WO2015033998A1 - 繊維強化樹脂およびその製造方法並びに成形品 - Google Patents
繊維強化樹脂およびその製造方法並びに成形品 Download PDFInfo
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- WO2015033998A1 WO2015033998A1 PCT/JP2014/073320 JP2014073320W WO2015033998A1 WO 2015033998 A1 WO2015033998 A1 WO 2015033998A1 JP 2014073320 W JP2014073320 W JP 2014073320W WO 2015033998 A1 WO2015033998 A1 WO 2015033998A1
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to a resin composition containing reinforcing fibers, a production method thereof, and a molded product (or fiber-reinforced composite material) formed from the resin composition.
- Carbon fiber reinforced composite material containing carbon fiber (carbon fiber) and matrix resin is excellent in strength, rigidity, etc., and used in various applications (for example, primary structural members of aircraft, automotive members, windmill blades, various electronic devices) Etc.).
- Particularly important physical properties in such applications include mainly physical strength, such as impact strength, elastic modulus, bending strength, interlayer toughness, and the like.
- CFRP has been devised to add various fillers in addition to matrix resin (for example, epoxy resin component) and carbon fiber.
- One of the typical fillers is inorganic compound particles represented by silica.
- Such a filler itself has a high elastic modulus and is suitable for improving the elastic modulus and bending strength of CFRP.
- the affinity at the interface with the matrix resin is not necessarily good, and as a result, physical properties such as impact strength and interlayer toughness are lowered.
- Patent Document 1 discloses a resin layer containing matrix resin, resin particles containing a specific alicyclic polyamide resin, and conductive particles having an average particle size larger than the resin particles. And a carbon fiber layer containing carbon fibers provided on both main surfaces of the resin layer, and the difference between the average thickness of the resin layer and the average particle diameter of the resin particles is 12 ⁇ m or less. Carbon fiber reinforced composite materials are disclosed.
- the difference between the average thickness in the resin layer and the average particle diameter of the resin particles is reduced to 12 ⁇ m or less in order to suppress a decrease in interlayer toughness due to variations in the thickness of the resin layer. And in order to make a difference small in this way, it is necessary to necessarily increase the ratio of the resin particles in the resin layer.
- the ratio of the resin particles in the resin layer is preferably 20 to 70% by volume, and in specific examples, all are based on 155 parts by weight of the thermosetting resin composition. 15 parts by weight of resin particles are used.
- JP 2012-211310 A (Claims, [0013], [0121], Examples)
- An object of the present invention is to provide a resin composition capable of efficiently obtaining a reinforcing effect by reinforcing fibers (particularly carbon fibers), a method for producing the same, and a molded product of the resin composition.
- Another object of the present invention is to provide a resin composition capable of effectively exerting the reinforcing performance of reinforcing fibers even when the amount of resin particles added is small, a method for producing the same, and a molded product of the resin composition. .
- Still another object of the present invention is to provide a resin composition capable of improving toughness inside a fiber assembly formed of reinforcing fibers in addition to interlayer toughness, a method for producing the same, and a molded product of the resin composition. There is.
- the difference between the thickness of the resin layer and the size (average diameter) of the resin particles is reduced (further, the ratio of the resin particles in the matrix resin) It has been considered that the shape and particle size of the resin particles itself has an influence on the reinforcing performance of the reinforcing fibers.
- the shape and particle size of the resin particles itself has an influence on the reinforcing performance of the reinforcing fibers.
- Patent Document 1 various methods are described as a method for producing resin particles.
- a chemical pulverization method is cited, and resin particles synthesized by a chemical pulverization method are also used in Examples.
- the chemical pulverization method particles that are relatively rounded but have irregularities on the surface (so-called potato-like or potato-like) are obtained, as described later, to obtain true spherical particles.
- various polyamide resin particles are used, but there is no recognition that the average particle size and shape of the particles are selected in combination.
- the present inventors have intensively studied to achieve the above-mentioned problems.
- the resin particles to be added to the composition containing the matrix resin and the reinforcing fibers have a specific shape (that is, a spherical shape) and a specific average.
- a reinforcing function for example, an effect of improving interlayer toughness
- the present inventors have found that a sufficient reinforcing function can be obtained and completed the present invention.
- the composition (composition for fiber reinforced composite material) of the present invention is a composition containing reinforcing fibers (A), resin particles (B) and matrix resin (C), and the resin particles (B) are average.
- the average particle size of the resin particles (B) may be about 15 to 60 ⁇ m.
- the average particle diameter of the resin particles (B) may be about 1 to 10 times the average fiber diameter of the reinforcing fibers (A).
- the composition of the present invention is a composition comprising reinforcing fibers (A), resin particles (B) and matrix resin (C), wherein the resin particles (B) are average fibers of the reinforcing fibers (A).
- Spherical resin small particles or resin microparticles (B1) having a particle size smaller than the diameter, and spherical resin large particles or resin coarse particles (B2) having a particle size equal to or larger than the average fiber diameter of the reinforcing fibers (A) And may be included.
- the resin small particles (B1) may include resin small particles (B1a) having a particle size distribution of 1 to 5 ⁇ m.
- the large resin particles (B2) may include large resin particles (B2a) having a particle size distribution of 10 to 30 ⁇ m.
- the total amount of the resin small particles (B1a) and the resin large particles (B2a) may be 50% by weight or more based on the entire resin particles (B).
- the ratio of the resin particles having a particle diameter exceeding 70 ⁇ m may be 20% by weight or less based on the entire resin particles (B).
- the reinforcing fiber (A) may typically contain carbon fiber.
- the resin particles (B) (small resin particles (B1) and large resin particles (B2)) may be polyamide resin particles (or the resin constituting the resin particles (B) is a polyamide resin).
- the resin particles (B) (small resin particles (B1) and large resin particles (B2)) may be alicyclic polyamide resin particles.
- the ratio of the resin particles (B) may be relatively small, and may be, for example, 15% by weight or less based on the total amount of the resin particles (B) and the matrix resin (C).
- the matrix resin (C) may be a thermosetting resin component.
- the resin particles (B) are true spherical polyamide resin particles having an average particle diameter of 20 to 40 ⁇ m, and the average particle diameter of the resin particles (B) is 2 to 2 of the average fiber diameter of the reinforcing fibers (A). 6 times, the ratio of the resin particles (B) is 1 to 5% by weight based on the total amount of the resin particles (B) and the matrix resin (C), and the matrix resin (C) is an epoxy resin component. Also good.
- the resin small particles (B1) are true spherical polyamide resin particles having an average particle diameter of 1 to 5 ⁇ m, and the resin large particles (B2) are true spherical polyamide resin particles having an average particle diameter of 10 to 30 ⁇ m.
- the average particle diameter of B2) is 2 to 6 times the average fiber diameter of the reinforcing fibers (A), and the ratio of the resin particles (B) is 3 with respect to the total amount of the resin particles (B) and the matrix resin (C). -15% by weight, and the matrix resin (C) may be an epoxy resin.
- the present invention includes a method for producing the composition by impregnating the reinforcing fiber (A) with a mixture containing the resin particles (B) and the matrix resin (C).
- the present invention also includes a molded article (fiber reinforced composite material, carbon fiber reinforced composite material) formed of the composition.
- a molded article may be a cured product of the composition when the matrix resin (C) is a thermosetting resin component.
- the resin particles (B) may be unevenly distributed in the vicinity of the reinforcing fibers (A).
- the resin particles (B) include resin small particles (B1) and resin large particles (B2), and the reinforcing fibers (A) form a fiber aggregate
- the resin small particles (B1) are the fibers.
- the resin large particles (B2) may be unevenly distributed between the fibers inside the aggregate and in the vicinity of the interface between the surface of the fiber aggregate and the matrix resin.
- the reinforcing function by the reinforcing fibers can be improved or improved. That is, such specific resin particles function as an additive for improving or improving the reinforcing function by the reinforcing fibers.
- the present invention adds the reinforcing fiber (A) [particularly, the reinforcing fiber (A) containing carbon fiber] and the composition containing the matrix resin (C) to reinforce the reinforcing fiber (A) (improvement in strength).
