WO2015045618A1 - 強化繊維用サイジング剤及びその用途 - Google Patents
強化繊維用サイジング剤及びその用途 Download PDFInfo
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- WO2015045618A1 WO2015045618A1 PCT/JP2014/070302 JP2014070302W WO2015045618A1 WO 2015045618 A1 WO2015045618 A1 WO 2015045618A1 JP 2014070302 W JP2014070302 W JP 2014070302W WO 2015045618 A1 WO2015045618 A1 WO 2015045618A1
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- weight
- reinforcing fiber
- unsaturated polyester
- resin
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- 0 COIN(*)C1CCC1 Chemical compound COIN(*)C1CCC1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
- D06M15/51—Unsaturated polymerisable polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
-
- 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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
- C08J2367/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Definitions
- the present invention relates to a sizing agent for reinforcing fibers and its use. Specifically, the present invention relates to a sizing agent for reinforcing fibers used to reinforce a matrix resin, a reinforcing fiber strand using the reinforcing fiber, and a fiber-reinforced composite material.
- Fiber reinforced composite materials in which plastic materials (called matrix resins) are reinforced with various synthetic fibers are widely used for automobile applications, aerospace applications, sports / leisure applications, general industrial applications, and the like.
- fibers used in these composite materials include various inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and various organic fibers such as aramid fibers, polyamide fibers, and polyethylene fibers.
- These various synthetic fibers are usually manufactured in a filament shape, and then processed into a sheet-like intermediate material called a unidirectional prepreg by a hot melt method or a drum winding method, processed by a filament winding method, or in some cases a textile Or it is used as a reinforced fiber through various high-order processing steps, such as being processed into a chopped fiber shape.
- Epoxy resins are widely used as matrix resins for reinforced fiber composite materials.
- unsaturated polyester resins, vinyl ester resins, acrylic resins, and the like are used as radical polymerization matrix resins.
- the adhesion between the matrix resin and the reinforced fiber is important, and the sizing that improves the adhesion of the reinforced fiber to the above epoxy resin and radical polymerization matrix resin.
- Agents for example, Patent Documents 1 and 2) have been proposed.
- Patent Document 1 and Patent Document 2 improve the adhesion of the reinforcing fibers to the epoxy resin or the radical polymerization matrix resin, the reinforcing fibers to which the sizing agent has been applied over time. There were cases in which the problem of fluff generation and a decrease in adhesion to the matrix resin occurred. Furthermore, problems may occur in the long-term storage stability of the sizing agent. Some reinforcing fibers have a low elongation and are brittle. These reinforcing fibers to which conventional sizing agents are applied may cause problems such as generation of fuzz and fiber cutting due to mechanical friction in the processing step.
- the affinity between the reinforcing fibers and the matrix resin can be increased and firmly adhered, and the fluff of the reinforcing fiber strands can be suppressed and the aging can be suppressed.
- Development of a sizing agent with excellent properties is desired.
- the object of the present invention is to provide excellent adhesion with a matrix resin to reinforcing fibers, to suppress generation of fluff and aging of reinforcing fiber strands, and to provide long-term storage stability. It is an object of the present invention to provide a sizing agent excellent in the above, a reinforcing fiber strand and a fiber-reinforced composite material using the same.
- the present inventors have used the epoxy resin (A) and the specific unsaturated polyester (B), and further by using the fatty acid ester (C). The present inventors have found that the problem can be solved and have reached the present invention.
- the sizing agent for reinforcing fibers of the present invention contains an epoxy resin (A), an unsaturated polyester (B) having an acid value of less than 5, and a fatty acid ester (C).
- the unsaturated polyester (B) is preferably 30 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin (A), and a total of 100 of the epoxy resin (A) and the unsaturated polyester (B).
- the fatty acid ester (C) is preferably 1 to 15 parts by weight with respect to parts by weight.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the unsaturated polyester (B) is preferably 1.2 to 2.1.
- the unsaturated polyester (B) preferably contains a condensate of an unsaturated dibasic acid (b1) and an alkylene oxide adduct (b2) of bisphenols.
- the unsaturated polyester (B) was obtained by reacting a reactive component containing an unsaturated dibasic acid (b1) and an alkylene oxide adduct (b2) of bisphenol at a ratio satisfying the following formula (I). It is preferable. Number of moles of unsaturated dibasic acid (b1) ⁇ number of moles of alkylene oxide adduct (b2) of bisphenol (I)
- the acid value of the unsaturated polyester (B) is preferably 4.5 or less.
- the melting point of the fatty acid ester (C) is preferably 5 ° C. or less.
- the fatty acid ester (C) is preferably an ester having a structure in which an unsaturated fatty acid having 10 to 24 carbon atoms and a monohydric alcohol having 8 to 20 carbon atoms are ester-bonded.
- the total weight ratio of the epoxy resin (A), the unsaturated polyester (B), and the fatty acid ester (C) in the nonvolatile content of the sizing agent is preferably 70% by weight or more.
- the reinforcing fiber strand of the present invention is obtained by adhering the above-described reinforcing fiber sizing agent to a raw material reinforcing fiber strand.
- the fiber-reinforced composite material of the present invention includes a matrix resin and the above-described reinforcing fiber strand.
- the matrix resin is preferably a thermosetting resin.
