoxy group-containing monomer such as glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate are preferable.
- the polyolefin skeleton may be an olefin such as ethylene, propylene, or butene, or a copolymer thereof. Further, the copolymerization may be random copolymerization or block copolymerization.
- the mass molecular weights of the compound (b) and the compound (c) may be appropriately selected according to the purpose, but are usually 3000 to 600,000.
- a compound having two or more amino groups is preferable, and specific examples thereof include diamines represented by the following formula (VI). It is done. H 2 N—R 6 —NH 2 (VI)
- R 6 represents an alkylene group having 1 to 12 carbon atoms (preferably an alkylene group having 1 to 8 carbon atoms), a cycloalkylene group having 5 to 17 carbon atoms (preferably a cycloalkylene having 6 to 10 carbon atoms). Group), an arylene group having 6 to 12 carbon atoms, an arylalkylene group having 7 to 12 carbon atoms (preferably an arylalkylene group having 8 to 10 carbon atoms), and a polyoxyalkylene group having 4 to 30 carbon atoms (preferably carbon 4 to 15 polyoxyalkylene groups).
- Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, and a hexamethylene group.
- Examples of the cycloalkylene group include a cyclohexylene group and a methylenecyclohexylmethylene group.
- Examples of the arylene group include phenylene and oxydiphenylene.
- Examples of the arylalkylene group include xylylene.
- Examples of the polyoxyalkylene group include a polyoxymethylene group, a polyoxyethylene group, and a polyoxypropylene group.
- diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, 1,7-diaminoheptane, and 1,8-diaminooctane.
- Linear or branched aliphatic alkylene such as 1,9-diaminononane, 1,10-diaminodecane, piperazinylaminoethane, 2,2,5-trimethylhexanediamine, 2,2,4-trimethylhexanediamine, etc.
- Diamines Diamines; isophorone diamine, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bisaminomethylhexahydro-4,7-methaneindane, 1,4-cyclohexanediamine, 1,3- Cyclohexanediamine, 2-methylcyclohexanediamine, Alicyclic diamines such as methylcyclohexanediamine and bis (4-amino-3,5-dimethylcyclohexyl) methane; arylalkyl diamines such as m-xylylenediamine and p-xylylenediamine; p-phenylenediamine, 4 And aryl diamines such as 4,4'-diaminodiphenyl ether; polyoxyalkylene diamines such as polyoxypropylene diamine and polyoxyethylene diamine.
- aliphatic and cycloaliphatic diamines particularly preferred are aliphatic and cycloaliphatic diamines.
- the salt of the above diamine is used, and either a partially neutralized salt (mono salt) or a completely neutralized salt (di salt) of diamine may be used. High efficiency is preferable.
- the diamine is preferably used as a partially neutralized salt of an acid.
- an acid it is desirable to select an acid having an acid strength higher than that of a carboxylic acid.
- sulfonic acids such as sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid; halogeno acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid; nitric acid, boric acid, phosphorus
- hydrochloric acid and toluenesulfonic acid are preferred.
- the molar ratio of the diamine to the acid should be in the form of a salt corresponding to a neutralization degree of 50 to 100% in terms of an acid equivalent based on the total amino groups of the diamine. Is preferred. If it is less than 50%, crosslinking or gelation tends to occur during the reaction. On the other hand, if it exceeds 100%, the reaction takes a long time, which is economically disadvantageous. A more preferred range is 50 to 80%.
- a diamine salt can be easily prepared by a neutralization reaction between a corresponding diamine and a corresponding acid.
- a diamine may be dropped into an acid alcohol solution, concentrated as necessary, and recrystallized with alcohol to be isolated and used as a raw material.
- a partially neutralized salt of diamine and acid may be formed in an aprotic polar solvent such as tetramethylurea and used directly in the reaction. In terms of operation, the latter is simple and preferable.
- the compound (a) can be obtained, for example, by reacting the compound (b) or the compound (c) with the diamine by a conventional method.
- the reaction between the compound (b-1) or the compound (b-2) and the diamine is an imidation reaction
- the reaction between the compound (b-3) and the diamine is an acid amidation reaction.
- limiting in particular as the method of reaction For example, after making the said compound (b) and the said diamine salt react (imidation reaction or acid amidation reaction), it contacts with a base and deacidifies.
- the compound (a) can be produced efficiently.
- the imidation reaction or acid amidation reaction can be performed in a solvent-free molten state using a screw extruder or the like, but it is desirable to use an inert solvent for the purpose of uniforming the reaction.
- the solvent that can be used for such purpose include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, ethyltoluene, propylbenzene, and diethylbenzene; methylcyclopentane, cyclohexane, ethylcyclopentane, methylcyclohexane, Alicyclic hydrocarbons such as 1,1-dimethylcyclohexane and ethylcyclohexane; Aliphatic hydrocarbons such as hexane, heptane, octane, decane, methylheptane, 3-ethylhexane and trimethylpentane; DMI, t
- reaction substrates having considerably different polarities are reacted with each other, and therefore it is generally preferable to use a nonpolar solvent and a polar solvent at the same time.
- the amount of the solvent to be used is not particularly limited and may be appropriately selected depending on the situation.
- the compounds (b-1) to (b-3) used as raw materials that is, substituted or non-reacting which reacts with an amino group
- the compound may have a mass ratio of 0.3 to 20 times, preferably 1 to 10 times that of the compound having a substituted succinic anhydride group or carboxyl group as a functional group.
- the imidation reaction or acid amidation reaction does not particularly require a catalyst, but when used, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline, 1,8-diazabicyclo (5 4.0) tertiary amines such as undecene-7 are preferred.
- the ratio of the raw material compound (b) and the diamine salt varies depending on the type and situation of the raw material used and cannot be uniquely determined.
- the amount is 1.0 to 10 times, preferably 1.05 to 5.0 times, based on the unneutralized amino acid of the diamine, with respect to 1 mol of a substituted or unsubstituted succinic anhydride group or carboxyl group contained in the raw material. If it is less than 1.0 times, a succinic anhydride group or a carboxyl group that remains without being imidized or acid amidated even after the completion of the reaction tends to be present. As a result, the primary amino group regenerated in the deoxidation step, which is a subsequent step, reacts with the succinic anhydride group or carboxyl group to cause gelation by amide crosslinking, which may reverse the effect of the present invention. On the other hand, when the molar ratio exceeds 10 times, there is an advantage that the reaction of imidization or acid amidation proceeds rapidly, but it requires a large amount of reaction reagent, which is economically disadvantageous.
- the reaction temperature and reaction time vary depending on the solvent used and the presence or absence of a catalyst, but are usually 100 to 300 ° C., preferably 130 to 260 ° C., and 1 to 20 hours.
- the reaction temperature is less than 100 ° C., the reaction may take a long time.
- the reaction temperature exceeds 300 ° C., the reaction product is colored and the physical properties are deteriorated due to thermal decomposition of the raw material compound.
- the order of charging the reaction raw materials is not particularly limited and can be carried out in various modes.
- the compound (b) as a raw material is uniformly dissolved in the solvent, and then the salt of the diamine and acid.
- the powder or solution is added gradually or vice versa.
- the charging during this time may be performed under heating and reflux of the solvent. Since the reaction proceeds with generation of water, the generated water azeotropes with the solvent used. Therefore, the reaction can proceed efficiently by removing the azeotropic water from the reaction system using a Dean-Stark water separator or the like.
- azeotropic water is no longer observed, and an increase in the absorption intensity of carbonyl of imide near 1700 cm ⁇ 1 is no longer observed by collecting a part of the reaction mixture and measuring the infrared absorption spectrum. This can be confirmed.
- the completion of the acid amidation reaction is that azeotropic water is no longer recognized, and that the absorption intensity of carbonyl of acid amide near 1650 cm ⁇ 1 is increased by collecting a part of the reaction mixture and measuring the infrared absorption spectrum. It can be confirmed that it is no longer recognized.
- the reaction mixture thus obtained contains a salt of the compound (a) in which the primary amino group is bonded through an imide bond or an acid amide bond.
- This reaction mixture is pulverized as it is or, if necessary, in a non-solvent such as methanol, isopropanol, isobutanol, hexane or the like, and then contacted with an aqueous base solution or, if necessary, a basic methanol / water mixed solution. Can be deacidified and converted to the free amine.
- bases used for deoxidation include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, methylamine, ethylamine, trimethylamine, triethylamine, etc. Any water-soluble base may be used. Of these, sodium hydroxide, sodium carbonate, and sodium bicarbonate are preferred for economic reasons.
- the repeating unit represented by the following formula (I) obtained by reacting the above (b-1) with the diamine represented by the above formula (VI) is converted into 70 to 99.
- a compound containing .98 mol% and 0.02 to 30 mol% of a repeating unit represented by the following formula (II) is preferable. More preferably, the repeating unit represented by the following formula (I) contains 75 to 99.70 mol% and the repeating unit represented by the following formula (II) contains 0.30 to 25 mol%. More preferably, the repeating unit represented by the formula (I) contains 80 to 99.50 mol% and the repeating unit represented by the following formula (II) contains 0.50 to 20 mol%.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl having 6 to 10 carbon atoms.
- Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
- Examples of the cycloalkyl group include a cyclohexyl group, a cyclooctyl group, and a cyclodecyl group.