- An additive for improving or improving (or promoting) the effect which includes an additive composed of spherical resin particles (B) having an average particle diameter of 12 to 70 ⁇ m.
- this invention is an additive for improving or improving the reinforcing effect of a reinforcing fiber (A), which is added to a composition containing a reinforcing fiber (A) containing carbon fiber and a matrix resin (C).
- a reinforcing effect for example, an effect of improving interlayer toughness
- reinforcing fibers particularly carbon fibers
- the reinforcing performance by the reinforcing fibers can be effectively exhibited.
- sufficient reinforcing performance can be realized with a small amount of resin particles.
- the addition amount of the resin particles can be reduced, an increase in viscosity in the composition (or mixture) containing the matrix resin and the resin particles can be easily suppressed, and workability can be easily improved.
- the interface between different materials can be reduced by reducing the amount of resin particles added, reduction in physical properties (for example, repeated fatigue resistance, long-term creep, etc.) can be efficiently suppressed.
- the ratio of the resin particles themselves can be reduced, it is easy to maintain characteristics or physical properties derived from the matrix resin (and reinforcing fibers) in the molded product (fiber reinforced composite material). Therefore, in this invention, the characteristic derived from matrix resin (and reinforcement fiber) is not impaired, expressing sufficient reinforcement effect by a reinforcement fiber.
- the reinforcing effect itself by the reinforcing fibers may be further improved as compared with the case where general resin particles are used.
- Such an improvement in the reinforcing effect can be realized even when the addition amount is smaller, and thus is extremely useful.
- the reason why the reinforcing performance by the reinforcing fibers can be effectively expressed is not clear, but by using specific resin particles, it is surprisingly easy to make the resin particles unevenly distributed in the vicinity of the reinforcing fibers in the matrix resin. Seems to be part of that. That is, the improvement effect such as interlayer toughness may be brought about by the resin particles mainly present in the vicinity of the reinforcing fibers among the resin particles dispersed in the matrix resin. Therefore, it is considered that a sufficient reinforcing function can be realized even with a small addition amount by unevenly distributing the resin particles in the vicinity of the reinforcing fibers.
- the resin small particles (B1) are unevenly distributed between the fibers inside the fiber assembly.
- the resin large particles (B2) can be unevenly distributed near the interface between the surface of the fiber aggregate and the matrix resin.
- the toughness inside the fiber aggregate can also be improved.
- composition of the present invention comprises reinforcing fibers (sometimes referred to as reinforcing fibers (A)), resin particles (sometimes referred to as resin particles (B)) and matrix resin (resin forming a matrix) component (matrix resin). (Sometimes referred to as (C)).
- the present invention is characterized in that resin particles containing at least specific resin particles are used as the resin particles.
- compositions for fiber-reinforced composite material can also be referred to as a composition.
- Reinforcing fibers can be used as components for reinforcing (or reinforcing) the matrix resin.
- the reinforcing fiber may be composed of non-carbon fiber, but usually contains carbon fiber in many cases.
- the carbon fiber is not particularly limited, and may be any of pitch-based fibers, polyacrylonitrile (PAN) -based carbon fibers, and the like.
- Non-carbon fibers include inorganic fibers (eg, glass fibers, boron fibers, aluminosilicate fibers, aluminum oxide fibers, silicon carbide fibers, metal fibers, potassium titanate fibers), organic fibers (eg, polyester fibers [eg, aromatic Group polyester fiber (for example, polyalkylene arylate fiber such as polyethylene terephthalate fiber)], polyamide fiber [for example, aromatic polyamide fiber (such as aramid fiber)], regenerated fiber (such as rayon) ⁇ .
- inorganic fibers eg, glass fibers, boron fibers, aluminosilicate fibers, aluminum oxide fibers, silicon carbide fibers, metal fibers, potassium titanate fibers
- organic fibers eg, polyester fibers [eg, aromatic Group polyester fiber (for example, polyalkylene arylate fiber such as polyethylene terephthalate fiber)], polyamide fiber [for example, aromatic polyamide fiber (such as aramid fiber)], regenerated fiber (such as rayon) ⁇
- the reinforcing fibers may be used alone or in combination of two or more.
- the ratio of carbon fiber to the entire reinforcing fiber is, for example, 30% by volume or more, preferably 50% by volume or more, and more preferably. It may be 70% by volume or more (particularly 90% by volume or more).
- the reinforcing fiber may be surface-treated.
- the average diameter of the reinforcing fibers can be selected from a range of about 0.5 to 1000 ⁇ m (for example, 1 to 500 ⁇ m), depending on the type, for example, 1 to 300 ⁇ m (for example, 2 to 100 ⁇ m), preferably 3 to It may be about 70 ⁇ m, more preferably about 5 to 50 ⁇ m (for example, 5 to 30 ⁇ m).
- the average diameter (average fiber diameter) of carbon fibers (or reinforcing fibers containing carbon fibers) is, for example, 1 to 100 ⁇ m (for example, 1.5 to 70 ⁇ m), preferably 2 to 50 ⁇ m (for example, 2.5 to 40 ⁇ m), more preferably 3 to 30 ⁇ m, particularly about 5 to 20 ⁇ m (for example, 6 to 15 ⁇ m), and usually about 5 to 15 ⁇ m (for example, 7 to 10 ⁇ m).
- the fiber diameter can be measured by a conventional method, for example, by measuring the diameter of 10 or more fibers using an electron microscope and calculating an average value.
- the reinforcing fiber may be either a short fiber or a long fiber, but may be a long fiber.
- the long fiber may be either a continuous fiber or a discontinuous fiber, or a combination of a continuous fiber and a discontinuous fiber.
- the reinforcing fiber may be in the form of a fabric (or cloth).
- the fabric (fiber assembly) include woven fabric (woven fabric), non-woven fabric, and knitted fabric (knitted fabric).
- the reinforcing fibers may be included in the composition together with the resin particles and the matrix resin in a mode in which the reinforcing fibers are aligned (arranged) in the same direction (or one direction).
- the fabric structure can be appropriately selected according to the type of fabric.
- examples of the woven fabric include plain weave, twill weave and satin weave, but are not particularly limited.
- examples of the knitted fabric structure include warp knitting (for example, tricot) and weft knitting (for example, flat knitting, knitting knitting, etc.).
- the resin constituting the resin particles may be either a thermoplastic resin or a thermosetting resin, but may usually be a thermoplastic resin.
- the thermoplastic resin is not particularly limited as long as it can improve (or assist) the reinforcing effect of the reinforcing fiber.
- polyamide resin polyamide resin, polyester resin (for example, aromatic polyester resin such as polyethylene terephthalate), polyacetal resin, and the like.
- Polycarbonate resin polyphenylene ether resin, polysulfide resin, polysulfone resin, polyether ketone resin, polyimide resin, polyolefin resin, polystyrene resin, acrylic resin, and the like.
- the thermoplastic resins may be used alone or in combination of two or more.
- the resin may be composed of at least a polyamide resin.
- the resin particle comprised with the polyamide resin tends to exhibit a reinforcing effect especially effectively in combination with the epoxy resin as a matrix resin.
- the polyamide resin is not particularly limited, and examples thereof include an aliphatic polyamide resin, an alicyclic polyamide resin, and an aromatic polyamide resin.
- the polyamide resin may be a homopolyamide or a copolyamide.
- homopolyamide includes an aliphatic diamine component [alkane diamine (for example, C 4-16 alkylene diamine such as tetramethylene diamine, hexamethylene diamine, dodecane diamine, preferably C 6-14 alkylene diamine, More preferably C 6-12 alkylene diamine etc.)] and aliphatic dicarboxylic acid component [eg C 4-20 alkane dicarboxylic acid such as alkane dicarboxylic acid (eg adipic acid, sebacic acid, dodecanedioic acid, preferably C Homo or copolyamide, lactam [ ⁇ -caprolactam, ⁇ -laurolactam, etc.
- alkane diamine for example, C 4-16 alkylene diamine such as tetramethylene diamine, hexamethylene diamine, dodecane diamine, preferably C 6-14 alkylene diamine, More preferably C 6-12 alkylene diamine etc.