- the sizing agent for reinforcing fibers of the present invention can impart excellent adhesiveness with the matrix resin to the reinforcing fibers. Moreover, generation
- the present invention is a sizing agent for reinforcing fibers used to reinforce a matrix resin, and contains an epoxy resin (A), a specific unsaturated polyester (B) and a fatty acid ester (C). Details will be described below.
- Epoxy resin (A) The epoxy resin (A) is an essential component of the sizing agent of the present invention.
- the epoxy resin (A) is a compound having two or more reactive epoxy groups in the molecular structure.
- the epoxy resin (A) is typically a glycidyl ether type obtained from epichlorohydrin and an active hydrogen compound, and other examples include glycidyl ester type, glycidyl amine type, and alicyclic type.
- the epoxy resin (A) may be used alone or in combination of two or more.
- the glycidyl ether type epoxy resin (A) for example, an epoxy resin having a functional group represented by the following general formula (1) produced using alcohols as a raw material, and a general formula ( Examples thereof include an epoxy resin having a functional group represented by 2).
- Examples of the glycidyl ester type epoxy resin (A) include an epoxy resin having a functional group represented by the following general formula (3), which is produced using a carboxylic acid such as a phthalic acid derivative or a synthetic resin fatty acid as a raw material.
- Examples of the glycidylamine type epoxy resin (A) include an epoxy resin having a functional group represented by the following general formula (4) and an epoxy resin having a functional group represented by the following general formula (5).
- Examples of the alicyclic epoxy resin (A) include an epoxy resin (A) having a functional group represented by the following general formula (6).
- an epoxy resin having a functional group represented by the general formula (2) is preferable for improving the adhesion between the fiber and the matrix resin.
- the epoxy equivalent of the epoxy resin (A) is preferably 100 to 1500 g / eq, more preferably 120 to 1000 g / eq, and further preferably 150 to 800 g / eq.
- the epoxy equivalent refers to that based on JIS-K7236.
- the weight average molecular weight of the epoxy resin (A) is preferably 100 to 10000, more preferably 100 to 8000, and further preferably 150 to 7000.
- the weight average molecular weight is less than 100, the heat resistance may be insufficient and volatilize in the drying step of the reinforcing fiber strand.
- the weight average molecular weight exceeds 10,000, the long-term storage stability of the sizing agent may be lowered.
- the epoxy resin (A) is preferably an aromatic epoxy resin having an aromatic ring in the molecular structure from the viewpoint of improving the adhesion between the reinforcing fiber and the matrix resin.
- the aromatic epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, and pyrocatechol; dihydroxynaphthalene, biphenol, bisphenol F, bisphenol A, phenol novolac, orthocresol novolak, resorcin novolak, Examples thereof include polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as bisphenol F novolak, bisphenol A novolak, dicyclopentadiene-modified phenol, triphenylmethane, and tetraphenylethane.
- a compound represented by the following general formula (7) a compound represented by the following general formula (8) are preferable, and a compound represented by the following general formula (7) is more preferable.
- R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or a methyl group.
- n is an integer of 0 to 30, preferably 0 to 20, and more preferably 0 to 10.
- m is an integer of 0 to 10, preferably 0 to 8, and more preferably 0 to 5.
- the method for producing the epoxy resin (A) is not particularly limited, and a known method can be employed. Moreover, the above-mentioned epoxy resin (A) is generally marketed, and these commercially available epoxy resins (A) can be used in the sizing agent for carbon fibers of the present invention.
- Unsaturated polyester (B) having an acid value of less than 5 is an essential component of the sizing agent of the present invention.
- the acid value is preferably 4.5 or less, more preferably 4 or less, and even more preferably 3.5 or less.
- the acid value is represented by the number of mg of potassium hydroxide necessary to neutralize 1 g of the sample, and is measured according to JIS K 2501: 2003.
- An unsaturated polyester refers to a polyester compound having one or more unsaturated bonds in the molecular structure.
- the unsaturated polyester 1) a condensate of an acid alone having at least one unsaturated bond and an alcohol, 2) a mixture of an acid having at least one unsaturated bond and an acid having no unsaturated bond, and an alcohol And 3) a condensate of an acid and an alcohol having one or more unsaturated bonds.
- an unsaturated dibasic acid and a dihydric alcohol condensate are particularly preferable.
- the unsaturated dibasic acid is a compound having an unsaturated double bond and two carboxylic acid groups, or an anhydride thereof.
- an aliphatic unsaturated dibasic acid having 4 to 6 carbon atoms is particularly preferable.
- divalent alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentanediol, hexanediol, bisphenols, and alkylene oxide adducts of bisphenols.
- alkylene oxide adducts of bisphenols are preferable. Bisphenols and alkylene oxide adducts of bisphenols will be described later.
- the unsaturated polyester (B) is an alkylene oxide adduct of the above unsaturated dibasic acid (hereinafter referred to as unsaturated dibasic acid (b1)) and a bisphenol from the viewpoint of improving the adhesion between the reinforcing fiber and the matrix resin. It is preferable to contain a condensate with b2).
- Bisphenols are compounds having two hydroxyphenyl groups, such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S.
- the alkylene oxide addition product (b2) of bisphenol is a compound obtained by addition polymerization of alkylene oxide to the bisphenol.
- the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.