- Examples of the aryl group include a phenyl group, a p-methylphenyl group, and an m-methylphenyl group.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
- alkoxycarbonyl group examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group.
- alkyl carboxyl group examples include a methyl carboxyl group, an ethyl carboxyl group, a propyl carboxyl group, and a butyl carboxyl group.
- R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
- R 5 is an alkylene group having 1 to 12 carbon atoms (preferably an alkylene group having 1 to 8 carbon atoms), a cycloalkylene group having 5 to 17 carbon atoms (preferably a cycloalkylene group having 6 to 10 carbon atoms), or 6 carbon atoms.
- Oxyalkylene group is an alkylene group having 1 to 12 carbon atoms (preferably an alkylene group having 1 to 8 carbon atoms), a cycloalkylene group having 5 to 17 carbon atoms (preferably a cycloalkylene group having 6 to 10 carbon atoms), or 6 carbon atoms.
- Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, and a hexamethylene group.
- Examples of the cycloalkylene group include a cyclohexylene group and a methylenecyclohexylmethylene group.
- Examples of the arylene group include phenylene and oxydiphenylene.
- Examples of the arylalkylene group include xylylene.
- Examples of the polyoxyalkylene group include a polyoxymethylene group, a polyoxyethylene group, and a polyoxypropylene group.
- R 1 to R 5 may be the same or different for each repeating unit.
- the content of the repeating unit represented by the above formula (II) is less than 0.02 mol%, the adhesion to the carbon fiber becomes insufficient, and when it exceeds 30 mol%, the affinity with the polyolefin resin is insufficient. It will be enough.
- maleic anhydride is preferable.
- the above formula (I) or a repeating unit other than the repeating unit represented by the formula (II) may be included.
- the molecular weight of the compound (a) is not particularly limited, but the intrinsic viscosity (measured in tetralin at 135 ° C.), which is a measure of the molecular weight, is preferably 0.05 to 1.0 dL / g.
- the intrinsic viscosity exceeds 1.0 dL / g, the number of polymer molecules per unit mass decreases, and the interfacial adhesion cannot be sufficiently increased.
- the intrinsic viscosity is less than 0.05 dL / g, the coupling effect in the interfacial phase between the carbon fiber and the resin is reduced, and sufficient adhesiveness cannot be obtained.
- the compound (a) preferably has an amino group content (mol%) of 0.02 to 30 mol%, more preferably 0.05 to 5.0 mol%.
- amino group content 0.02 to 30 mol%, more preferably 0.05 to 5.0 mol%.
- the amino group content is less than 0.02 mol%, the interaction between the carbon fiber bundle and the single fiber surface is insufficient, and high interfacial adhesion is difficult to obtain.
- the amino group content exceeds 30 mol%, the affinity with the polyolefin resin becomes insufficient, and as a result, the entanglement with the molecule becomes insufficient and it becomes difficult to enhance the interfacial adhesion.
- poly-N-vinylacetamide or the like can also be used as the compound (a).
- poly-N-vinylacetamide may be a copolymer with ethylene, propylene, butene or the like, and the copolymer may be either a random copolymer or a block copolymer.
- the carbon fiber used in the present invention is not particularly limited, and may be a single fiber or a bundle of carbon fibers, but the highest and lowest portions in the region of circumferential length 2 ⁇ m ⁇ fiber axial direction length 1 ⁇ m.
- a carbon fiber bundle in which a plurality of single fibers each having a plurality of wrinkles having a height difference of 40 nm or more on the surface is collected is preferable.
- the difference in height between the highest part and the lowest part in a region having a circumferential length of 2 ⁇ m and a fiber axis direction length of 1 ⁇ m is preferably 10% or less of the diameter of the single fiber.
- the depth of the wrinkles present on the surface of the single fiber of the carbon fiber bundle is defined by the difference in height between the highest part and the lowest part in the region of circumferential length 2 ⁇ m ⁇ fiber axis direction length 1 ⁇ m.
- the wrinkle on the surface of a single fiber refers to the form of irregularities having a length of 1 ⁇ m or more in a certain direction.
- the direction is not particularly limited, and the direction may be parallel to, perpendicular to, or at a certain angle to the fiber axis direction. Due to a general method for producing carbon fiber bundles, wrinkles that are substantially parallel to the fiber axis direction exist on the surface of ordinary carbon fibers.
- the height difference can be estimated based on the surface shape obtained by scanning the surface of a single fiber using a scanning atomic force microscope (AFM).
- AFM scanning atomic force microscope
- the ratio of the major axis to the minor axis (major axis / minor axis) of the cross section is preferably 1.03 to 2.00, particularly preferably 1.05 to 1.70. If the major axis / minor axis is smaller than 1.03, the sizing agent will strongly bond the single fibers to each other after sizing treatment. The product may not be obtained. On the other hand, when the major axis / minor axis is larger than 2.00, the carbon fiber bundle is weak and easily broken, and the stability of the predetermined length cutting process and the shape stability of the carbon fiber bundle after cutting are improved. It may get worse.
- Examples of such a carbon fiber bundle having a plurality of single fibers include TR50S, TR30S, TRH50, TR40, MR60H (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and the like.
- a single fiber which comprises a carbon fiber bundle it is obtained by fiberizing and carbonizing the acrylonitrile polymer, the pitch obtained from petroleum, coal, etc.
- the carbon fiber bundle before sizing treatment with a sizing agent as described later is a carbon fiber bundle after carbonization treatment, one obtained by introducing an oxygen-containing functional group on the surface by electrolytic oxidation treatment, and pre-sizing treatment as will be described in detail later. It can also be used.
- the carbon fiber bundle may be in a continuous fiber state or may be cut into a predetermined length.
- the basis weight is preferably 0.2 to 15 g / m, more preferably 0.4 to 10 g / m, and particularly preferably 0.8 to 8 g / m. is there.
- the basis weight of the carbon fiber bundle is less than 0.2 g / m, it is economically disadvantageous.
- the basis weight exceeds 15 g / m, it is difficult to completely penetrate the carbon fiber bundle of the sizing agent aqueous dispersion, and it may be difficult to produce a carbon fiber bundle having a stable shape.
- the resin impregnation in the modified carbon fiber bundle in the resin impregnation tank is not uniform, An unimpregnated part may occur.
- the basis weight is preferably 0.4 to 15 g / m, more preferably 0.6 to 10 g / m, and particularly preferably 0. .8 to 8 g / m. If the basis weight of the carbon fiber bundle is less than 0.4 g / m, it is economically disadvantageous, and the modified carbon fiber bundle introduction processability in the pellet manufacturing process may be further deteriorated. On the other hand, when the basis weight exceeds 15 g / m, it is difficult to completely penetrate the carbon fiber bundle of the sizing agent aqueous dispersion, and it may be difficult to produce a carbon fiber bundle having a stable shape.
- the cutting length (the length of the carbon fiber bundle) is preferably 2 to 30 mm, more preferably 4 to 24 mm, and particularly preferably 6 to 20 mm.
- the cutting length can be adjusted by adjusting the tooth tip interval of the apparatus to be used.
- the carbon fiber bundle in the case of a carbon fiber bundle with a thick basis weight exceeding 1.5 g / m, the carbon fiber bundle can be opened as much as possible, and the sizing agent aqueous dispersion can be uniformly adhered to the inside of the carbon fiber bundle.
- the carbon fiber bundle cut to a predetermined length is liable to be longitudinally cracked along the fiber orientation direction when the width is wide, and it tends to be difficult to maintain the form during use after production or after production. . This is particularly noticeable in thick carbon fiber bundles. Therefore, it is preferable to control the width of the carbon fiber bundle by adjusting the width of the guide attached to the rotary cutter so that the ratio (width / thickness) of the width and thickness of the carbon fiber bundle is 3 to 10. If the width / thickness is 3 or more, the occurrence of miscuts in the cutting process with a rotary cutter can be suppressed.
- the carbon fiber bundle is preferably cut into the wet carbon fiber bundle after the sizing agent aqueous dispersion is adhered to the carbon fiber bundle.
- This utilizes the convergence effect due to the surface tension of the sizing agent aqueous dispersion and the prevention of fiber cracking by absorbing the impact shearing force at the time of cutting in a wet and flexible state.
- the moisture content of the carbon fiber bundle is 20 to 60% by mass, particularly 25 to 50% by mass. If the water content is less than 20% by mass, there is a risk that fiber breakage and fluff are likely to occur during cutting.
- the surface of the single fiber is excessively attached to the surface of the single fiber, so that the single fiber converges in a round shape due to the surface tension of the water, resulting in miscutting and clogging of the blade. There is a risk of increasing the frequency.
- the water content is measured by drying a carbon fiber bundle cut to a predetermined length at 110 ° C. for 1 hour, and measuring the mass change before and after the drying as the water content.
- Examples of the method for drying the carbon fiber bundle after cutting include a hot air drying method.
- the hot air drying method it is preferable to perform drying while transporting in a vibrated state in order to improve moisture evaporation efficiency and prevent adhesion between the carbon fiber bundles. If the vibration during drying is too strong, fiber cracking is likely to occur, and the ratio of the width and thickness of the carbon fiber bundle (width / thickness) is less than 3. On the other hand, if the vibration is too weak, pseudo-bonding between the fibers occurs, resulting in a dumpling shape. Therefore, it is necessary to set an appropriate vibration condition.