- lactam preferably 4 carbon atoms such as 5-18 alkanedicarboxylic acid, more preferably C 6-16 alkanedicarboxylic acid, etc.
- a homo- or co-polymer of an aminocarboxylic acid eg, a C 4-20 aminocarboxylic acid such as ⁇ -aminoundecanoic acid, preferably a C 4-16 aminocarboxylic acid, more preferably a C 6-14 aminocarboxylic acid.
- aminocarboxylic acid eg, a C 4-20 aminocarboxylic acid such as ⁇ -aminoundecanoic acid, preferably a C 4-16 aminocarboxylic acid, more preferably a C 6-14 aminocarboxylic acid.
- Examples include polyamides, aliphatic diamine components, aliphatic dicarboxylic acid components, and copolyamides of lactams or aminocarboxylic acids.
- aliphatic polyamide resin examples include polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 613, polyamide 1010, polyamide 1012, polyamide 6, polyamide 11, polyamide 12, polyamide 611, polyamide 612, and polyamide 66. / 11, polyamide 66/12, polyamide 6/12/612, and the like.
- the alicyclic polyamide resin examples include a homopolyamide or a copolyamide having at least one selected from an alicyclic diamine component and an alicyclic dicarboxylic acid component as constituents, such as a diamine component and a dicarboxylic acid component.
- an alicyclic polyamide obtained by using an alicyclic diamine and / or an alicyclic dicarboxylic acid as at least a part of the components can be used.
- the diamine component and dicarboxylic acid component it is preferable to use the aliphatic diamine component and / or aliphatic dicarboxylic acid component exemplified above together with the alicyclic diamine component and / or alicyclic dicarboxylic acid component.
- Such an alicyclic polyamide resin has high transparency and is known as a so-called transparent polyamide.
- Examples of the alicyclic diamine component include diaminocycloalkanes such as diaminocyclohexane (diamino C 5-10 cycloalkanes); bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 2, Bis (aminocycloalkyl) alkanes such as 2-bis (4′-aminocyclohexyl) propane [bis (aminoC 5-8 cycloalkyl) C 1-3 alkanes and the like]; hydrogenated xylylenediamine and the like.
- diaminocycloalkanes such as diaminocyclohexane (diamino C 5-10 cycloalkanes); bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 2, Bis (aminocycloalkyl) al
- the alicyclic diamine component has a substituent such as an alkyl group (a C 1-6 alkyl group such as a methyl group or an ethyl group, preferably a C 1-4 alkyl group, more preferably a C 1-2 alkyl group). It may be.
- alkyl group a C 1-6 alkyl group such as a methyl group or an ethyl group, preferably a C 1-4 alkyl group, more preferably a C 1-2 alkyl group.
- the alicyclic dicarboxylic acid include cycloalkane dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid (C 5-10 cycloalkane-dicarboxylic acid and the like).
- Typical alicyclic polyamide resins include, for example, an alicyclic diamine component [eg, bis (aminocyclohexyl) alkane and the like] and an aliphatic dicarboxylic acid component [eg, alkane dicarboxylic acid (eg, C 4-20 alkane dicarboxylic acid). Condensates with acid components, etc.].
- an alicyclic diamine component eg, bis (aminocyclohexyl) alkane and the like
- an aliphatic dicarboxylic acid component eg, alkane dicarboxylic acid (eg, C 4-20 alkane dicarboxylic acid). Condensates with acid components, etc.].
- the aromatic polyamide resin includes an aliphatic polyamide resin in which at least one of an aliphatic diamine component and an aliphatic dicarboxylic acid component is an aromatic component, for example, a polyamide in which a diamine component is an aromatic diamine component [
- a condensate of an aromatic diamine such as metaxylylenediamine
- an aliphatic dicarboxylic acid for example, MXD-6 or the like
- a polyamide whose dicarboxylic acid component is an aromatic component for example, an aliphatic diamine (trimethyl) Hexamethylenediamine, etc.
- aromatic dicarboxylic acids terephthalic acid, isophthalic acid, etc.
- the aromatic polyamide resin may be a wholly aromatic polyamide (aramid) such as a polyamide [poly (m-phenyleneisophthalamide) or the like] in which the diamine component and the dicarboxylic acid component are aromatic components.
- Polyamide resins may be used alone or in combination of two or more.
- alicyclic polyamide resins are particularly preferable because the resin particles (B) are likely to be unevenly distributed in the vicinity of the reinforcing fibers (A).
- resin particles (B) are particularly preferable because the resin particles (B) are likely to be unevenly distributed in the vicinity of the reinforcing fibers (A).
- true spherical alicyclic polyamides produced by utilizing a phase separation phenomenon or the like. Resins are particularly preferred.
- the number average molecular weight of the polyamide resin may be, for example, about 8,000 to 200,000, preferably 9000 to 150,000, and more preferably about 10,000 to 100,000.
- the number average molecular weight can be measured by gel permeation chromatography using polystyrene or the like as a standard substance.
- the melting point is not particularly limited, but a polyamide resin having a relatively high melting point may be suitably used.
- a polyamide resin can easily obtain the reinforcing effect by the reinforcing fibers because the spherical shape is easily maintained at a high level in the production of the composition or the molded product.
- the melting point of such a polyamide resin is, for example, 150 ° C. or higher (eg, 155 to 350 ° C.), preferably 160 ° C. or higher (eg, 165 to 300 ° C.), More preferably, it may be 170 ° C.
- the melting point (or softening point) of the polyamide resin is higher than the molding temperature of the composition [for example, the curing temperature of a curable resin (eg, epoxy resin) as a matrix resin] or higher (or higher than the molding temperature of the composition). Temperature).
- Aromatic polyamide resins may not have a melting point (amorphous), but they have a high melting temperature and are easy to maintain a spherical shape. can do.
- the shape of the resin particles (B) is spherical.
- an indefinite shape, a potato shape, a spherical shape, and the like are known, but such a shape is usually determined depending on a method for producing the particle.
- a freeze pulverization method for example, a method in which a resin is cooled and embrittled with liquid nitrogen or the like and then pulverized or pulverized by physical force.
- Chemical pulverization method for example, a method in which a resin is dissolved in a solvent and then dropped into a poor solvent to precipitate
- Polymerization method for example, polymerization while forming particles by suspension polymerization, emulsion polymerization, etc.
- (4) forced emulsification method for example, materials incompatible with resin [for example, water-soluble materials such as water-soluble polymers (polyethylene glycol, etc.), saccharides (polysaccharides, oligosaccharides, etc.)]
- water-soluble materials such as water-soluble polymers (polyethylene glycol, etc.), saccharides (polysaccharides, oligosaccharides, etc.)
- a method of removing the incompatible material from the dispersion, etc. ⁇
- spherical particles can be obtained by methods utilizing interfacial tension such as (3) polymerization method, (4) forced emulsification method, and (5) laser method. Therefore, even if the resin particles (B) are resin particles produced by a method using interfacial tension (for example, (3) polymerization method, (4) forced emulsification method, (5) laser method, etc.). Good.
- the fractured surface is formed by crushing, so that it cannot be spherical, and (2) the chemical pulverization method is preferable as in the freeze pulverization method.
- the surface is relatively rounded, but the surface is uneven (so-called potato or potato) and not spherical.
- spherical resin particles having a smooth surface are particularly preferable.
- a smooth spherical particle having an average particle diameter of 21 ⁇ m a potato-like particle having a low surface smoothness is obtained while the specific surface area by the BET method is about 0.2 to 0.4 m 2 / g.
- the BET specific surface area is about 1.5 to 3 m 2 / g.
- a preferable BET specific surface area can be selected according to the particle diameter, and is, for example, about 0.05 to 2 m 2 / g, preferably about 0.1 to 1 m 2 / g.
- the average particle diameter (average particle diameter) of the resin particles (B) can be selected from the range of 12 ⁇ m or more (for example, 13 to 85 ⁇ m), for example, 14 ⁇ m or more (for example, 15 to 80 ⁇ m), preferably 16 ⁇ m or more (for example, 17 to 75 ⁇ m), more preferably 18 ⁇ m or more (for example, 19 to 70 ⁇ m), particularly 20 ⁇ m or more (for example, 21 to 60 ⁇ m), and usually 12 to 70 ⁇ m (for example, 15 to 60 ⁇ m, preferably 18 to 50 ⁇ m). More preferably, it may be about 20 to 45 ⁇ m, particularly 20 to 40 ⁇ m, particularly preferably 20 to 30 ⁇ m.