- the number of moles of alkylene oxide added is preferably 10 moles or less, more preferably 5 moles or less, and most preferably 2 to 4 moles. If added in excess of 10 mol, the rigidity of the bisphenols may be lost, and the adhesion with the matrix resin may be reduced.
- the unsaturated polyester (B) is an unsaturated dibasic acid (b1) and an alkylene oxide adduct (b2) of bisphenols represented by the following formula (b) from the viewpoints of suppression of aging of the reinforcing fiber strand and storage stability of the sizing agent. It is preferably obtained by reacting a reactive component that is contained in a proportion satisfying I). Number of moles of unsaturated dibasic acid (b1) ⁇ number of moles of alkylene oxide adduct (b2) of bisphenol (I)
- the molar ratio (b1 / b2) of the unsaturated dibasic acid (b1) to the alkylene oxide adduct (b2) of bisphenols is preferably 70/100 to 99/100, more preferably 75/100 to 90/100, 80/100 to 85/100 is more preferable.
- the total proportion of the unsaturated dibasic acid (b1) and the alkylene oxide adduct (b2) of bisphenols in the reactive component is preferably 90 mol% or more, 95 mol% or more is more preferable, and 100 mol% is further more preferable.
- the reactive component does not substantially contain an esterified product of an unsaturated dibasic acid from the viewpoint of improving the adhesion between the reinforcing fiber and the matrix resin.
- the proportion of the esterified product of unsaturated dibasic acid in the reactive component is preferably 2 mol% or less, more preferably 1 mol% or less, and even more preferably 0 mol%.
- the proportion of the compound having a monofunctional active hydrogen group in the reactive component is preferably 2 mol% or less, more preferably 1 mol% or less, and even more preferably 0 mol%.
- the compound having a monofunctional active hydrogen group include monohydric alcohols, secondary amines, and monovalent thiols.
- the weight average molecular weight of the unsaturated polyester (B) is preferably 500 to 5000, more preferably 800 to 4500, and still more preferably 1000 to 3500.
- the molecular weight is less than 500, neither good adhesiveness nor heat resistance may be obtained.
- the molecular weight exceeds 5000, the solution stability may deteriorate.
- the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the unsaturated polyester (B) is preferably 1.2 to 2.1, more preferably 1.4 to 2.0. 1.6 to 1.9 are more preferable.
- the molecular weight ratio is less than 1.2, neither good adhesiveness nor heat resistance may be obtained.
- the molecular weight ratio exceeds 2.2, the solution stability may deteriorate.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) referred to in the present invention were measured with a separation column (Showa Denko) using a high-speed gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation at a sample concentration of 2 mg / ml.
- This is a value calculated from a chart measured by a RI detector after being injected into Shodex (registered trademark) KF-G, KF-402HQ, KF-403HQ, manufactured by Co., Ltd.
- Tetrahydrofuran (THF) was used for the mobile phase
- polyethylene glycol (PEG) was used for the calibration curve preparation standard substance, and the measurement was performed at a column temperature of 40 ° C. and a flow rate of 0.3 ml / min.
- the method for producing the unsaturated polyester (B) is not particularly limited, and a known method can be employed.
- it can be obtained by polycondensation of an unsaturated dibasic acid (b1) and an alkylene oxide adduct (b2) of bisphenols.
- the reaction temperature during polycondensation is preferably 110 ° C. to 180 ° C., more preferably 130 ° C. to 160 ° C., from the viewpoint of promoting esterification and reducing the acid value of the reaction product.
- the reaction time during the polycondensation is 1 to 10 hours, more preferably 2 to 5 hours, from the viewpoint of promoting esterification and lowering the acid value of the reaction product.
- An esterification catalyst may be used to promote the polycondensation reaction.
- the fatty acid ester (C) is an essential component of the sizing agent of the present invention.
- the sizing agent for reinforcing fibers of the present invention is a matrix resin for the reinforcing fibers. And excellent adhesion can be imparted. Moreover, generation
- the fatty acid ester (C) is a compound having a structure in which a fatty acid and a monohydric alcohol are ester-bonded.
- the fatty acid include saturated fatty acids having 10 to 24 carbon atoms and unsaturated fatty acids having 10 to 24 carbon atoms. From the viewpoint of suppressing the fluff of the reinforcing fiber strand, an unsaturated fatty acid having 10 to 24 carbon atoms is preferable.
- the number of carbon atoms of the fatty acid is preferably 10 to 22, more preferably 12 to 20, and still more preferably 14 to 20.
- Specific examples of fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid, behenic acid, lignoselenic acid and the like.
- Examples of the monohydric alcohol include monohydric alcohols having 8 to 20 carbon atoms. More specifically, a saturated monohydric alcohol having 8 to 20 carbon atoms or an unsaturated monohydric alcohol having 8 to 20 carbon atoms can be used.
- the carbon number of the monohydric alcohol is preferably 12 to 22, more preferably 14 to 20, and still more preferably 16 to 20.
- Specific examples of monohydric alcohols include octyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, oleyl alcohol, nonadecyl alcohol, and branched alcohols thereof. .
- the fatty acid ester (C) is a compound having a structure in which an unsaturated fatty acid having 10 to 24 carbon atoms and a monohydric alcohol having 8 to 20 carbon atoms are ester-bonded.
- the unsaturated fatty acid preferably has 10 to 22 carbon atoms, more preferably 12 to 20 carbon atoms, and still more preferably 14 to 20 carbon atoms.