- auxiliary means such as infrared radiation can be used in combination.
- the modified carbon fiber used in the present invention can be obtained by adhering 0.2 to 5.0% by mass of the compound (a) on the surface of the above-described carbon fiber monofilament or carbon fiber bundle.
- the compound (a) is preferably attached to the carbon fiber bundle and then subjected to a heat treatment at 200 to 300 ° C. for 5 seconds to 3 minutes.
- the compound (a) adhering to the surface of the carbon fiber bundle is subjected to mild thermal decomposition and is more firmly bonded to the surface of the carbon fiber bundle.
- the coupling action of the carbon fiber bundle by the compound (a) and the olefinic resin is improved, and a modified carbon fiber bundle excellent in interfacial adhesion with the olefinic resin can be obtained.
- the heat treatment time is preferably 5 seconds to 3 minutes.
- the heat treatment time is less than 5 seconds, the above-described thermal decomposition may be insufficient, and the effect of improving the coupling action may not be sufficiently obtained.
- the heat treatment time exceeds 3 minutes, the degree of thermal decomposition becomes excessive, the molecular weight is lowered, and the decomposition and scattering of deposits become remarkable, which may cause a reduction in coupling action.
- More preferable heat treatment conditions are 200 to 300 ° C. for 5 seconds to 3 minutes, more preferably 200 to 260 ° C. for 15 seconds to 3 minutes, and particularly preferably 220 to 240 ° C. for 20 seconds to 40 seconds. It is.
- a hot air dryer When performing the heat treatment, a hot air dryer, a panel heater dryer, a muffle furnace, a roll dryer or the like can be used.
- the carbon fiber bundle can be continuously passed through the dryer, or the carbon fiber bundle is wrapped around a tubular one, and these are batch processed with a hot air dryer or a panel dryer. You can also.
- a preferred heat treatment method is a continuous treatment capable of uniform heat treatment.
- the atmosphere for the heat treatment is not particularly limited, and the heat treatment can be performed in air, nitrogen, or an inert gas.
- a sizing agent aqueous dispersion is prepared by dissolving or dispersing the compound (a) alone or with the other sizing agent as a sizing agent. And the method (sizing process) which adheres this sizing agent aqueous dispersion to a carbon fiber bundle is preferable.
- the adhesion amount of the compound (a) can be adjusted by adjusting the solid content concentration of the sizing agent aqueous dispersion as described above.
- drying treatment is performed, and further heat treatment is performed.
- the drying treatment the water in the sizing agent aqueous dispersion adhering to the carbon fiber bundle can be evaporated before the heat treatment, and the thermal decomposition product of the compound (a) can be suppressed from scattering together with the water. Therefore, by applying a drying treatment before the heat treatment, the compound (a) can be adhered to the surface of the carbon fiber bundle more firmly and stably.
- the drying process may be any method as long as the water in the sizing agent aqueous dispersion adhering to the carbon fiber bundle can be evaporated before the heat treatment, but the drying process can also be performed at 100 to 200 ° C.
- the concentration of the sizing agent aqueous dispersion is not particularly limited, but is preferably diluted with water so that the concentration of the sizing agent is 5 to 60% by mass.
- the sizing agent aqueous dispersion may contain an olefinic thermoplastic elastomer resin as an auxiliary component.
- the olefin-based thermoplastic elastomer resin imparts sufficient convergence and drape to the carbon fiber bundle. Moreover, sufficient affinity with polyolefin resin can be ensured.
- the olefin thermoplastic elastomer resin include hydrogenated styrene thermoplastic elastomer, ethylene propylene diene monomer copolymer, and the like.
- the olefinic thermoplastic elastomer preferably has a Vicat softening point of 120 ° C. or less, more preferably 110 ° C. or less, and particularly preferably 90 ° C. or less, measured according to ASTM D1525-70. This is because the sizing agent aqueous dispersion is attached to the surface of the single fiber of the carbon fiber bundle and then the water is evaporated (drying process) at 100 to 200 ° C., while the olefinic thermoplastic elastomer resin is used. This is because the convergence of the carbon fiber bundle after drying becomes better when the is sufficiently softened.
- the minimum content is determined independently in order to effectively express the role. These are preferably in a mass ratio (compound (a) / olefin-based thermoplastic elastomer) of 15/1 to 1/1.
- an aqueous emulsion in which a sizing agent is dispersed in water from the viewpoint of safety and economy in consideration of industrial production.
- a surfactant is used as an emulsifier for the purpose of uniformly dispersing the constituent components in water.
- the emulsifier is not particularly limited, and anionic, cationic, nonionic emulsifiers and the like can be used. Among these, anionic or nonionic emulsifiers are preferable from the viewpoint of emulsification performance and low cost.
- a nonionic emulsifier is particularly preferred from the viewpoint of the stability of the silane coupling agent in water and the physical properties of the molded product.
- Nonionic emulsifiers include polyethylene glycol type (higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, etc.), polyhydric alcohol type (glycerin fatty acid ester, sorbitol fatty acid) Emulsifiers such as esters and fatty acid alkanolamides).
- the HLB of the nonionic emulsifier is usually 8-20. If a nonionic emulsifier having an HLB outside this range is used, a stable aqueous emulsion may not be obtained.
- anionic emulsifiers carboxylate type (potassium oleate, sodium oleate, etc.), sulfonate type (sodium dodecylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, etc.), sulfate ester type ( Sodium lauryl sulfate, ammonium lauryl sulfate, etc.).
- Examples of the emulsification method include a method using a batch equipped with a stirring blade, a method using a ball mill, a method using a shaker, and a method using a high shear emulsifier such as a Gaurin homogenizer.
- the emulsifier is not particularly limited as long as it can emulsify the sizing agent, but it is usually added in an amount of about 5 to 30% by mass.
- silane coupling agents for example, vinyl acetate resin emulsions, urethane resin emulsions, acrylic resin emulsions, epoxy resin emulsions, etc.
- silane coupling agents for example, vinyl acetate resin emulsions, urethane resin emulsions, acrylic resin emulsions, epoxy resin emulsions, etc.
- silane coupling agent a silane coupling agent having any one of an epoxy group, a vinyl group, an amino group, a methacryl group, an acrylic group, and a linear alkyl group in the molecule can be used.
- a silane coupling agent may be used individually by 1 type, and 2 or more types can also be mixed and used for it.
- silane coupling agents epoxy silanes, amino silanes, and linear alkyl silanes having an epoxy group, an amino group, and a linear alkyl group in the molecule are particularly preferable.
- epoxy group of the epoxysilane-based silane coupling agent a glycidyl group, an alicyclic epoxy group, or the like is suitable.
- a silane coupling agent A-186, A-187, AZ- manufactured by Nihon Unicar Company, Ltd. are used. Specific examples include 6137, AZ-6165 (trade name) and the like.
- aminosilane-based silane coupling agents include those having a primary amine, a secondary amine, or both. A-1100, A-1110, A-1120, Y-9669, A manufactured by Nihon Unicar Co., Ltd. Specific examples include 1160 (above, product name).
- Examples of the straight chain aralkyl group of the straight chain alkylsilane-based silane coupling agent include those having a hexyl group, an octyl group, and a decyl group.
- a silane coupling agent AZ-6171 manufactured by Nippon Unicar Co., Ltd. AZ-6177 (trade name), KBE-3103C (trade name) manufactured by Shin-Etsu Silicone Co., Ltd., and the like.
- the addition amount of the silane coupling agent is preferably 5% by mass or less, more preferably 4% by mass or less, with respect to 100% by mass of the total amount of components other than water (total solid content) of the aqueous emulsion in which the sizing agent is dispersed. is there.
- the addition amount exceeds 5% by mass, the crosslinking of the silane coupling agent proceeds, the carbon fiber bundle becomes hard and brittle, and vertical cracks are likely to occur. In addition, it may cause a decrease in interfacial adhesion.
- An example of a method for sizing using an aqueous sizing agent dispersion is a method of bringing a carbon fiber bundle into contact with the aqueous sizing agent dispersion. Specifically, after a part of the roll is dipped in the sizing agent aqueous dispersion and the surface is transferred, a touch roll method in which a carbon fiber bundle made of a single fiber is brought into contact with this roll to attach the sizing agent aqueous dispersion, Examples include a dipping method in which a carbon fiber bundle composed of single fibers is directly immersed in a sizing agent aqueous dispersion and then passed through a nip roll as necessary to control the amount of the sizing agent aqueous dispersion attached.
- a method in which a carbon fiber bundle is brought into contact with a plurality of touch rolls and a sizing agent aqueous dispersion is attached in a plurality of stages is particularly suitable from the viewpoint of controlling the amount of sizing agent attached and controlling the bundle width. .
- After the sizing treatment it is preferable to sequentially perform the drying treatment and the heat treatment as described above.
- the carbon fiber bundle Prior to the sizing treatment, the carbon fiber bundle may be presized with a presizing agent.
- the presizing process in this invention is a process which makes a presizing agent adhere to a carbon fiber bundle.
- a presizing agent made of an epoxy resin can be used as the presizing agent.
- a presizing agent is suitable because it is excellent in affinity with carbon fiber single fibers and handleability, and can converge the single fibers in a small amount.