- the average particle diameter is represented by a number average primary particle diameter, and can be measured by a laser diffraction scattering method or the like in accordance with JIS R9301-2-2.
- the resin particles (B) have a particle size range (for example, resin particles having a particle diameter of 15 to 60 ⁇ m) of 50% or more (for example, 60% or more), preferably 70% or more, The resin particles may preferably be 80% or more, particularly 90% or more.
- the average particle diameter of the resin particles (B) can also be selected according to the average diameter of the reinforcing fibers (A).
- the average particle diameter (average fiber diameter) of the reinforcing fibers (A) is 0.5 to 15 times (for example, 0.7 to 12 times), preferably about 1 to 10 times (for example, 1.5 to 8 times), more preferably about 1.8 to 7 times (for example, 2 to 6 times). Usually, it may be about 1.5 to 15 times (for example, 2 to 10 times).
- the resin particles (B) include spherical resin small particles or small resin particles (B1) having a particle diameter smaller than the average fiber diameter of the reinforcing fibers (A), and the reinforcing fibers (A). It is preferable to contain large spherical resin particles or large diameter resin particles (B2) having a particle diameter equal to or larger than the average fiber diameter.
- the particle size distribution (particle size or particle size range) of the resin small particles (B1) may be distributed in a range smaller than the average fiber diameter of the reinforcing fibers (A), but the average fiber diameter of the reinforcing fibers (A) may be When D ( ⁇ m) is selected, the particle diameter can be selected from a range of about D-5 to D-1 ⁇ m.
- the specific particle size distribution can be selected according to the fiber diameter of the reinforcing fiber, but may be, for example, 5 ⁇ m or less (for example, 1 to 5 ⁇ m), preferably 2 to 4 ⁇ m, and more preferably about 1 to 3 ⁇ m.
- the resin small fine particles (B1) include resin large particles (B1a) having a particle size distribution of 1 to 5 ⁇ m.
- the particle size distribution can also be measured by a laser diffraction scattering method or the like.
- the average particle diameter of the resin small particles (B1) can also be selected from the same range as the particle size distribution, and is, for example, 5 ⁇ m or less, preferably 1 to 5 ⁇ m (for example, 2 to 4 ⁇ m), and more preferably about 1 to 3 ⁇ m.
- the average particle diameter of the resin small particles (B1) is 0.05 to 0.9 times, preferably 0.1 to 0.8 times, more preferably 0.15 times the average fiber diameter of the reinforcing fibers (A). It may be about 0.6 times (particularly 0.2 to 0.5 times). If the average particle size is too large, the resin small particles may not enter between the fibers, or the reinforcing effect of the reinforcing fibers may be reduced. Even if the average particle size is too small, the particles tend to aggregate and be distributed uniformly. May be difficult, the reinforcing effect of the reinforcing fiber may be reduced.
- the particle size distribution (particle size or particle size range) of the large resin particles (B2) may be distributed in a range equal to or larger than the average fiber diameter of the reinforcing fibers (A), but the average fiber diameter of the reinforcing fibers (A) is D. ( ⁇ m), the particle diameter can be in the range of D to D + 30 ⁇ m (particularly D + 1 to D + 20 ⁇ m).
- the specific particle size distribution can be selected according to the fiber diameter of the reinforcing fiber. For example, it is 10 ⁇ m or more (for example, 10 to 70 ⁇ m), preferably 10 to 50 ⁇ m (for example, 12 to 40 ⁇ m), and more preferably 10 to 30 ⁇ m. It may be about (especially 12 to 25 ⁇ m).
- the resin large fine particles (B2) include resin large particles (B2a) having a particle size distribution of 10 to 30 ⁇ m.
- the average particle size of the large resin particles (B2) can also be selected from the same range as the particle size distribution, for example, 10 ⁇ m or more (for example, 10 to 70 ⁇ m), preferably 10 to 50 ⁇ m (for example, 12 to 40 ⁇ m), more preferably It is about 10 to 30 ⁇ m (particularly 12 to 25 ⁇ m).
- the average particle size of the large resin particles (B2) is 1 to 10 times, preferably 1.5 to 8 times, more preferably 2 to 6 times (particularly 2.5 times) the average fiber size of the reinforcing fibers (A). About 5 times).
- the average particle diameter is too large, it may be difficult to make the large resin particles unevenly distributed in the vicinity of the reinforcing fibers (when the reinforcing fibers form a fabric, in the vicinity of the interface between the surface of the fabric and the matrix resin) Even if the particle diameter is too small, it may be difficult to make the large resin particles unevenly distributed in the vicinity of the reinforcing fibers.
- the total amount of the resin small particles (B1a) and the resin large particles (B2a) may be 50% by weight or more with respect to the whole resin particles (B), for example, 50 to 100% by weight, preferably 60 to 95%. % By weight, more preferably about 70 to 90% by weight (especially 75 to 85% by weight). If the total amount of both particles is too small, the reinforcing effect of the reinforcing fibers may be reduced.
- the resin particles (B) preferably have a small proportion of resin particles having a particle diameter of more than 70 ⁇ m from the viewpoint of being easily distributed near the interface of the reinforcing fibers.
- the proportion of the resin particles having a particle diameter exceeding 70 ⁇ m may be 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the entire resin particles (B). Good.
- the ratio of such large particle diameter resin particles increases, the ratio of the resin particles unevenly distributed in the vicinity of the reinforcing fibers decreases, which may reduce the reinforcing effect of the reinforcing fibers.
- the matrix resin is a resin component that becomes a matrix of the reinforcing fibers (A) (and further the resin particles (B)), and can be appropriately selected depending on the application and desired characteristics.
- Such a matrix resin can be composed of at least a resin (resin component).
- the resin can be selected according to the application and desired properties or physical properties, and is a thermoplastic resin [for example, acrylic resin, polyolefin resin (for example, polypropylene), polyamide resin (for example, the above exemplified polyamide resin), polyester resin (for example, , Aromatic polyester resins such as polyethylene terephthalate), polycarbonate resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyether ketone resins, polyether ether ketone resins, polyimide resins, polyetherimide resins, etc.], thermosetting Any of resin (heat
- the resins may be used alone or in combination of two or more.
- thermosetting resin in the present invention, can be suitably used in combination with the resin particles (B) from the viewpoint of strength and thermal characteristics. Therefore, the resin may be composed of at least a thermosetting resin.
- thermosetting resin examples include epoxy resin, unsaturated polyester resin, vinyl ester resin, acrylic resin, phenol resin, urea resin, melamine resin, aniline resin, polyimide resin, bismaleimide resin, and the like.
- Thermosetting resins may be used alone or in combination of two or more.
- an epoxy resin is particularly preferable.
- the epoxy resin include glycidyl ether type epoxy resin, glycidyl amine type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidylaminocresol, diglycidylaniline, N, N-diglycidyl-4 -Glycidyloxyaniline, etc.), glycidyl ester type epoxy resins [eg dicarboxylic acids (eg aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or hydrogenated products thereof) Diglycidyl ester, etc.], alkene oxides (eg, vinylcyclohexene dioxide, etc.), triglycidyl isocyanurate and the like.
- dicarboxylic acids
- glycidyl ether type epoxy resin examples include bisphenol type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, brominated bisphenol type epoxy resins and the like, and alkylene oxide adducts thereof) Reacted with epichlorohydrin), phenol type epoxy resin (phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, biphenyl skeleton containing Phenol novolac resin, xylylene skeleton-containing phenol novolak resin, etc.), dicyclopentadiene type epoxy resin, naphthalene skeleton Epoxy resins having an aromatic skeleton such as glycidyl ether [for example, di (glycidyloxy) naphthalene such as 1,5-di (glycidyloxy) naphthalene, bis [
- the number of moles of alkylene oxide added relative to 1 mol of hydroxyl group of bisphenol is, for example, 1 mol or more (eg, 1 to 20 mol), preferably 1 to 15 mol, more preferably May be about 1 to 10 moles.