- the carbon number of the monohydric alcohol is preferably 12 to 22, more preferably 14 to 20, and still more preferably 16 to 20.
- the fatty acid ester (C) can be represented by the following general formula (9).
- R 9 is an alkyl group, alkenyl group or alkynyl group having 9 to 23 carbon atoms.
- R 9 is an alkenyl group are preferred.
- R 9 may be linear or branched.
- R 9 preferably has 12 to 22 carbon atoms, more preferably 14 to 20 carbon atoms, and still more preferably 16 to 20 carbon atoms.
- R 10 is an alkyl group, alkenyl group or alkynyl group having 8 to 20 carbon atoms.
- R 10 may be linear or branched.
- R 10 preferably has 10 to 20 carbon atoms, more preferably 12 to 20 carbon atoms, and still more preferably 14 to 20 carbon atoms.
- fatty acid ester (C) examples include, for example, octyl laurate, decyl laurate, lauryl laurate, tridecyl laurate, myristyl laurate, cetyl laurate, heptadecyl laurate, stearyl laurate, oleyl laurate, laurin
- Nonadecyl acid octyl myristate, decyl myristate, lauryl myristate, tridecyl myristate, myristyl myristate, cetyl myristate, heptadecyl myristate, stearyl myristate, oleyl myristate, nonadecyl myristate, octyl palmitate , Lauryl palmitate, tridecyl palmitate, myristyl palmitate, cetyl palmitate, heptadecyl palmitate, steary
- the fatty acid ester (C) has a melting point of 5 ° C. or less, more preferably 5 ° C. to ⁇ 10 ° C., and further preferably 5 ° C. to ⁇ 5 ° C., from the viewpoint of suppressing the fluff of the reinforcing fiber strand. If the melting point is more than 5 ° C, when the reinforcing fiber strand is stored for a long time in winter, the fatty acid ester becomes solid and the effect of suppressing fluff may be reduced.
- the melting point in the present invention was measured as follows. A measurement sample is collected to a height of about 10 mm in a capillary tube (both inner diameter 1 mm, outer diameter 2 mm or less, length 50 to 80 mm) with both ends open.
- melting point measuring apparatus M-565 manufactured by BUCHI
- the temperature is raised at a rate of 1 ° C./min from a temperature below the melting point.
- the temperature at which the measurement sample melts and becomes transparent is defined as the melting point.
- the weight average molecular weight of the fatty acid ester (C) is preferably 300 to 700, more preferably 400 to 600, and most preferably 500 to 600.
- the molecular weight is less than 300, the heat resistance of the fatty acid ester is lowered and volatilized in the drying step of the reinforced strand, which may reduce the fluff suppressing effect.
- the molecular weight is more than 700, friction increases and the fluff suppressing effect of the reinforcing fiber strand may be reduced.
- the sizing agent for reinforcing fibers of the present invention contains the aforementioned epoxy resin (A), unsaturated polyester (B) and fatty acid ester (C) as essential components.
- the unsaturated polyester (B) is preferably 30 to 300 parts by weight, more preferably 35 to 250 parts by weight, and still more preferably 40 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
- the amount is less than 30 parts by weight, the adhesiveness of the reinforcing fibers may be reduced with respect to the radical polymerization matrix resin.
- the texture of the reinforcing fiber strands becomes hard, and it may be easy to generate scratches in the processing step.
- the fatty acid ester (C) is preferably 1 to 15 parts by weight, more preferably 3 to 12 parts by weight, based on 100 parts by weight of the total of the epoxy resin (A) and the unsaturated polyester (B). More preferred is 10 parts by weight.
- the amount is less than 1 part by weight, the fluff suppressing effect of the reinforcing fiber strand may be reduced.
- the adhesiveness of the reinforcing fibers may be lowered with respect to the matrix resin.
- the total weight ratio of the epoxy resin (A), unsaturated polyester (B) and fatty acid ester (C) in the non-volatile content of the sizing agent is preferably 70% by weight or more, more preferably 70 to 95% by weight. Preferably, it is 75 to 90% by weight. When the amount is less than 70% by weight, the adhesiveness of the reinforcing fibers may be lowered with respect to the matrix resin.
- the non-volatile content in the present invention refers to an absolutely dry component when the sizing agent is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
- the sizing agent of the present invention may contain water from the viewpoints of safety to the human body during handling, prevention of disasters such as fire, and prevention of pollution of the natural environment.
- An organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, or methyl ethyl ketone may be used as long as the effects of the present invention are not impaired.
- the sizing agent of the present invention is self-emulsified and / or emulsified and dispersed in water.
- the average particle size of the sizing agent is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 0.01 to 1 ⁇ m, still more preferably 0.01 to 0.5 ⁇ m. When the average particle size is more than 10 ⁇ m, not only the sizing agent can be uniformly adhered to the reinforcing fibers, but also the sizing agent itself may be separated in a few days, and the storage stability may be poor and impractical.
- the average particle diameter as used in the field of this invention means the average value computed from the particle size distribution measured with the laser diffraction / scattering type particle size distribution measuring apparatus (LA-910 by Horiba).
- the sizing agent of the present invention may contain components other than the epoxy resin (A), unsaturated polyester (B) and fatty acid ester (C) described above as long as the effects of the present invention are not impaired.