- the carbon fiber bundle that has been presized with such a presizing agent has excellent process passability such that the carbon fiber bundle is not wound around the roller in the subsequent sizing process.
- wettability with the sizing agent is improved by the presizing agent treatment, and the sizing agent can be uniformly attached.
- an aqueous presizing agent solution in which a water-soluble or water-dispersible epoxy resin is dissolved or dispersed in water is usually used. It does not specifically limit as a water-soluble or water-dispersible epoxy resin, A well-known thing can be used. Also, a modified epoxy resin can be used as long as it can be used in an aqueous system. These epoxy resins may be used individually by 1 type, and 2 or more types can also be mixed and used for them. Moreover, from the viewpoint of the permeability in the above-described sizing process, it is more preferable to use a combination of a liquid and a solid epoxy resin at room temperature.
- water-soluble epoxy resins include those having glycidyl groups at both ends of the ethylene glycol chain, those having ethylene oxide added to both ends of bisphenols such as A-type, F-type and S-type, and having glycidyl groups at both ends. Is mentioned. Moreover, what has an alicyclic epoxy group can also be used instead of a glycidyl group.
- water-dispersible epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, naphthalene skeleton type epoxy resins, Aliphatic epoxy resin, dicyclopentadiene type epoxy resin (for example, HP7200 (trade name) manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin, DPP novolac type epoxy resin (for example, Epicoat 157S65 manufactured by Japan Epoxy Resin Co., Ltd.) (Trade name)).
- glycidyl group for example, Epicoat 157S65 manufactured by Japan Epoxy Resin Co., Ltd.
- a presizing agent made of a water-dispersible epoxy resin it is preferable to perform a presizing treatment using an aqueous emulsion to which an emulsifier is further added.
- the emulsifier is not particularly limited, and anionic, cationic, nonionic emulsifiers, and the like can be used. Of these, anionic or nonionic emulsifiers are preferred because of their good emulsification performance and low cost. In addition, a nonionic emulsifier is particularly preferable because it does not inhibit the stability of the sizing agent.
- the adhesion amount of the presizing agent that adheres to the carbon fiber bundle by the presizing treatment is preferably 0.1 to 2.0 mass%, more preferably 0.2 to 1.2 mass% with respect to the entire carbon fiber bundle.
- the molecular layer of the presizing agent covering the single fiber surface of the carbon fiber is preferably about 1 to 3 layers.
- the adhesion amount is less than 0.1% by mass, the effect of adhering the presizing agent is not expressed, and a carbon fiber bundle excellent in process passability, handling property, and affinity with the sizing agent may not be obtained. is there.
- the adhesion amount of the presizing agent is measured in accordance with JIS R7604 by the soxhlet extraction method using methyl ethyl ketone.
- the modified carbon fiber used in the present invention is a modified carbon fiber in which 0.2 to 5.0% by mass of an amino group-containing modified polyolefin resin (compound (a)) is attached to a carbon fiber single fiber or a carbon fiber bundle.
- the modified carbon fiber may be a single fiber of modified carbon fiber or a modified carbon fiber bundle.
- the amino group in the molecule enhances the interaction with the surface of the carbon fiber, while the strong interaction between the compound (a) and the acid-modified polyolefin resin and the polyolefin chain of these skeletons are entangled in the molecule. Therefore, it is a component that acts as an effective coupling agent that causes a strong bond with the polyolefin resin.
- the modified carbon fiber of the present invention in which the compound (a) is adhered to the surface of the carbon fiber in an amount of 0.2 to 5% by mass can exhibit good interfacial adhesiveness with the polyolefin resin and is suitable for compounding.
- the modified carbon fiber obtained by adhering 0.2 to 5% by mass of the compound (a) to the surface of the carbon fiber, followed by heat treatment at 200 to 300 ° C. for 5 seconds to 3 minutes is combined with the polyolefin resin.
- a thermoplastic resin composition that is superior in tensile fracture stress, bending strength, impact strength, and bending elastic modulus can be obtained.
- the blending ratio (mass ratio) of components (A) to (C) in the composition of the present invention is (A) :( B) is 0 to 99.5: 100 to 0.5.
- the ratio is preferably 80 to 99:20 to 1.
- [(A) + (B)] :( C) is 40 to 97:60 to 3, and preferably 50 to 95:50 to 5 in terms of mass ratio. If (C) is less than 3, the effect of improving the physical properties of the molded product may be insufficient. On the other hand, if it exceeds 60, no further significant improvement effect can be obtained, the process stability at the time of producing the pellet is lowered, and the pellet has spots and the quality stability of the molded product may be deteriorated.
- additives such as an antioxidant, a colorant, an antistatic agent, a stabilizer, and a foaming agent can be added depending on the application.
- inorganic fillers such as glass fiber, talc, mica, and calcium carbonate, can be added as necessary.
- the fiber reinforced resin composition of the present invention is preferably long fiber pellets, and can be produced, for example, by the following method.
- the long fiber reinforced resin pellet is obtained by guiding a bundle of thousands of modified carbon fibers (C) to an impregnation die and uniformly impregnating the melted polyolefin resin (A) and acid-modified polyolefin resin (B) between the filaments. It is obtained by cutting to the required length.
- the molten resin is supplied from the extruder into an impregnation die provided at the tip of the extruder, while the continuous modified carbon fiber bundle is passed through, and the modified carbon fiber bundle is impregnated with the molten resin and then passed through the nozzle.
- a method of drawing and pelletizing to a predetermined length is used.
- Short fiber pellets can be produced by melting and kneading the components (A) to (C).
- the pellet length is preferably 3 to 100 mm, more preferably 5 to 50 mm.
- the resin composition of the present invention includes the carbon fiber reinforced resin composition of the present invention and a thermoplastic resin (diluted resin).
- the thermoplastic resin may be the same as or different from the polyolefin resins (A) and (B) contained in the carbon fiber reinforced resin composition.
- the dilution resin is not particularly limited, but the polyolefin resin is preferable.
- the modified carbon fiber (C) content contained in the resin composition is 3 to 60% by mass, preferably 5 to 50% by mass.
- the diluted resin is usually added in an amount of 0 to 1900 parts by mass with respect to 100 parts by mass of the carbon fiber reinforced resin composition so that the content of the modified carbon fiber (C) in the entire resin composition is included in the above range. Preferably, 10 to 500 parts by mass are added.
- the resin composition is preferably produced by mixing a pellet-like carbon fiber reinforced resin composition and a pellet-like diluted resin.
- the molded article of the present invention is produced from the above carbon fiber reinforced resin composition or resin composition.
- the molded article is made of carbon fiber reinforced resin composition or resin composition, such as injection molding method, extrusion molding method, hollow molding method, compression molding method, injection compression molding method, gas injection injection molding method, foam injection molding method, etc. It can be produced by a known molding method.
- the molded product may contain an antioxidant, a light stabilizer, a light absorber, a metal deactivator, a pigment, rubbers, a filler and the like.
- the depth of the wrinkle present on the surface of the single fiber of the carbon fiber bundle is the highest in the region of circumferential length 2 ⁇ m ⁇ length in the fiber axis direction 1 ⁇ m. It is defined by the height difference between the part and the lowest part.
- the height difference was measured based on the surface shape obtained by scanning the surface of a single fiber using a scanning atomic force microscope (AFM). Specifically, it is as follows. Several single fibers of a carbon fiber bundle were put on a sample stage, both ends were fixed, and dotite was further coated around to make a measurement sample.
- the intrinsic viscosity [ ⁇ ] of the amino group-containing modified polyolefin resin was measured using an automatic viscometer (“VNR-53 type” manufactured by Kogai Co., Ltd.).
- VNR-53 type manufactured by Kogai Co., Ltd.
- BHT 2,6-di-t-butyl-4-methylphenol
- Measurement was performed under conditions of a concentration of 0.8 to 1.6 g / L.
- the amino group content of the amino group-containing modified polyolefin resin was measured according to the method described in Macromolecules, Vol. 26, pages 2087-2088, (1993). First, 1.0 g of amino group-containing modified polyolefin, 50 mL of p-xylene, 10 mL of pyridine, and 5 mL of benzoyl chloride are added to a 200 mL two-necked eggplant flask, and heated and stirred at 140 ° C. for 6 hours in a nitrogen atmosphere to obtain a polymer solution. Obtained. Next, the obtained polymer solution was added to 1 L of methanol and sufficiently stirred, and the precipitated solid part (polymer) was collected by filtration.
- the polymer thus obtained was press-molded at 190 ° C., and the infrared absorption spectrum was measured.
- the ratio of absorbance between the absorption (1645 cm ⁇ 1 ) of the carbonyl group (C ⁇ O) produced by the reaction of the amino group and benzoyl chloride and the absorption band specific to the polyolefin was used.
- a calibration curve was prepared from an infrared absorption spectrum of a blend of polyolefin powder and various amounts of 1-butyl (2-methylpropyl) benzamide (190 ° C., press-molded product), and this calibration curve was used.
- melt flow rate Based on JIS K7210, it measured on condition of temperature 230 degreeC and load 2.16kg.
- a sizing agent aqueous dispersion was prepared as follows. First, the amino group-containing modified polyolefin resin, which is the main component of the sizing agent, is pulverized into a powder having a particle size of 20 ⁇ m or less, and this powder and a nonionic surfactant (“Pluronic F108 (trade name)” manufactured by Asahi Denka Co., Ltd.) Were mixed at a mass ratio (powder / surfactant) of 80/20 to obtain a sizing agent.