- ⁇ Epoxy resins may be used alone or in combination of two or more.
- an epoxy resin having an aromatic skeleton such as a bisphenol type epoxy resin, is preferable in terms of strength and the like. Therefore, the epoxy resin may be composed of at least an epoxy resin having an aromatic skeleton, and a combination of an epoxy epoxy resin having an aromatic skeleton and another epoxy resin (for example, an epoxy resin having an aliphatic skeleton). Also good.
- the epoxy resin is a monofunctional epoxy compound (or diluent) [eg, monoglycidyl ether [eg, alkyl glycidyl ether (eg, 2-ethylhexyl glycidyl ether), etc.] alkenyl glycidyl ether (eg, allyl glycidyl ether). Etc.), aryl glycidyl ether (eg, phenyl glycidyl ether, etc.), alkene oxide (eg, octylene oxide, styrene oxide, etc.), etc.] may be used in combination.
- the ratio of the former / the latter for example, 99/1 to 50/50, preferably 97/3 to 60/40, Preferably, it may be about 95/5 to 70/30.
- the epoxy resin (or the composition with the epoxy resin and the monofunctional epoxy compound) may be solid or liquid at normal temperature (for example, about 20 to 30 ° C.).
- the viscosity (25 ° C.) of the liquid epoxy resin is, for example, 50 to 50000 mPa ⁇ s, preferably 100 to 40000 mPa ⁇ s (eg 200 to 35000 mPa ⁇ s), and more preferably 300 to 30000 mPa ⁇ s (eg, 500 to 25000 mPa ⁇ s), or 1000 mPa ⁇ s or more (for example, 2000 to 50000 mPa ⁇ s, preferably 3000 to 30000 mPa ⁇ s, and more preferably 5000 to 25000 mPa ⁇ s).
- the matrix resin may contain a curing agent or a curing accelerator. That is, the matrix resin may be composed of a resin (thermosetting resin) and a curing agent or curing accelerator for this resin.
- the curing agent can be appropriately selected according to the type of resin.
- the curing agent when the resin is an epoxy resin, for example, an amine-based curing agent, a phenol resin-based curing agent (for example, a phenol novolak resin, cresol). Novolak resins, etc.), acid anhydride-based curing agents [eg, aliphatic dicarboxylic anhydrides (such as dodecenyl succinic anhydride), alicyclic dicarboxylic anhydrides (tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
- aliphatic dicarboxylic anhydrides such as dodecenyl succinic anhydride
- alicyclic dicarboxylic anhydrides tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
- aromatic dicarboxylic anhydrides phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, etc.
- polymercaptan curing agents polymercaptan curing agents
- latent curing agents trifluoride
- Boron-amine complexes dicyandiamide, carboxylic acid hydrazide, etc.
- amine-based curing agents include aromatic amine-based curing agents [eg, polyaminoarene (eg, diaminoarene such as paraphenylenediamine, metaphenylenediamine), polyamino-alkylarene (eg, diamino-alkyl such as diethyltoluenediamine).
- aromatic amine-based curing agents eg, polyaminoarene (eg, diaminoarene such as paraphenylenediamine, metaphenylenediamine), polyamino-alkylarene (eg, diamino-alkyl such as diethyltoluenediamine).
- Group amine curing agents for example, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, etc.
- alicyclic amine curing agents for example, mensendiamine, isophoronediamine, bis ( 4-amino-3-methylcyclo Xyl) methane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, norbornanediamine, etc.
- imidazoles for example, 2-methylimidazole, 2 -Alkyl imidazoles such as phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Arylimidazoles such as imi
- the curing agents may be used alone or in combination of two or more.
- the curing agent may act as a curing accelerator.
- amine-based curing agents for example, aromatic amine-based curing agents
- aromatic amine-based curing agents may be suitably used.
- the proportion of the curing agent can be appropriately selected depending on the type of epoxy resin (epoxy equivalent, etc.), the type of curing agent, and the like. For example, 0.1 to 300 parts by weight, preferably 100 parts by weight of epoxy resin The amount may be 1 to 250 parts by weight, more preferably 3 to 200 parts by weight (for example, 4 to 150 parts by weight), particularly about 5 to 100 parts by weight.
- the curing accelerator can also be appropriately selected according to the type of resin.
- the curing accelerator when the resin is an epoxy resin, for example, phosphines (for example, ethylphosphine, propylphosphine, trialkylphosphine, phenyl) Phosphine, triphenylphosphine, etc.), amines (eg, triethylamine, piperidine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, tris (dimethylaminomethyl) phenol, N, N-dimethylpiperazine, etc. To tertiary amines or salts thereof).
- the curing accelerators may be used alone or in combination of two or more.
- the proportion of the curing accelerator can be appropriately selected depending on the kind of the curing agent, and the like. Preferably, it may be about 1 to 30 parts by weight.
- the resin particles (B) and the matrix resin (C) (the total amount with the resin when a curing agent and a curing accelerator are included) with respect to the total amount of the resin particles (
- the proportion of B) can be selected from the range of 50% by weight or less (for example, about 0.1 to 40% by weight), for example, 30% by weight or less (for example, 0.5 to 25% by weight), preferably 20% by weight.
- % Or less for example, 1 to 18% by weight), more preferably about 15% by weight or less (for example, 2 to 12% by weight), or about 10% by weight or less (for example, 0.5 to 8% by weight, Preferably, it may be 1 to 5% by weight.
- the ratio of the resin particles (B) is based on the total amount of the resin particles (B) and the matrix resin (C). 20% by weight or less (eg, 1 to 20% by weight), preferably 17% by weight or less (eg, 2 to 17% by weight), more preferably 15% by weight or less (eg, 3 to 15% by weight). May be.
- the resin relative to the total amount of the resin particles (B) and the matrix resin (C) (the total amount with the resin when a curing agent or a curing accelerator is included).
- the ratio of the particles (B) can be selected from a range of 30% by volume or less (eg, about 0.01 to 25% by volume), for example, 20% by volume or less (eg, 0.1 to 15% by volume), preferably It may be about 10% by volume or less (for example, 0.3 to 8% by volume), more preferably about 5% by volume or less (for example, 0.5 to 3% by volume).
- the reinforcing effect by the reinforcing fibers can be sufficiently obtained.
- the ratio of the total amount of the resin particles (B) and the matrix resin (C) is, for example, 1 to 70 with respect to 100 parts by weight of the reinforcing fiber (A). It may be about 2 to 50 parts by weight, more preferably about 3 to 30 parts by weight.
- composition of the present invention may contain other components as necessary as long as the effects of the present invention are not impaired.
- the other components can be appropriately selected depending on the application, and examples include stabilizers, fillers (non-fibrous fillers), colorants, dispersants, preservatives, antioxidants, antifoaming agents, and the like. It is done. These other components may be used alone or in combination of two or more.
- composition of this invention may contain electroconductive particle like the said patent document 1, Usually, it does not need to contain electroconductive particle.
- the form of the composition of the present invention only needs to contain reinforcing fibers (A), resin particles (B), and matrix resin (C) (and other components as necessary, the same shall apply hereinafter).
- the fiber (A) may be impregnated (attached) with a mixture containing the resin particles (B) and the matrix resin (C) (or a matrix resin (C) containing the resin particles (B)).
- Such a form can also be said to be a form in which the reinforcing fibers (A) and the resin particles (B) are dispersed in the matrix resin (C).
- such a composition may be a prepreg (molding intermediate material).
- the matrix resin (C) is a thermosetting resin component [for example, an epoxy resin component (such as a composition of an epoxy resin and a curing agent)]
- the composition may be semi-cured.
- a specific form can be selected according to the shape of the reinforcing fiber (A).
- a plurality of reinforcing fibers (A) aligned in the same direction (or one direction) are impregnated with the mixture.
- examples thereof include (ii) a form in which the above-mentioned mixture is impregnated into the cloth-like reinforcing fibers (A).
- the prepreg is known as a UD prepreg
- the prepreg in the composition in the form (ii) is known as a cross prepreg.