- the other components include various surfactants, various smoothing agents, antioxidants, flame retardants, antibacterial agents, crystal nucleating agents, antifoaming agents, and the like. It may be used.
- the surfactant contains an epoxy resin (A), unsaturated polyester (B), fatty acid ester (C) or other resin that is water-insoluble or hardly soluble in the sizing agent
- the surfactant is used as an emulsifier. Emulsification can be carried out efficiently.
- the surfactant is not particularly limited, and a known one can be appropriately selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Surfactant may use together 1 type (s) or 2 or more types.
- Nonionic surfactants include, for example, alkylene oxide addition nonionic surfactants (higher alcohols, higher fatty acids, alkylphenols, styrenated phenols, benzylphenols, glycerin, pentaerythritol, sorbits, sorbitans, sorbitan esters, castors Oils, hydrogenated castor oil, higher aliphatic amines, fatty acid amides, oils and fats added with alkylene oxides such as ethylene oxide and propylene oxide (two or more types can be used together), and higher fatty acids added to polyalkylene glycols And the like, ethylene oxide / propylene oxide copolymers, esters of polyhydric alcohols and fatty acids, aliphatic alkanolamides, and the like.
- alkylene oxide addition nonionic surfactants higher alcohols, higher fatty acids, alkylphenols, styrenated phenols, benzylphenols, g
- nonionic surfactant examples include polyoxyalkylene straight chain such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, and polyoxyethylene cetyl ether.
- Polyalkylene branched primary alkyl ethers such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether; polyoxyethylene 1-hexyl hexyl ether, polyoxyethylene 1- Octyl hexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentyl heptyl ether, polyoxyethylene 1-heptyl pet Polyoxyalkylene branched secondary alkyl ethers such as tilether; polyoxyalkylene alkenyl ethers such as polyoxyethylene oleyl ether; polyoxys such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecylphenyl ether Alkylenealkylphenyl ether; polyoxyethylene tristyryl phenyl ether, polyoxyethylene distyryl phenyl
- anionic surfactant examples include carboxylic acid (salt), sulfate ester salt of higher alcohol / higher alcohol ether, sulfonate salt, phosphate ester salt of higher alcohol / higher alcohol ether, and the like.
- anionic surfactant examples include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, triethanolamine oleate; hydroxyacetic acid, potassium hydroxyacetate, Hydroxyl group-containing carboxylic acids (salts) such as lactic acid and potassium lactate; polyoxyalkylene alkyl ether acetic acid (salt) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); potassium trimellitic acid, potassium pyromellitic acid, etc.
- alkylbenzene sulfonic acid such as dodecylbenzene sulfonic acid (sodium salt); polyoxyalkylene alkyl ether sulfonic acid such as polyoxyethylene 2-ethylhexyl ether sulfonic acid (potassium salt) Salt); higher fatty acid amide sulfonic acid (salt) such as stearoylmethyltaurine (sodium), lauroylmethyltaurine (sodium), myristoylmethyltaurine (sodium), palmitoylmethyltaurine (sodium); N such as lauroylsarcosine acid (sodium) Acyl sarcosine acid (salt); alkyl phosphonic acid (salt) such as octyl phosphonate (potassium salt); aromatic phosphonic acid (salt) such as phenyl phosphonate (potassium
- cationic surfactant examples include lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl.
- Ammonium chloride beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methosulphate, oleyldimethylethylammonium ethosulphate, dioctyldimethylammonium chloride, di Alkyl quaternary ammonium salts such as uril dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, octadecyl diethyl methyl ammonium sulfate; (polyoxyethylene) lauryl amino ether lactate, stearyl amino ether lactate, di (polyoxyethylene) lauryl Methyl amino ether dimethyl phosphate, oleyl methyl ethyl ammonium etosulphate, di (polyoxyethylene) lauryl ethyl ammonium etosulphate, di (pol
- amphoteric surfactants include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt.
- 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaine stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amide betaine, sulfobetaine, etc.
- Examples include betaine amphoteric surfactants; amino acid amphoteric surfactants such as N-laurylglycine, N-lauryl ⁇ -alanine, N-stearyl ⁇ -alanine, sodium laurylaminopropionate, and the like.
- the weight ratio of the surfactant to the nonvolatile content of the sizing agent is preferably 5 to 30% by weight, more preferably 10 to 25% by weight, and further preferably 15 to 25% by weight.
- the concentration of the non-volatile content of the sizing agent of the present invention is not particularly limited, and is appropriately selected in consideration of the stability as an aqueous dispersion, the viscosity easy to handle as a product, and the like.
- the weight ratio of the non-volatile content in the entire sizing agent is preferably 10 to 100% by weight, more preferably 15 to 100% by weight, and particularly preferably 20 to 100% by weight.
- the total weight ratio of water and non-volatile components in the entire sizing agent is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 99% by weight or more, and particularly preferably 100% by weight.
- the above-mentioned aqueous dispersion and aqueous solution may contain a solvent other than water, such as an organic solvent, from the viewpoint of preventing thickening and solidification of the aqueous dispersion and aqueous solution over time. Even if it is not contained or contained, it is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less based on the entire sizing agent.
- the method for producing the sizing agent of the present invention as an aqueous dispersion is not particularly limited, and a known method can be employed. As described above, when each component constituting the sizing agent is produced, each is made into an aqueous dispersion, a method of mixing them, and each component constituting the sizing agent is put into warm water under stirring and emulsified and dispersed.