- a nonionic surfactant (“Pluronic F108 (trade name)” manufactured by Asahi Denka Co., Ltd.)
- the sizing agent was dispersed in water with a homomixer having a high shear stirring blade so that the concentration was 35% by mass. Subsequently, the mixture was passed three times through an ultra-high pressure homogenizer (manufactured by Mizuho Kogyo Co., Ltd., “Microfluidizer M-110-E / H”) to obtain a stable water emulsion (aqueous sizing agent dispersion). The concentration of the sizing agent in the obtained sizing agent aqueous dispersion was 34% by mass, and the average particle size was 0.2 ⁇ m.
- CF-1 modified carbon fiber bundle
- aqueous dispersion prepared using the compound (a-1) as an amino group-containing modified polyolefin resin with a solution diluted to a concentration of 2.0% by mass. Then, the carbon fiber bundle was immersed, and then subjected to a hot-air drying treatment at 150 ° C. for 1 minute, and then wound around a bobbin to obtain a modified carbon fiber bundle (CF-1).
- Table 2 shows the adhesion amount of the sizing agent of the obtained modified carbon fiber bundle (CF-1).
- Modified carbon fiber bundle (CF-2) In the production of the modified carbon fiber bundle (CF-1), the carbon fiber bundle (CF-1) is taken out from the bobbin-wrapped carbon fiber bundle and heat-treated at 230 ° C. for 25 seconds in a muffle furnace. Then, it was wound around a bobbin again to obtain a modified carbon fiber bundle (CF-2). The atmosphere of the heat treatment was performed in air. Table 2 shows the adhesion amount of the sizing agent of the obtained modified carbon fiber bundle (CF-2).
- the modified carbon fiber bundle (CF-3) was produced in the same manner as in the production of the modified carbon fiber bundle (CF-1) except that it was immersed in an immersion tank having a free roller filled with the sizing agent aqueous dispersion. Obtained.
- Table 2 shows the adhesion amount of the sizing agent of the obtained modified carbon fiber bundle (CF-3).
- PP-1, PP-2 and MPP-1 were mixed in the blending amounts shown in Table 3, melted at 280 ° C., and supplied from the extruder to the impregnation tank in the die.
- a modified carbon fiber bundle having a blending amount shown in Table 3 was preheated through a preheating portion having a heat temperature of 200 ° C., and then led to an impregnation tank to which the molten resin heated to 280 ° C. was supplied.
- the feed rate is adjusted to 10 m / min, the modified carbon fiber bundle is fed into the die, impregnated with molten resin in an impregnation tank, pulled out from the die, cooled, cut by a pelletizer, and 8 mm long and 2.2 mm in diameter. Carbon fiber-containing pellets were obtained.
- the molded products obtained in Examples 1 to 5 are excellent in tensile fracture stress, bending strength, bending elastic modulus, and Charpy impact strength, and in an excellent balance of these.
- the carbon fiber reinforced resin composition of the present invention and a molded product obtained using the same are automotive parts (front end, fan shroud, cooling fan, engine cover, engine under cover, radiator box, side door, back door inner, back Door outers, outer panels, door handles, luggage boxes, wheel covers, cooling modules, air cleaner cases, pedals, etc., motorcycles and bicycle parts, housing-related parts (bathroom parts, warm water flush toilet seats, chair feet, valves, Used in meter boxes, etc.)
Abstract
Description
1.(A)ポリオレフィン樹脂、(B)酸変性ポリオレフィン樹脂、(C)アミノ基含有変性ポリオレフィン樹脂の付着量が0.2~5.0質量%である変性炭素繊維からなり、(A):(B)の質量比が0~99.5:100~0.5で、かつ[(A)+(B)]:(C)の質量比が40~97:60~3である炭素繊維強化樹脂組成物。
2.(A):(B)の質量比が80~99:20~1である1記載の炭素繊維強化樹脂組成物。
3.[(A)+(B)]:(C)の質量比が50~95:50~5である1又は2記載の炭素繊維強化樹脂組成物。
4.前記変性炭素繊維(C)は、前記アミノ基含有変性ポリオレフィン樹脂を炭素繊維の表面に付着させた後、200~300℃で5秒~3分熱処理して得られるものである1~3のいずれか記載の炭素繊維強化樹脂組成物。
5.前記変性炭素繊維(C)は、前記アミノ基含有変性ポリオレフィン樹脂を炭素繊維の表面に付着させた後、220~240℃で20秒~40秒熱処理して得られるものである1~3のいずれか記載の炭素繊維強化樹脂組成物。
6.前記アミノ基含有変性ポリオレフィン樹脂が、135℃のテトラリン中で測定した極限粘度が0.05~1.0dL/gである1~5のいずれか記載の炭素繊維強化樹脂組成物。
7.前記アミノ基含有変性ポリオレフィン樹脂が、エチレン-エチルアクリレート-無水マレイン酸共重合体、無水マレイン酸グラフトポリエチレン系樹脂、及び無水マレイン酸グラフトポリプロピレン系樹脂からなる群より選ばれた1種の化合物と、2つ以上のアミノ基を有する化合物との反応物である1~6のいずれか記載の炭素繊維強化樹脂組成物。
8.前記アミノ基含有変性ポリオレフィン樹脂が、アミノ基を有し、かつ分子内に下記式(I)で表わされる反復単位を70~99.98モル%と、下記式(II)で表わされる反復単位を0.02~30モル%含有する共重合体である1~7のいずれか記載の炭素繊維強化樹脂組成物。
9.1~8のいずれか記載の炭素繊維強化樹脂組成物と、熱可塑性樹脂とを含み、前記変性炭素繊維(C)を3~60質量%含有する樹脂組成物。
10.1~8のいずれか記載の炭素繊維強化樹脂組成物又は9記載の樹脂組成物から製造される成形品。