- such a composition can be produced by mixing the reinforcing fibers (A), the resin particles (B), and the matrix resin (C). Usually, the resin particles (B) are added to the reinforcing fibers (A). And a mixture containing the matrix resin (C) can be impregnated (or adhered).
- the particle group including the resin small particle (B1) and the particle group including the resin large particle (B2) are mixed. May be.
- the liquid mixture may be a liquid (liquid at normal temperature) matrix resin (C) or an appropriate solvent (a poor solvent for the resin particles (B)). Moreover, a liquid mixture can also be obtained by melting the matrix resin (C).
- the molded article of the said composition (molded article formed with the said composition) is also contained in this invention. Since such a molded article includes the reinforcing fiber (A) and the matrix resin (C) in which the reinforcing fiber (A) is dispersed, the composite material [fiber reinforced composite material (particularly, carbon fiber composite material)]. It can also be said.
- the manufacturing method (molding method) of the molded product can be selected according to the form of the composition and the kind of the constituent components.
- the matrix resin (C) is a thermosetting resin component
- the composition is cured to form a molded product.
- the matrix resin (C) is a thermosetting resin component
- the molding method can also be selected depending on whether the thermosetting resin component is uncured or semi-cured.
- the shape of the molded product may be any one of a one-dimensional shape (such as a rod), a two-dimensional shape (such as a sheet), and a three-dimensional shape.
- Specific molding methods include hand lay-up molding method, SMC (sheet molding compound) press molding method, RIMP (resin infusion) molding method, prepreg press molding method, prepreg autoclave method, winding method (filament winding method, pin Winding molding method), pultrusion molding method, BMC (bulk molding compound) molding method and the like.
- the reinforcing function for example, interlayer toughness
- the reinforcing fiber (A) can be efficiently reinforced by the resin particles (B).
- the resin particles (B) having a specific shape and particle size, and even if the proportion of the resin particles (B) is relatively small, it is sufficient. Can be realized.
- the resin particles (B) are included in the molded product (or composition) in a form that is uniformly dispersed in the matrix resin (C). It is considered that one of the factors is that the matrix resin (C) is included in the vicinity of (in the vicinity of) the reinforcing fiber (A).
- the resin small particles (B1) and the resin large particles (B2) are in the vicinity of the reinforcing fibers (A) in different regions.
- the reinforcing function is further improved. That is, in a general CFRP including a cured resin such as carbon fiber and epoxy resin, a fabric formed of bundled carbon fibers is placed on an uncured cured resin (liquid), and the cured resin is placed on the fabric. When it penetrates, it is produced by repeatedly applying the cured resin on the fabric in which the cured resin has penetrated and placing the fabric, and then heating and curing.
- the obtained CFRP has a structure in which a layer formed of a cured resin and a layer formed of a woven fabric containing the cured resin are alternately repeated.
- the resin large particles (B2) are unevenly distributed in the vicinity of the interface between the cured resin layer and the woven fabric to suppress cracks between the cured resin layer and the fabric, and the resin small particles (B1) are formed between the fibers in the fabric.
- Estimated to suppress cracks between fibers by entering into the fiber (specifically, entering between the fibers of a bundle of fibers and generating cracks, and then entering between intersecting fiber bundles to generate cracks) it can.
- Aliphatic polyamide particles (A1) True spherical particles of polyamide 12, a ratio of particles having an average particle size of 25 ⁇ m (particle size of 12 to 70 ⁇ m (especially 15 to 60 ⁇ m)) of 90% or more, a laser conforming to JIS R9301-2-2 Diffraction scattering method (measured by “LA-920” manufactured by HORIBA, Ltd., the same applies to others), polyamide 12 (manufactured by Daicel Evonik, “Vestamide L1500”, melting point 178 ° C.) and incompatible Prepared by melt-kneading and forcibly emulsifying using hot-melt saccharide as a material and eluting the saccharide.
- Particle size distribution 3.5% by weight of particles of 1 to 5 ⁇ m, 88.1% by weight of particles of 10 to 30 ⁇ m, less than 1% by weight of particles of 70 ⁇ m or more Aliphatic polyamide particles (A4): True spherical particles of polyamide 12, average particles 52 ⁇ m in diameter, polyamide 12 (manufactured by Daicel-Evonik Co., Ltd., “Daiamide L1901”) and sorbitol as an incompatible material, melt-kneaded and forcibly emulsified, and prepared by eluting sorbitol.
- Particle size distribution 1.3% by weight of 1-5 ⁇ m particles, 11.3% by weight of 10-30 ⁇ m particles, 39.8% by weight of 70 ⁇ m or more particles.
- Alicyclic polyamide particles (B1) True spherical particles of alicyclic polyamide, average particle size of 23 ⁇ m (particle ratio of 12 to 70 ⁇ m (especially 15 to 60 ⁇ m) is 90% or more), alicyclic polyamide (Daicel) -Made by Evonik Co., Ltd., "Trogamide CX7233", melting point 247 ° C) and incompatible material, using polyethylene glycol, melt-kneaded and forcibly emulsified, and prepared by eluting polyethylene glycol.
- Alicyclic polyamide particles (B2) spherical particles of alicyclic polyamide An average particle size of 36 ⁇ m (the ratio of particles having a particle size of 12 to 70 ⁇ m (especially 15 to 60 ⁇ m) is 90% or more), alicyclic polyamide (manufactured by Daicel-Evonik Co., Ltd., “Trogamide CX7323”, melting point 247 ° C.) and Polyethylene glycol is used as an incompatible material, melt-kneaded and forcedly emulsified, and prepared by eluting polyethylene glycol.
- Aromatic polyamide particles (C1) Spherical spherical particles of aromatic polyamide, average particle diameter of 28 ⁇ m (the ratio of particles having a particle diameter of 12 to 70 ⁇ m (especially 15 to 60 ⁇ m) is 90% or more), aromatic polyamide (Daicel Evonik (Daicel)) Co., Ltd., “Trogamide T5000”, amorphous, non-melted at 175 ° C.) and incompatible material, prepared by eluting polyethylene glycol by melt-kneading and forcibly emulsifying with polyethylene glycol (C2): Aromatic polyamide amorphous particles, average particle size 31 ⁇ m, prepared by freeze-grinding aromatic polyamide (“Trogamide T5000” manufactured by Daicel-Evonik Co., Ltd., amorphous, not melted at 175 ° C.).
- the interlaminar shear strength was measured for this test piece.
- a three-point bending test jig (Tensilon Universal Testing Machine, “RTC-1350A”) was used (3 points in the length direction: 20 mm, 70 mm, and 120 mm), and the test speed was 0.5 mm / min. It was.
- the cured laminate was cut into a length of 80 mm and a width of 15 mm so that the warp direction was the longitudinal direction to obtain a test piece. Then, a three-point bending test (three points in the length direction of 20 mm, 40 mm, and 60 mm) was performed on this test piece using a jig for a three-point bending test (Tensilon universal testing machine, “RTC-1350A”). The bending strength was measured. In the measurement, the span interval was 60 mm, and the test speed was 1 mm / min.
- Example 1 to 4 and Comparative Examples 1 to 5 Table 1 for matrix resin [epoxy resin (Mitsubishi Chemical Corporation, “jER828”) plus amine curing agent (Mitsubishi Chemical Corporation, “jER Cure W”)]
- the resin particles were added at the ratio shown in (3% by weight, 5% by weight, 7% by weight, or 9% by weight) and stirred for 24 hours at 100 ° C. and 600 rpm using a hot stirrer. Then, it was further degassed by leaving it in a vacuum vessel for 1 hour to obtain a matrix resin containing resin particles.
- a woven fabric made using carbon fibers (TC-33, HONLU TECHNOLOGY CO. LTD, average fiber diameter of about 7 ⁇ m) is laminated on the matrix resin containing the obtained resin particles by the hand lay-up method. While impregnating, a laminate was obtained.
- the laminates were produced in two types, that is, a laminate in which 12 layers of woven fabric were laminated, and a laminate in which a total of 13 layers of 12 layers of woven fabric and 1 layer of polyimide film were laminated.