- the reinforcing fiber strand of the present invention is obtained by adhering the above-mentioned reinforcing fiber sizing agent to the raw material reinforcing fiber strand, and is a reinforcing fiber for reinforcing the matrix resin.
- the reinforcing fiber strand of the present invention is excellent in adhesiveness with the matrix resin.
- the matrix resin is preferably a thermosetting matrix resin because the effect of improving the adhesion by the sizing agent of the present invention is higher.
- the reinforcing fiber strand of the present invention is excellent in process passability due to less fluff generation, and excellent in long-term storage because there is no or little change in the sizing agent for reinforcing fibers over time.
- the adhering amount of the non-volatile component of the sizing agent to the raw material reinforcing fiber strand can be appropriately selected and may be set to a necessary amount for the reinforcing fiber strand to have a desired function, but the adhering amount is 0 with respect to the raw material reinforcing fiber strand. It is preferably 1 to 20% by weight.
- the adhesion amount is more preferably 0.1 to 10% by weight, and further preferably 0.5 to 5% by weight with respect to the raw material reinforcing fiber strand.
- the strand in the form of chopped fiber is more preferably 0.5 to 20% by weight, and further preferably 1 to 10% by weight.
- the adhesion amount of the sizing agent is small, the effects of the present invention relating to heat resistance, resin impregnation property, and adhesiveness are difficult to obtain, and the binding property of the reinforcing fiber strands is insufficient, and the handling property may be deteriorated.
- the amount of the sizing agent attached is too large, the reinforcing fiber strands become too stiff and the handling property becomes worse, and the resin impregnation property becomes worse at the time of composite molding.
- a method for producing a reinforcing fiber strand includes a treatment liquid containing the above-described sizing agent, having a nonvolatile weight ratio of 0.5 to 10% by weight, and a total weight ratio of water and nonvolatile components of 90% by weight or more. And a preparation step of preparing, and an attachment step of attaching the treatment liquid to the raw material reinforcing fiber strand so that the amount of non-volatile matter attached to the raw material reinforcing fiber strand is 0.1 to 20% by weight.
- the weight ratio of the nonvolatile content in the treatment liquid is more preferably 0.5 to 10% by weight, and further preferably 1 to 5% by weight.
- the total weight ratio of water and nonvolatile components is more preferably 95% by weight or more, further preferably 99% by weight or more, and particularly preferably 100% by weight.
- the preferable adhering amount of the nonvolatile content is as described in the previous paragraph.
- the method for adhering the sizing agent to the raw material reinforcing fiber strand is not particularly limited as long as the sizing agent is attached to the raw material reinforcing fiber strand by a kiss roller method, roller dipping method, spray method or other known methods. Good. Among these methods, the roller dipping method is preferable because the sizing agent can be uniformly attached to the raw material reinforcing fiber strand.
- the drying method of the obtained deposit For example, it can heat-dry with a heating roller, a hot air, a hot plate, etc.
- all the constituent components of the sizing agent may be attached after mixing, or the constituent components may be attached separately in two or more stages. .
- it is other than an epoxy resin (A), unsaturated polyester (B), and fatty acid ester (C),
- Thermosetting resins such as vinyl ester resin and a phenol resin, and / or
- a thermoplastic resin such as a polyolefin resin, a polyester resin, a nylon resin, or an acrylic resin may be attached to the raw material reinforcing fiber strand.
- the reinforcing fiber strand of the present invention is used as a reinforcing fiber of a composite material using various resins as a matrix resin, and the form to be used may be a long fiber form or a chopped fiber form.
- various inorganic fibers such as carbon fiber, glass fiber and ceramic fiber, aramid fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate
- strands such as various organic fibers such as fibers, polyarylate fibers, polyacetal fibers, PBO fibers, polyphenylene sulfide fibers, and polyketone fibers.
- the (raw material) reinforced fiber strand includes carbon fiber, aramid fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal. At least one strand selected from fibers, PBO fibers, polyphenylene sulfide fibers and polyketone fibers is preferable, and carbon fiber strands are more preferable.
- the fiber-reinforced composite material of the present invention includes a matrix resin and the above-described reinforcing fiber strand. Reinforcing fiber strands are treated with the sizing agent of the present invention, and the sizing agent is uniformly attached to the fibers, so that the affinity with the reinforcing fiber strands and the matrix resin is good, and a fiber-reinforced composite material having excellent adhesion is obtained.
- the matrix resin refers to a matrix resin made of a thermosetting resin or a thermoplastic resin, and may include one or more kinds.
- thermosetting resin An epoxy resin, a phenol resin, unsaturated polyester resin, a vinyl ester resin, an acrylic resin, cyanate ester resin, a polyimide resin etc. are mentioned.
- the thermoplastic matrix resin is not particularly limited, and is a polyolefin resin, polyamide resin, polycarbonate resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, polymethyl methacrylate resin, polyphenylene sulfide resin, polyetherimide resin, Examples include polyether ketone resins.
- thermosetting matrix resin is preferable, an epoxy resin, an unsaturated polyester resin, and a vinyl ester resin are more preferable, and an epoxy resin is most preferable because the adhesive improvement effect by the sizing agent of the present invention is higher.
- the epoxy resin is a compound having a reactive epoxy group in the molecular structure, and is cured by mixing the curing agent and heating the epoxy group to form a crosslinked network.