ポリプロピレン系樹脂は市販のものを使用でき、有機過酸化物で流動性を調整したものも使用できる。
付着量(%)=100×(W1-W2)/W1・・・(1)
W1:熱分解処理前の炭素繊維の質量
W2:熱分解処理後の炭素繊維の質量
化合物(a)は、主鎖が炭素-炭素結合で形成され、側鎖又は主鎖の末端の少なくとも一部にアミノ基を有する。
特に、化合物(b)又は化合物(c)と、2つ以上のアミノ基を有する化合物との反応物が、1級アミノ基を有することから、化合物(a)として好適である。1級アミノ基を有すれば、ポリオレフィン系樹脂や炭素繊維表面での相互作用が良好となり、より強固な結合を生じさせる。
このような化合物(b)としては、例えば以下に示すものが挙げられる。
下記式(I)及び下記式(III)で表される骨格を有する酸変性ポリオレフィン樹脂
式(III)中、R3及びR4は各々独立に水素原子又は炭素数1~6のアルキル基を示す。
R1~R4は、それぞれ反復単位ごとに同一でもよいし、異なってもよい。
上記式(I)で表される骨格を主鎖に有し、下記式(IV)で表される基を側鎖に有する酸変性ポリオレフィン樹脂
ここで、ポリオレフィン樹脂としては、例えば、エチレン、プロピレン、ブテン等のオレフィンの単独あるいは複数を、いわゆるチィーグラー・ナッタ触媒等の重合触媒の存在下、重合させて得られるポリオレフィン樹脂が挙げられる。好ましくは、ポリプロピレン単独重合体である。
ラジカル開始剤としては特に制限はなく、例えばブチルペルオキシド、ジクミルペルオキシド、ベンゾイルペルオキシド等が挙げられる。ラジカル開始剤の使用量は、ポリオレフィン樹脂100質量部に対して、0.01~1質量部程度使用すればよい。
また、溶融混練温度は一般に160~270℃程度である。
上記式(I)で表される骨格を主鎖に有し、下記式(V)で表される基を側鎖に有する酸変性ポリオレフィン樹脂
不飽和カルボン酸としては、アクリル酸、メタクリル酸、フマル酸等が挙げられる。一方、不飽和カルボン酸エステルとしては、メチルアクリレート、エチルアクリレート、プロピルアクリレート等のアクリル酸エステル、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート等のメタクリル酸エステル、さらには酢酸ビニル等が挙げられる。
また、ここで使用できるオレフィンとしては、先に例示したオレフィンが挙げられる。重合条件、加水分解条件は特に制限なく、公知の方法で行えばよい。
各化合物において、構成単位や基の含有量がそれぞれ上記の下限値未満であると、炭素繊維との接着性が不十分となり、それぞれ上記の上限値を超えると、ポリオレフィンとの親和性が不十分となる。
化合物(b)においては、本発明の効果を損なわない範囲内で、上記式(I)、(III)以外の反復単位や、上記式(IV)、(V)で表される側鎖以外の側鎖を含んでもよい。
化合物(b)としては、市販のものを使用することができる。例えば三洋化成工業社製のユーメックスシリーズ(商品名、無水マレイン酸グラフトポリエチレン、無水マレイン酸グラフトポリプロピレン)、アトフィナ社製のボンダインシリーズ(商品名、エチレン-エチルアクリレート-無水マレイン酸共重合体)、日本ポリオレフィン社製のレクスパールETシリーズ(商品名、エチレン-エチルアクリレート-無水マレイン酸共重合体)、クラリアント社製のHostamont AR503、AR504(商品名、無水マレイン酸グラフトポリプロピレン)等が挙げられる。
ポリオレフィン骨格としては、エチレン、プロピレン、ブテン等のオレフィンの単独でもよく、これらの共重合でもよい。さらに共重合は、ランダム共重合でもよく、ブロック共重合でもよい。
化合物(b)及び化合物(c)の質量分子量は、目的に応じて適宜選択すればよいが、通常、3000~60万である。
H2N-R6-NH2 (VI)
アルキレン基としては、メチレン基、エチレン基、プロピレン基、テトラメチレン基、ヘキサメチレン基等が挙げられる。
シクロアルキレン基としては、シクロヘキシレン基、メチレンシクロヘキシルメチレン基等が挙げられる。
アリーレン基としては、フェニレン,オキシジフェニレン等が挙げられる。
アリールアルキレン基としては、キシリレン等が挙げられる。
ポリオキシアルキレン基としては、ポリオキシメチレン基、ポリオキシエチレン基、ポリオキシプロピレン基等が挙げられる。
ジアミン化合物の塩を製造するに当たっては、上記ジアミンと上記酸のモル比は、ジアミンの全アミノ基を基準にして酸の当量で50~100%の中和度に相当する塩の形となることが好ましい。50%未満であると反応時に架橋やゲル化が起こりやすくなる。また100%を超えると反応に長時間を要し経済的に不利となる。より好ましい範囲は50~80%である。
化合物(b-1)又は化合物(b-2)と上記ジアミンとの反応は、イミド化反応であり、化合物(b-3)と上記ジアミンとの反応は酸アミド化反応である。
反応の方法としては特に制限はないが、例えば上記化合物(b)と、上記ジアミンの塩とを反応(イミド化反応又は酸アミド化反応)させた後、塩基と接触させて脱酸することにより、化合物(a)を効率よく製造できる。
溶媒の使用量は、特に制限はなく状況に応じて適宜選定すればよいが、通常は原料として使用する化合物(b-1)~(b-3)(即ち、アミノ基と反応する置換若しくは非置換無水コハク酸基又はカルボキシル基を官能基として有する化合物)に対し、質量比で0.3~20倍、好ましくは1倍~10倍の範囲で定めればよい。0.3倍より少ない場合は、希釈効果が不十分となるため反応混合物が高粘度になり、取り扱い上、困難をきたす場合がある。一方、20倍よりも多くしても、使用量に相当する効果の向上は特に認められず、経済的に不利となる。
また、イミド化反応又は酸アミド化反応では、原料の化合物(b)と、ジアミンの塩との使用比率は、使用する原料の種類や状況により異なり、一義的に定めることはできないが、通常は原料中に含まれる置換若しくは非置換無水コハク酸基又はカルボキシル基1モルに対し、ジアミンの未中和アミノ基準で1.0~10倍、好ましく1.05~5.0倍である。1.0倍未満であると反応完結後もイミド化又は酸アミド化されずに残る無水コハク酸基又はカルボキシル基が存在しやすくなる。その結果、後工程である脱酸工程で再生される第一級アミノ基と該無水コハク酸基又はカルボキシル基が反応してアミド架橋によりゲル化を起こし、本発明の効果を覆す恐れがある。一方、モル比が10倍を超えるとイミド化や酸アミド化の反応自体は速く進行する利点はあるが、反応試薬を多量に要するため、経済的に不利となる。
反応は、水の生成を伴いながら進行するので、生成した水が用いた溶媒と共に共沸してくる。従って、この共沸する水をディーン・スターク分水器等により反応系外へ除去することにより、効率的に反応を進行させることができる。
イミド化反応の完結は、共沸水がもはや認められなくなること、及び反応混合物を一部採取して赤外吸収スペクトルの測定により1700cm-1付近のイミドのカルボニルの吸収強度の増大がもはや認められなくなったことで確認できる。また、酸アミド化反応の完結は、共沸水がもはや認められなくなること、及び反応混合物を一部採取して赤外吸収スペクトルの測定により1650cm-1付近の酸アミドのカルボニルの吸収強度の増大がもはや認められなくなったことで確認できる。
脱酸に用いられる塩基の具体例を挙げれば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、重炭酸カリウム、アンモニア、メチルアミン、エチルアミン、トリメチルアミン、トリエチルアミン等水溶性塩基であればよい。そのうち、経済的な理由から、水酸化ナトリウム、炭酸ナトリウム、重炭酸ナトリウムが好ましい。
アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等が挙げられる。
シクロアルキル基としては、シクロヘキシル基、シクロオクチル基、シクロデシル基等が挙げられる。
アリール基としては、フェニル基、p-メチルフェニル基、m-メチルフェニル基等が挙げられる。
アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられる。
アルコキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基等が挙げられる。
アルキルカルボキシル基としては、メチルカルボキシル基、エチルカルボキシル基、プロピルカルボキシル基、ブチルカルボキシル基等が挙げられる。
アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられる。
アルキレン基としては、メチレン基、エチレン基、プロピレン基、テトラメチレン基、ヘキサメチレン基等が挙げられる。
シクロアルキレン基としては、シクロヘキシレン基、メチレンシクロヘキシルメチレン基等が挙げられる。
アリーレン基としては、フェニレン、オキシジフェニレン等が挙げられる。
アリールアルキレン基としては、キシリレン等が挙げられる。
ポリオキシアルキレン基としては、ポリオキシメチレン基、ポリオキシエチレン基、ポリオキシプロピレン基等が挙げられる。
なお、R1~R5は、それぞれ反復単位ごとに同一でもよいし、異なってもよい。
上記式(II)の骨格を導入するための化合物としては、無水マレイン酸が好ましい。
上記式(I)で表される反復単位と、上記式(II)で表される反復単位とで構成される化合物(a)においては、本発明の効果を損なわない範囲内で、上記式(I)で表される反復単位や、上記式(II)で表される反復単位以外の反復単位を含んでもよい。
極限粘度が1.0dL/gを超えると、単位質量あたりのポリマーの分子数が減少し、界面接着性を十分に強くすることができなくなる。一方、極限粘度が0.05dL/g未満であると、炭素繊維と樹脂の界面相におけるカップリング効果が小さくなり、十分な接着性を得ることができなくなる。
アミノ基含有率が0.02mol%未満であると、炭素繊維束の単繊維表面との相互作用が不十分であり、高い界面接着性が得られにくくなる。アミノ基含有率が30mol%を超えると、ポリオレフィン系樹脂との親和性が不十分となり、その結果、分子との絡み合いが不十分となり、界面接着性を強くすることが困難となる。