- Each laminate was placed in a thermostatic bath under a pressure of about 8 MPa, and allowed to stand at 100 ° C. for 2 hours and at 175 ° C. for 4 hours to perform a curing treatment.
- cured material was about 2.8 micrometers.
- the interlaminar shear strength and bending strength were measured.
- the presence position (dispersion form) of the resin particles in the matrix resin was observed for the obtained cured product.
- the location is determined by embedding the test piece used for the measurement of bending strength with an epoxy resin, polishing the cross section, and observing with an optical microscope, near the interface with the laminate (or fiber) (epoxy When it is unevenly distributed in the vicinity of the interface between the resin layer and the fabric surface), “near the interface” is defined as “uniform” when no uneven distribution is observed and the matrix resin is uniformly dispersed.
- Table 1 also shows the results of the cured products produced in the same manner as described above except that no resin particles were used (or the ratio of the resin particles was 0% by weight). .
- the delamination strength and the bending strength increase at 3% by weight of the resin particles having the smallest weight ratio, whereas in the comparative example, at 7% by weight, These strengths were the largest. That is, it was found that the comparative example required a large amount of resin particles to obtain sufficient strength as compared with the example. Moreover, in the examples, the maximum strength (particularly, the delamination strength) was surprisingly higher than that of the comparative example, although the amount of resin particles was smaller than that of the comparative example.
- Comparative Example 3 and Comparative Example 4 when the average particle size is outside the scope of the present invention, the shape of the particles is potato-like and Not only in the case of an indefinite shape but also in the case of a true sphere, the strength (particularly the delamination strength) was reduced, including the maximum strength.
- Example 2 or 3 and Comparative Example 2 and the results of Example 4 and Comparative Example 5 if the particles are indefinite, the average particle diameter is the same as in the Example, The strength including the strength (particularly the delamination strength) was reduced.
- Examples 5 to 9, Reference Example 1 and Comparative Examples 6 to 7 Total ratio (3% by weight, 5% by weight, 10% by weight) in the composition shown in Table 2 with respect to the matrix resin [the epoxy resin (jER828) plus amine-based curing agent (jER Cure W)] 15 wt% or 20 wt%), and the resin particles were added and stirred for 24 hours at 100 ° C. and 600 rpm using a hot stirrer. Then, it was further degassed by leaving it in a vacuum vessel for 1 hour to obtain a matrix resin containing resin particles.
- the matrix resin the epoxy resin (jER828) plus amine-based curing agent (jER Cure W)
- a woven fabric (plain weave) produced using carbon fibers (TC-33) by a hand lay-up method is impregnated while being laminated on a matrix resin containing the obtained resin particles, and a laminate in which 12 layers of the woven fabric are laminated.
- Each laminate was placed in a thermostatic bath under a pressure of about 8 MPa, and allowed to stand at 100 ° C. for 2 hours and at 175 ° C. for 4 hours to perform a curing treatment.
- cured material was about 2.8 micrometers.
- Table 2 also shows the results for the cured product produced in the same manner as described above except that the resin particles were not used.
- the composition of the present invention can be used as a composition for a fiber-reinforced composite material.
- Such composite materials are structural members (structural materials) in various fields, such as vehicles (for example, airplanes, helicopters, rockets, automobiles, motorcycles, bicycles, trains, ships, wheelchairs, etc.), artificial satellites, windmills, sports. It can be applied to products (golf shafts, tennis rackets), casings (notebook PC casings, etc.), medical products (artificial bones, etc.), IC trays, suspension rods, piers, etc.
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Abstract
Description
本発明の組成物は、強化繊維(強化繊維(A)などということがある)、樹脂粒子(樹脂粒子(B)などということがある)およびマトリックス樹脂(マトリックスを形成する樹脂)成分(マトリックス樹脂(C)などということがある)を含む。そして、本発明では、前記樹脂粒子として、特定の樹脂粒子を少なくとも含む樹脂粒子を使用することに特徴がある。
強化繊維(補強繊維、繊維状強化材、繊維状フィラー、繊維状充填剤)は、マトリックス樹脂を補強(又は強化)する成分として用いることができる。
樹脂粒子(樹脂粒子(B))を構成する樹脂としては、熱可塑性樹脂、熱硬化性樹脂のいずれであってもよいが、通常、熱可塑性樹脂であってもよい。
マトリックス樹脂は、補強繊維(A)(さらには樹脂粒子(B))のマトリックスとなる樹脂成分であり、用途や所望の特性に応じて、適宜選択できる。
本発明の組成物の形態は、強化繊維(A)、樹脂粒子(B)およびマトリックス樹脂(C)(さらには必要に応じて他の成分、以下同じ)を含んでいればよく、通常、強化繊維(A)に、樹脂粒子(B)およびマトリックス樹脂(C)を含む混合物(又は樹脂粒子(B)を含むマトリックス樹脂(C))が含浸(付着)した形態であってもよい。このような形態は、強化繊維(A)および樹脂粒子(B)が、マトリックス樹脂(C)中に分散した形態ということもできる。