- an epoxy resin the thing similar to the above-mentioned epoxy resin (A) which is an essential component of a sizing agent can be mentioned.
- These matrix resins may be partially or wholly modified for the purpose of further improving the adhesiveness with the reinforcing fiber strands.
- the method for producing the fiber reinforced composite material is not particularly limited, and known methods such as compound injection molding using chopped fibers and long fiber pellets, press molding using UD sheets and woven sheets, and other filament winding molding can be employed.
- the curing agent is mixed and heated under pressure or normal pressure to produce a fiber reinforced composite material, and the curing agent and curing accelerator are mixed.
- the content of the reinforcing fiber strand in the fiber reinforced composite material is not particularly limited, and may be appropriately selected depending on the type of fiber, the form, the type of matrix resin, and the like. 70% by weight is preferable, and 20 to 60% by weight is more preferable.
- the composite material interface property evaluation apparatus HM410 manufactured by Toei Sangyo Co., Ltd. was used, and the adhesiveness was evaluated by the microdroplet method. Carbon fiber filaments are taken out from the carbon fiber strands obtained in the examples and comparative examples, and set in a sample holder. A drop of each matrix resin mixed with a curing agent and a curing accelerator was formed on the carbon fiber filament, and the drop was cured by the following curing method to obtain a measurement sample.
- the measurement sample was set in the apparatus, the drop was sandwiched between apparatus blades, the carbon fiber filament was run on the apparatus at a speed of 0.06 mm / min, and the maximum extraction load F when the drop was extracted from the carbon fiber filament was measured.
- the matrix resin is an epoxy resin in Examples 1 to 10 and Comparative Examples 1 to 4, and 7 to 9, an unsaturated polyester resin in Examples 11 to 14 and Comparative Example 5, and in Examples 15 to 18 and Comparative Example 6. Vinyl ester resin was used.
- Epoxy resin A drop of matrix resin adjusted to 100 parts by weight of epoxy resin JER828 (manufactured by Mitsubishi Chemical Corporation) and 3 parts by weight of DICY (manufactured by Mitsubishi Chemical Corporation) is heated at 80 ° C. ⁇ 1 hour, 150 ° C. ⁇ 3 hours. Cured.
- Unsaturated polyester resin Unsaturated polyester resin Rigolac M540 (manufactured by Showa Denko KK) 100 parts by weight, Parmec N (manufactured by NOF Corporation) 2 parts by weight, drop of matrix resin 80 ° C. ⁇ 1 hour, 150 C. for 3 hours to cure.
- Vinyl ester resin Vinyl ester resin Lipoxy R-806 (manufactured by Showa Denko KK) 100 parts by weight, Percure O (manufactured by NOF Corporation) 2 parts by weight, drop of matrix resin 80 ° C. ⁇ 1 hour, 150 C. for 3 hours to cure.
- ⁇ Fiber storage> The carbon fiber strands obtained in Examples and Comparative Examples are stored at 100 ° C. for 10 days, and the difference between the hardness of the carbon fiber strand after storage and the hardness of the carbon fiber strand before storage is determined. Judged to be less.
- the hardness of the carbon fiber strand (length: about 50 cm) was measured with a texture tester (HANDLE-O-METERHOM-2, manufactured by Daiei Kagaku Seisakusho Co., Ltd., slit width 10 mm).
- Example 1 JER1001, unsaturated polyester (B-1), oleyl oleate, POE (150) hydrogenated castor oil ether, PO / EO (25/75) polyether (so that the non-volatile composition of the treating agent shown in Table 1 is obtained)
- the molecular weight of 16000 was charged into an emulsifier, and water was gradually added under stirring to phase-invert and emulsify to obtain an aqueous dispersion of a sizing agent having a nonvolatile content concentration of 30 wt%.
- the obtained sizing agent aqueous dispersion is diluted with water to prepare a sizing agent emulsion having a non-volatile content concentration of 3% by weight, and dipped and impregnated with sizing agent-untreated carbon fiber strands (fineness 800 tex, number of filaments 12,000). After that, it was dried with hot air at 105 ° C. for 15 minutes to obtain a sizing agent-treated carbon fiber strand having a theoretical adhesion amount of 1.0%. About this sizing agent and this strand, each characteristic value was evaluated by the above-mentioned method. Adhesiveness and fuzziness were evaluated using carbon fiber strands before evaluation of fiber storability and carbon fiber strands after evaluation of fiber storability. The results are shown in Table 1.
- Example 1 a sizing agent-treated carbon fiber strand was obtained in the same manner as in Example 1 except that the sizing agent emulsion was adjusted so that the non-volatile composition of the treating agents shown in Tables 1 to 3 was obtained. Evaluated. The evaluation results of each characteristic value are shown in Tables 1 to 3.
- the sizing agents of the examples are excellent in long-term stability.
- the fiber strand of an Example is excellent in adhesiveness with a matrix resin, and fluff generation
- the fiber storage property is excellent, the adhesiveness is excellent even after fiber storage, and the occurrence of fluff is suppressed.
- the fiber reinforced composite material in which the matrix resin is reinforced with the reinforcing fiber is used for automobile applications, aerospace applications, sports / leisure applications, general industrial applications, and the like.