円周長さ2μm×繊維軸方向長さ1μmの領域での最高部と最低部の高低差は、単繊維の直径の10%以下であることが好ましい。
なお、炭素繊維束を構成する単繊維としては、アクリロニトリル重合体や、石油、石炭から得られるピッチ等を繊維化し炭素化することで得られるものである。後述するようなサイジング剤でサイジング処理される前の炭素繊維束は、炭素化処理後のもの、電解酸化処理して表面に酸素含有官能基を導入したものや、詳しくは後述するがプレサイジング処理された状態のものも使用できる。
ロータリーカッター方式での切断に際しては、炭素繊維束の厚みが厚くなり過ぎると切り損じを生じたり、ロータに炭素繊維束が巻き付いて操作不能になったり、切断後の形状不良が生じたりするので、炭素繊維束の厚みは薄い方が有利である。また、炭素繊維束の目付けが1.5g/mを超える太目付けの炭素繊維束の場合、炭素繊維束をできるだけ開繊させ、炭素繊維束内部までサイジング剤水分散液を均一に付着させることが好ましい。従って、ガイドロール、コームガイド、スプレッダーバー等を用いて、炭素繊維束の幅/厚みが大きくなるように制御しながら、かつ炭素繊維束には実質的に撚りの無いように走行させることが好ましい。
本発明においては、化合物(a)を炭素繊維束に付着させた後、200~300℃で5秒~3分熱処理を施すことが好ましい。熱処理を施すことにより、炭素繊維束の表面に付着した化合物(a)が穏やかな熱分解を受け、より強固に炭素繊維束の表面に結合するようになる。その結果、化合物(a)による炭素繊維束とオレフィン系樹脂とのカップリング作用が向上し、オレフィン系樹脂との界面接着性により優れた変性炭素繊維束とすることができる。
熱処理の雰囲気は特に制限はなく、空気中、窒素中、あるいは不活性ガス中で処理することができる。
化合物(a)の付着量は、上述したように、サイジング剤水分散液の固形分濃度を調整することにより、調節できる。
また、サイジング剤水分散液には、補助成分としてオレフィン系熱可塑性エラストマー樹脂を含有させてもよい。オレフィン系熱可塑性エラストマー樹脂は、炭素繊維束に十分な収束性とドレープ性を付与するものである。またポリオレフィン系樹脂との十分な親和性を確保することができる。
オレフィン系熱可塑性エラストマー樹脂としては、水添スチレン系熱可塑性エラストマー、エチレンプロピレンジエンモノマー共重合体等が挙げられる。
化合物(a)とオレフィン系熱可塑性エラストマーは、上述のような重要な役割を担っていることから、その役割を効果的に発現させるために、それぞれ独立して最低の含有量が決定される。これらは質量比(化合物(a)/オレフィン系熱可塑性エラストマー)で15/1~1/1であることが好ましい。
乳化剤としては特に限定されるものではなく、アニオン系、カチオン系、ノニオン系乳化剤等を用いることができる。中でも、アニオン系又はノニオン系乳化剤が、乳化性能及び低価格の点から好ましい。また、後述するように、水性エマルジョンにシランカップリング剤を添加する場合、シランカップリング剤の水中での安定性、さらには成形品の物性安定性の点からノニオン系乳化剤が特に好ましい。
また、前記乳化剤は、サイジング剤を乳化できれば特に制限はないが、通常5~30質量%程度添加すればよい。
シランカップリング剤としては、分子中にエポキシ基、ビニル基、アミノ基、メタクリル基、アクリル基、及び直鎖アルキル基のいずれか1つを有するシランカップリング剤等が使用できる。シランカップリング剤は1種を単独で用いてもよいし、2種以上を混合して用いることもできる。シランカップリング剤の中でも、特に、分子中にエポキシ基、アミノ基、直鎖アルキル基を有するエポキシシラン系、アミノシラン系、直鎖アルキルシラン系が好適である。
アミノシラン系シランカップリング剤の例としては、1級アミン、2級アミン或いはその双方を有するものが挙げられ、日本ユニカー社製のA-1100、A-1110、A-1120、Y-9669、A―1160(以上、商品名)等が具体的に挙げられる。
直鎖アルキルシラン系シランカップリング剤の直鎖アラルキル基の例としては、ヘキシル基、オクチル基、デシル基を有するものが挙げられ、かかるシランカップリング剤としては、日本ユニカー社製のAZ-6171、AZ―6177(以上、商品名)、信越シリコーン(株)製KBM-3103C(商品名)等が具体的に挙げられる。
なお、タッチロール方式の場合、炭素繊維束を複数のタッチロールに接触させ、複数段階でサイジング剤水分散液を付着させる方式が、サイジング剤の付着量や束幅制御の観点から特に好適である。
サイジング処理の後は、上述したように乾燥処理及び熱処理を順次行うのが好ましい。
なお、本発明におけるプレサイジング処理とは、炭素繊維束にプレサイジング剤を付着させる処理のことである。このプレサイジング処理により、炭素繊維束の収束性を高めると同時に、炭素繊維束と前述したサイジング剤との親和性を高めることが可能となる。
水溶性又は水分散性のエポキシ樹脂としては特に限定されるものではなく、公知のものを用いることができる。また、水系で使用できるものであれば、変性エポキシ樹脂を用いることもできる。これらエポキシ樹脂は1種を単独で用いてもよいし、2種以上を混合して用いることもできる。また、前述したサイジング処理の工程における通過性等の観点から、エポキシ樹脂は、室温で液状のものと固状のものとを併用することがより好ましい。
水分散性のエポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン骨格型エポキシ樹脂、脂肪族系エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂(例えば大日本インキ化学工業社製のHP7200(商品名))、グリシジルアミン型エポキシ樹脂、DPPノボラック型エポキシ樹脂(例えばジャパンエポキシレジン社製のエピコート157S65(商品名))等が挙げられる。また、グリシジル基の代わりに、脂環式エポキシ基を有するものを用いることもできる。
化合物(a)は、その分子中のアミノ基が炭素繊維表面との相互作用を増強する一方、化合物(a)と酸変性ポリオレフィン樹脂との強い相互作用及びこれらの骨格のポリオレフィン鎖が分子の絡み合いにより、ポリオレフィン系樹脂と強固な結合を生じさせる、有効なカップリング剤として働く成分である。従って化合物(a)が炭素繊維の表面に0.2~5質量%付着した本発明の変性炭素繊維は、ポリオレフィン系樹脂との良好な界面接着性を発現でき、複合化に適している。
特に、化合物(a)を炭素繊維の表面に0.2~5質量%付着させ、その後に200~300℃で5秒~3分熱処理を施すことで得られる変性炭素繊維をポリオレフィン系樹脂と複合化すれば、引張破壊応力、曲げ強度、衝撃強度、曲げ弾性率により優れた熱可塑性樹脂組成物が得られる。
また、[(A)+(B)]:(C)は、質量比で、40~97:60~3であり、好ましくは50~95:50~5である。(C)が、3未満であると成形品の物性向上効果が不十分となる恐れがある。また、60を超えると、それ以上の著しい向上効果が得られないとともに、ペレット製造時の工程安定が低下し、またペレットに斑等が生じ、成形品の品質安定性が悪化する恐れがある。
さらに必要によりガラス繊維、タルク、マイカ、炭酸カルシウム等の無機充填剤を添加することができる。
希釈樹脂は、樹脂組成物全体に占める変性炭素繊維(C)の含有量が上記の範囲に含まれるように、炭素繊維強化樹脂組成物100質量部に対し、通常0~1900質量部加える。好ましくは、10質量部から500質量部加える。
成形品は、炭素繊維強化樹脂組成物又は樹脂組成物を用いて射出成形法、押出成形法、中空成形法、圧縮成形法、射出圧縮成形法、ガス注入射出成形法、発泡射出成形法等の公知の成形法により製造できる。
なお、本実施例における各種特性の測定及び評価は、以下の方法により行った。
炭素繊維束の単繊維表面に存在する皺の深さは、円周長さ2μm×繊維軸方向長さ1μmの領域での最高部と最低部の高低差によって規定される。高低差は、走査型原子間力顕微鏡(AFM)を用いて単繊維の表面を走査して得られる表面形状を基に測定した。具体的には以下の通りである。
炭素繊維束の単繊維を数本試料台上にのせ、両端を固定し、さらに周囲にドータイトを塗り測定サンプルとした。原子間力顕微鏡(セイコーインスツルメンツ社製、「SPI3700/SPA-300(商品名)」)により、シリコンナイトライド製のカンチレバーを使用して、AFMモードにて単繊維の円周方向に2~7μmの範囲を、繊維軸方向長さ1μmに渡り少しずつずらしながら繰り返し走査した。得られた測定画像を二次元フーリエ変換にて低周波成分をカットした後、逆変換を行った。そうして得られた単繊維の曲率を除去した断面の平面画像より、円周長さ2μm×繊維軸方向長さ1μmの領域での最高部と最低部の高低差を読み取って評価した。
内径1mmの塩化ビニル樹脂製のチューブ内に測定用の炭素繊維束を通した後、これをナイフで輪切りにして試料とした。
ついで、試料を断面が上を向くようにしてSEM試料台に接着し、さらにAuを約10nmの厚さにスパッタリングしてから、走査型電子顕微鏡(PHILIPS社製、「XL20(商品名)」)により、加速電圧7.00kV、作動距離31mmの条件で断面を観察し、単繊維断面の長径及び短径を測定することで評価した。
JIS R7608に準拠して測定した。
SACMA法のSRM14-90に準拠し、熱分解法により、熱分解処理前後における質量差から炭素繊維束に付着したサイジング剤合計の量を測定し、熱分解処理前の炭素繊維束に対する付着率として、下記式(1)より付着量を求めた。
付着量(%)=100×(W1-W2)/W1 ・・・(1)
W1:熱分解処理前の炭素繊維の質量
W2:熱分解処理後の炭素繊維の質量
アミノ基含有変性ポリオレフィン樹脂の極限粘度[η]は、自動粘度計((株)離合社製、「VNR-53型」)を用いて測定した。溶媒には、酸化防止剤として2,6-ジ-t-ブチル-4-メチルフェノール(以下、BHT)を1g/L添加したテトラリンを用い、ウベローデ型毛管粘度計で、測定温度135℃、試料濃度0.8~1.6g/Lの条件で測定を行った。