本発明には、前記組成物の成形品(前記組成物で形成された成形品)も含まれる。このような成形品は、強化繊維(A)と、この強化繊維(A)を分散させるマトリックス樹脂(C)とを含んでいるため、複合材料[繊維強化複合材料(特に炭素繊維複合材料)]ということもできる。
脂肪族ポリアミド粒子(A1):ポリアミド12の真球状粒子、平均粒子径25μm(粒子径12~70μm(特に15~60μm)の粒子の割合が90%以上、JIS R9301-2-2に準拠したレーザー回折散乱法((株)堀場製作所製「LA-920」)による測定値、他も同じ)、ポリアミド12(ダイセル・エボニック(株)製、「ベスタミドL1500」、融点178℃)および非相溶な材料として熱溶融性糖類を用い、溶融混練して強制乳化し、前記糖類を溶出して調製
脂肪族ポリアミド粒子(A2):ダイセル・エボニック(株)製「ベストジント2070」、ポリアミド12のジャガイモ状粒子(化学粉砕品)、平均粒子径8μm
脂肪族ポリアミド粒子(A3):ポリアミド12の真球状粒子、平均粒子径19μm、ポリアミド12(ダイセル・エボニック(株)製、「ダイアミドL1600」)および非相溶な材料としてソルビトールを用い、溶融混練して強制乳化し、ソルビトールを溶出して調製。粒度分布:1~5μmの粒子3.5重量%、10~30μmの粒子88.1重量%、70μm以上の粒子1重量%未満
脂肪族ポリアミド粒子(A4):ポリアミド12の真球状粒子、平均粒子径52μm、ポリアミド12(ダイセル・エボニック(株)製、「ダイアミドL1901」)および非相溶な材料としてソルビトールを用い、溶融混練して強制乳化し、ソルビトールを溶出して調製。粒度分布:1~5μmの粒子1.3重量%、10~30μmの粒子11.3重量%、70μm以上の粒子39.8重量%。
脂環族ポリアミド粒子(B2):脂環族ポリアミドの真球状粒子、平均粒子径36μm(粒子径12~70μm(特に15~60μm)の粒子の割合が90%以上)、脂環族ポリアミド(ダイセル・エボニック(株)製、「トロガミドCX7323」、融点247℃)および非相溶な材料としてポリエチレングリコールを用い、溶融混練して強制乳化し、ポリエチレングリコールを溶出して調製
脂環族ポリアミド粒子(B3):脂環族ポリアミドの不定形粒子、平均粒子径34μm、脂環族ポリアミド(ダイセル・エボニック(株)製、「トロガミドCX7323」、融点247℃)を冷凍粉砕して製造したもの
脂環族ポリアミド粒子(B4):脂環族ポリアミドの真球状粒子、平均粒子径11μm、脂環族ポリアミド(ダイセル・エボニック(株)製、「トロガミドCX7323」、融点247℃)および非相溶な材料としてポリエチレングリコールを用いた強制乳化法により製造したもの
脂環族ポリアミド粒子(B5):脂環族ポリアミドの真球状粒子、平均粒子径89μm、脂環族ポリアミド(ダイセル・エボニック(株)製、「トロガミドCX7323」、融点247℃)および非相溶な材料としてポリエチレングリコールを用い、溶融混練して強制乳化し、ポリエチレングリコールを溶出して調製
脂環族ポリアミド粒子(B6):脂環族ポリアミドの真球状粒子、平均粒子径5.1μm、脂環族ポリアミド(ダイセル・エボニック(株)製、「トロガミドCX7323」、融点247℃)および非相溶な材料としてポリエチレングリコールを用い、溶融混練して強制乳化し、ポリエチレングリコールを溶出して調製。粒度分布:1~5μmの粒子49.5重量%、10~30μmの粒子2.5重量%、70μm以上の粒子1重量%未満。
芳香族ポリアミド粒子(C2):芳香族ポリアミドの不定形粒子、平均粒子径31μm、芳香族ポリアミド(ダイセル・エボニック(株)製「トロガミドT5000」、非晶質、175℃において非溶融)を冷凍粉砕して調製。
予亀裂を導入するため、後述する織物の6層目と7層目との間に、厚み25μmのポリイミドフィルム(東レ・デュポン(株)製「カプトン」)を挿入し、この積層物[織物12層、ポリイミドフィルム1層(織物の6層目と7層目との間に積層)の13層の積層物]を硬化させた。硬化後の積層物を、経糸方向が長手方向になるよう、長さ140mm、幅25mmに切り出し、試験片を得た。
硬化後の積層物を、経糸方向が長手方向になるよう、長さ80mm、幅15mmに切り出し、試験片を得た。そして、この試験片について、3点曲げ試験用の治具(テンシロン万能試験機、「RTC-1350A」)を用いて、3点曲げ試験(長さ方向20mm、40mm、60mmの3点)を行い、曲げ強度を測定した。なお、測定において、スパン間は60mmとし、試験速度は1mm/分とした。
マトリックス樹脂[エポキシ樹脂(三菱化学(株)製、「jER828」)に対して、アミン系硬化剤(三菱化学(株)製、「jERキュアW」)を加えたもの]に対して、表1に示す割合(3重量%、5重量%、7重量%、又は9重量%)で樹脂粒子を添加し、ホットスターラーを用いて、100℃、600rpmの条件で24時間攪拌した。その後、さらに、真空容器中で1時間放置することで脱泡し、樹脂粒子を含むマトリックス樹脂を得た。
マトリックス樹脂[エポキシ樹脂(jER828)に対して、アミン系硬化剤(jERキュアW)を加えたもの]に対して、表2に示す組成で合計割合(3重量%、5重量%、10重量%、15重量%、又は20重量%)で樹脂粒子を添加し、ホットスターラーを用いて、100℃、600rpmの条件で24時間攪拌した。その後、さらに、真空容器中で1時間放置することで脱泡し、樹脂粒子を含むマトリックス樹脂を得た。
Claims (19)
- 強化繊維(A)、樹脂粒子(B)およびマトリックス樹脂(C)を含む組成物であって、強化繊維(A)が炭素繊維を含み、かつ樹脂粒子(B)が平均粒子径12~70μmを有する球状の樹脂粒子である組成物。
- 樹脂粒子(B)の平均粒子径が15~60μmである請求項1記載の組成物。
- 樹脂粒子(B)の平均粒子径が、強化繊維(A)の平均繊維径の1~10倍である請求項1又は2記載の組成物。
- 強化繊維(A)、樹脂粒子(B)およびマトリックス樹脂(C)を含む組成物であって、強化繊維(A)が炭素繊維を含み、かつ樹脂粒子(B)が、前記強化繊維(A)の平均繊維径よりも小さい粒径を有する球状の樹脂小粒子(B1)と、前記強化繊維(A)の平均繊維径以上の粒径を有する球状の樹脂大粒子(B2)とを含む組成物。
- 樹脂小粒子(B1)が、粒度分布が1~5μmの樹脂小粒子(B1a)を含み、かつ樹脂大粒子(B2)が、粒度分布10~30μmの樹脂大粒子(B2a)を含む請求項4記載の組成物。
- 樹脂小粒子(B1a)と樹脂大粒子(B2a)との重量割合が、前者/後者=5/95~50/50である請求項4又は5記載の組成物。
- 樹脂小粒子(B1a)及び樹脂大粒子(B2a)の総量が、樹脂粒子(B)全体に対して50重量%以上であり、かつ70μmを超える粒径を有する樹脂粒子の割合が、樹脂粒子(B)全体に対して20重量%以下である請求項6記載の組成物。
- 樹脂粒子(B)が、ポリアミド樹脂粒子である請求項1~7のいずれかに記載の組成物。
- 樹脂粒子(B)が、脂環族ポリアミド樹脂粒子である請求項1~8のいずれかに記載の組成物。
- 樹脂粒子(B)の割合が、樹脂粒子(B)およびマトリックス樹脂(C)の総量に対して15重量%以下である請求項1~9のいずれかに記載の組成物。
- マトリックス樹脂(C)が熱硬化性樹脂である請求項1~10のいずれかに記載の組成物。
- 樹脂粒子(B)が平均粒子径20~40μmの真球状ポリアミド樹脂粒子であり、樹脂粒子(B)の平均粒子径が強化繊維(A)の平均繊維径の2~6倍であり、樹脂粒子(B)の割合が、樹脂粒子(B)およびマトリックス樹脂(C)の総量に対して1~5重量%であり、マトリックス樹脂(C)がエポキシ樹脂である請求項1~3のいずれかに記載の組成物。
- 樹脂小粒子(B1)が平均粒子径1~5μmの真球状ポリアミド樹脂粒子であり、樹脂大粒子(B2)が平均粒子径10~30μmの真球状ポリアミド樹脂粒子であり、樹脂大粒子(B2)の平均粒子径が強化繊維(A)の平均繊維径の2~6倍であり、樹脂粒子(B)の割合が、樹脂粒子(B)およびマトリックス樹脂(C)の総量に対して3~15重量%であり、マトリックス樹脂(C)がエポキシ樹脂である請求項4~7のいずれかに記載の組成物。
- 強化繊維(A)に、樹脂粒子(B)およびマトリックス樹脂(C)を含む混合物を含浸させ、請求項1~13のいずれかに記載の組成物を製造する方法。
- 請求項1~13のいずれかに記載の組成物で形成された成形品。
- 樹脂粒子(B)が、強化繊維(A)の近傍に偏在している請求項15記載の成形品。
- 樹脂粒子(B)が樹脂小粒子(B1)と樹脂大粒子(B2)とを含み、かつ強化繊維(A)が繊維集合体を形成するとともに、前記樹脂小粒子(B1)が前記繊維集合体内部の繊維間に偏在し、かつ前記樹脂大粒子(B2)が前記繊維集合体の表面とマトリックス樹脂との界面近傍に偏在している請求項15又は16記載の成形品。
- 炭素繊維を含む強化繊維(A)、およびマトリックス樹脂(C)を含む組成物に添加し、強化繊維(A)の補強効果を向上又は改善するための添加剤であって、平均粒子径12~70μmを有する球状の樹脂粒子(B)で構成された添加剤。
- 炭素繊維を含む強化繊維(A)、およびマトリックス樹脂(C)を含む組成物に添加し、強化繊維(A)の補強効果を向上又は改善するための添加剤であって、前記強化繊維(A)の平均繊維径よりも小さい粒径を有する球状の樹脂小粒子(B1)と、前記強化繊維(A)の平均繊維径以上の粒径を有する球状の樹脂大粒子(B2)とを組み合わせた添加剤。
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JP6542123B2 (ja) | 2019-07-10 |
US10316181B2 (en) | 2019-06-11 |
JP2019183161A (ja) | 2019-10-24 |
EP3042926B1 (en) | 2019-07-03 |
EP3042926A4 (en) | 2017-04-05 |
TW201518405A (zh) | 2015-05-16 |
TWI648341B (zh) | 2019-01-21 |
CN105518060B (zh) | 2019-10-22 |
US20160200910A1 (en) | 2016-07-14 |
KR102261674B1 (ko) | 2021-06-08 |
EP3042926A1 (en) | 2016-07-13 |
KR20160052638A (ko) | 2016-05-12 |
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JPWO2015033998A1 (ja) | 2017-03-02 |
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