アミノ基含有変性ポリオレフィン樹脂のアミノ基含有率は、Macromolecules、第26巻、2087-2088頁、(1993年)に記載された方法に準拠して測定した。
まず、アミノ基含有変性ポリオレフィン1.0g、p-キシレン50mL、ピリジン10mL、ベンゾイルクロライド5mLを、200mLの二口ナスフラスコに加え、窒素雰囲気下、140℃で6時間、加熱攪拌し、ポリマー溶液を得た。
次いで、得られたポリマー溶液を1Lのメタノールに加え十分に攪拌し、析出した固体部(ポリマー)を濾過回収した。更に、これをメタノールで数回洗浄した後、80℃で6時間真空乾燥した。こうして得られたポリマーを190℃でプレス成形した後、赤外吸収スペクトルを測定した。
アミノ基の定量には、アミノ基とベンゾイルクロライドの反応で生成したカルボニル基(C=O)の吸収(1645cm-1)と、ポリオレフィンに特有な吸収バンドとの吸光度の比を用いた。定量に際しては、ポリオレフインパウダーと種々量の1-ブチル(2-メチルプロピル)ベンズアミドのブレンド物(190℃、プレス成形品)の赤外吸収スペクトルより検量線を作成し、この検量線を使用した。
JIS K 7210に準拠し、温度230℃、荷重2.16kgの条件で測定した。
JIS K 7161に従って測定した。
JIS K 7171に従って測定した。
JIS K 7111従って測定した。
<アミノ基含有変性ポリオレフィン樹脂(化合物(a-1))の製造>
(1)エチレンジアミンのp-トルエンスルホン酸部分中和塩の調製
温度計、攪拌機、滴下ロート、還流冷却器を備えた内容積5Lのセパラブルフラスコに、メタノール1.5Lとp-トルエンスルホン酸・1水和物475g(2.5モル)を仕込み溶解した。氷浴で冷却しながら、エチレンジアミン750g(12.5モル)をメタノール1.5Lに溶解した液を、温度を10~20℃に保つような速度で滴下した。滴下終了後、70℃に加熱し、次いで減圧にして、メタノール及び未反応のエチレンジアミンを留去したところ、663gの白色固体が析出した。
得られた白色固体を取り出し、トルエン1.5Lでスラリー状にして濾過し、更に0.5Lのトルエンで2回洗浄し、得られた白色粉末を減圧乾燥した。収量は540gであった。この白色粉末を、ブロモフェノールブルーを指示薬として0.5規定の塩酸で滴下したところ、4.21×10-3eq/gであり、エチレンジアミンのp-トルエンスルホン酸の一中和塩であることが確認された。
温度計、攪拌機、滴下ロート、ディーン・スターク分水器を備えた内容積5Lのセパラブルフラスコに、p-キシレン3L、エチレン-エチルアクリレート-無水マレイン酸(質量比:67.8/29.1/3.1)共重合体(質量平均分子量:Mw=50000、数平均分子量:20000)500gを仕込み、オイルバスを用い、加熱して140℃、p-キシレン還流下で溶解した。
ついで、(1)で調製したエチレンジアミンのp-トルエンスルホン酸部分中和塩75.0gを含む、1,3-ジメチル-2-イミダゾリジノン(DMI)の溶液390gを3時間かけて徐々に滴下した。この間、反応混合物はp-キシレン還流下の温度に保持され、イミド化の結果、生成し共沸してくる水をディーン・スターク分水器で系外へ除去した。
上記ジアミンの部分中和塩の滴下開始より10時間反応を続けた後、冷却し、反応混合物を25Lのメタノール中へ投入し、生成物を沈殿物として回収した。この沈殿物を、炭酸カリウム30gを含む水/メタノール(容積比1/1)溶液に一夜浸漬した後、濾別し、水及びメタノールで十分洗浄後、乾燥し、化合物(a-1)を得た。収量は500gであった。
こうして得られた化合物(a-1)の一部を190℃でプレス成形し、これの赤外吸収スペクトルを測定したところ、3400cm-1にアミノ基の吸収が、1775cm-1及び1695cm-1にはイミド環に基づく吸収が観測され、目的のアミノ基含有変性ポリオレフィン樹脂が得られていることが確認された。
また、得られた化合物(a-1)の極限粘度(135℃のテトラリン中で測定)は0.3dL/gであった。また、アミノ基含有率は、1.0mol%であった。
<変性炭素繊維束の製造>
(1)サイジング剤水分散液の調製
製造例1で得られたアミノ基含有変性ポリオレフィン樹脂(化合物(a-1))を用い、以下のようにしてサイジング剤水分散液を調製した。
まず、サイジング剤主成分であるアミノ基含有変性ポリオレフィン樹脂を粒子径20μm以下の粉体に粉砕し、この粉体とノニオン系界面活性剤(旭電化社製、「プルロニックF108(商品名)」)を、質量比(粉体/界面活性剤)80/20で混合し、サイジング剤とした。該サイジング剤を濃度が35質量%となるように、高せん断攪拌翼を有するホモミキサーにより水中に分散させた。引き続き、超高圧ホモジナイザー(みづほ工業(株)製、「マイクロフルイダイザー M-110-E/H」)に3回通過させ、安定な水乳化物(サイジング剤水分散液)を得た。
得られたサイジング剤水分散液中のサイジング剤の濃度は34質量%、平均粒子径は、0.2μmであった。
炭素繊維束として、ポリアクリル繊維を原料とする炭素繊維束(三菱レイヨン社製、「TR50S-15L」、いずれもプレサイジング未処理品)を用いた。炭素繊維束の物性を表1に示す。
先の変性炭素繊維束(CF-1)の製造において、ボビン巻きしてある炭素繊維束から、炭素繊維束(CF-1)を引き取り、マッフル炉にて230℃で25秒熱処理を行った後、再度ボビンに巻き取り、変性炭素繊維束(CF-2)を得た。熱処理の雰囲気は、空気中で実施した。得られた変性炭素繊維束(CF-2)のサイジング剤の付着量を表2に示す。
化合物(a)の代わりに、無水マレイン酸変性ポリプロピレン樹脂(東洋化成社製、「H-1100P」、135℃のテトラリン中で測定した極限粘度[η]:0.58dl/g、無水マレイン酸含量:5.6質量%)を用いた以外は、先に示したサイジング剤水分散液の調製方法と同様にして、サイジング剤水分散液(濃度2.8質量%)を調製した。該サイジング剤水分散液で満たしてあるフリーローラーを有する浸漬槽内に浸漬させた以外は、変性炭素繊維束(CF-1)の製造と同様にして、変性炭素繊維束(CF-3)を得た。得られた変性炭素繊維束(CF-3)のサイジング剤の付着量を表2に示す。
表3に示す種類と配合量のポリオレフィン樹脂、酸変性ポリオレフィン樹脂及び変性炭素繊維束を用い、以下のようにして炭素繊維含有ペレットを製造した。
なお、表3に示す樹脂は、以下の通りである。
(1)ポリオレフィン樹脂(A)
PP-1:ポリプロピレン単独重合体(プライムポリマー社製、「J-3000GV」、MFR=30g/10分)
PP-2:ポリプロピレン単独重合体(プライムポリマー社製、「H-50000」、MFR=500g/10分)
(2)酸変性ポリオレフィン樹脂(B)
MPP-1:無水マレイン酸変性ポリプロピレン(東洋化成社製、「H-1100P」、135℃のテトラリン中で測定した極限粘度[η]:0.58dl/g、無水マレイン酸含量:5.6wt%)
別途、表3に示す配合量の変性炭素繊維束を熱温度200℃の予熱部を通して予熱した後、280℃に加熱した上記の溶融された樹脂が供給されている含浸槽へ導いた。供給速度を10m/分に調整して変性炭素繊維束をダイ内に送り込み、含浸槽で溶融樹脂を含浸させ、ダイから引き出して冷却し、ペレタイザーで切断して長さ8mm、直径2.2mmの炭素繊維含有ペレットを得た。
得られた炭素繊維強化ポリプロピレン樹脂ブレンドを用いて射出成形し、前記評価項目の測定規格用の試験片を作製した。該試験片の機械的性能(引張破壊応力、曲げ強さ、曲げ弾性率、及びシャルピー衝撃強さ)を評価した。結果を表3に示す。
Claims (10)
- (A)ポリオレフィン樹脂、(B)酸変性ポリオレフィン樹脂、(C)アミノ基含有変性ポリオレフィン樹脂の付着量が0.2~5.0質量%である変性炭素繊維からなり、(A):(B)の質量比が0~99.5:100~0.5で、かつ[(A)+(B)]:(C)の質量比が40~97:60~3である炭素繊維強化樹脂組成物。
- (A):(B)の質量比が80~99:20~1である請求項1記載の炭素繊維強化樹脂組成物。
- [(A)+(B)]:(C)の質量比が50~95:50~5である請求項1又は2記載の炭素繊維強化樹脂組成物。
- 前記変性炭素繊維(C)は、前記アミノ基含有変性ポリオレフィン樹脂を炭素繊維の表面に付着させた後、200~300℃で5秒~3分熱処理して得られるものである請求項1~3のいずれか記載の炭素繊維強化樹脂組成物。
- 前記変性炭素繊維(C)は、前記アミノ基含有変性ポリオレフィン樹脂を炭素繊維の表面に付着させた後、220~240℃で20秒~40秒熱処理して得られるものである請求項1~3のいずれか記載の炭素繊維強化樹脂組成物。
- 前記アミノ基含有変性ポリオレフィン樹脂が、135℃のテトラリン中で測定した極限粘度が0.05~1.0dL/gである請求項1~5のいずれか記載の炭素繊維強化樹脂組成物。
- 前記アミノ基含有変性ポリオレフィン樹脂が、エチレン-エチルアクリレート-無水マレイン酸共重合体、無水マレイン酸グラフトポリエチレン系樹脂、及び無水マレイン酸グラフトポリプロピレン系樹脂からなる群より選ばれた1種の化合物と、2つ以上のアミノ基を有する化合物との反応物である請求項1~6のいずれか記載の炭素繊維強化樹脂組成物。
- 前記アミノ基含有変性ポリオレフィン樹脂が、アミノ基を有し、かつ分子内に下記式(I)で表わされる反復単位を70~99.98モル%と、下記式(II)で表わされる反復単位を0.02~30モル%含有する共重合体である請求項1~7のいずれか記載の炭素繊維強化樹脂組成物。
- 請求項1~8のいずれか記載の炭素繊維強化樹脂組成物と、熱可塑性樹脂とを含み、前記変性炭素繊維(C)を3~60質量%含有する樹脂組成物。
- 請求項1~8のいずれか記載の炭素繊維強化樹脂組成物又は請求項9記載の樹脂組成物から製造される成形品。
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