- the reinforcing fiber include various inorganic fibers such as carbon fiber, glass fiber, and ceramic fiber, and various organic fibers such as aramid fiber, polyamide fiber, and polyethylene fiber.
- the sizing agent of this invention can be used conveniently with respect to the reinforced fiber for reinforcing a matrix resin.
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Abstract
Description
強化繊維複合材料の機械強度を向上させるためには、マトリックス樹脂と強化繊維の接着性が重要となり、上記のエポキシ樹脂、ラジカル重合系のマトリックス樹脂に対して、強化繊維の接着性が向上するサイジング剤(例えば、特許文献1、2等)が提案されている。
また、強化繊維によっては、伸度が小さく、且つ脆い性質を有するものもある。従来のサイジング剤が付与されたこれらの強化繊維は、加工工程における機械的摩擦等によって、毛羽発生や繊維切断などの問題が起こることがあった。
よって、繊維強化複合材料の分野において、強化繊維とマトリックス樹脂との親和性を高めて、強固に接着させることができ、強化繊維ストランドの毛羽抑制、経時硬化抑制を可能とし、さらには長期保管安定性に優れたサイジング剤の開発が望まれている。
不飽和二塩基酸(b1)のモル数<ビスフェノール類のアルキレンオキサイド付加物(b2)のモル数 (I)
前記マトリックス樹脂は、熱硬化性樹脂であることが好ましい。
本発明の強化繊維ストランドは、サイジング剤の経時的な変化がない又は少ないため、長期間保管しても擦過毛羽性及びマトリックス樹脂との接着性の低下を抑制できる。本発明の強化繊維ストランドを使用することにより、優れた物性を有する強化繊維複合材料が得られる。
エポキシ樹脂(A)は、本発明のサイジング剤の必須成分である。エポキシ樹脂(A)とは、分子構造内に反応性のエポキシ基を2個以上有する化合物である。エポキシ樹脂(A)としては、エピクロルヒドリンと活性水素化合物から得られるグリシジルエーテル型が代表的であり、その他にグリシジルエステル型、グリシジルアミン型、脂環型等が挙げられる。エポキシ樹脂(A)は、1種でもよく、2種以上を併用してもよい。
上記の芳香族エポキシ樹脂としては、ハイドロキノン、レゾルシン、ピロカテコールなどの単核多価フェノール化合物のポリグリシジルエーテル化合物;ジヒドロキシナフタレン、ビフェノール、ビスフェノールF、ビスフェノールA、フェノールノボラック、オルソクレゾールノボラック、レゾルシンノボラック、ビスフェノールFノボラック、ビスフェノールAノボラック、ジシクロペンタジエン変性フェノール、トリフェニルメタン、テトラフェニルエタンなどの多核多価フェノール化合物のポリグリシジルエーテル化合物などが挙げられる。
酸価5未満の不飽和ポリステル(B)は、本発明のサイジング剤の必須成分である。当該酸価が5以上の場合、強化繊維ストランドが経時的に硬くなり、かつ、サイジング剤の長期保管安定性が低下する。当該酸価は、4.5以下が好ましく、4以下がより好ましく、3.5以下がさらに好ましい。ここで酸価とは、試料1gを中和するのに必要な水酸化カリウムのmg数で表わし、JIS K 2501:2003に準拠して測定したものをいう。
二価のアルコールとしては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ブチレングリコール、ペンタンジオール、ヘキサンジオール、ビスフェノール類、ビスフェノール類のアルキレンオキサイド付加物等が挙げられる。これらの中でも、ビスフェノール類のアルキレンオキサイド付加物が好ましい。ビスフェノール類及びビスフェノール類のアルキレンオキサイド付加物については、後述する。
不飽和二塩基酸(b1)のモル数<ビスフェノール類のアルキレンオキサイド付加物(b2)のモル数 (I)
また、強化繊維とマトリックス樹脂の接着性向上の点から、反応性成分は、不飽和二塩基酸のエステル化物を実質的に含まないほうが好ましい。具体的には、反応性成分に占める不飽和二塩基酸のエステル化物の割合は、2モル%以下が好ましく、1モル%以下がより好ましく、0モル%がさらに好ましい。
1官能の活性水素基を有する化合物としては、1価アルコール、2級アミン、1価チオール等が挙げられる。
脂肪酸エステル(C)は、本発明のサイジング剤の必須成分である。エポキシ樹脂(A)及びエポキシ樹脂(A)と不飽和ポリエステル(B)に加え、さらには脂肪酸エステル(C)を含むことにより、本発明の強化繊維用サイジング剤は、強化繊維に対してマトリックス樹脂との優れた接着性を付与できる。また、強化繊維ストランドの毛羽発生及び経時硬化を抑制できる。さらには、長期保管安定性に優れる。
脂肪酸としては、炭素数10~24の飽和脂肪酸又は炭素数10~24の不飽和脂肪酸が挙げられる。強化繊維ストランドの毛羽抑制の点から、炭素数10~24の不飽和脂肪酸が好ましい。脂肪酸の炭素数は、10~22が好ましく、12~20がより好ましく、14~20がさらに好ましい。
脂肪酸の具体例としては、カプリン酸、ラウリン酸、ミリスチル酸、パルミチル酸、ステアリン酸、オレイン酸、アラキン酸、ベヘニン酸、リグノセレン酸等が挙げられる。
一価アルコールの具体例として、オクチルアルコール、デシルアルコール、ラウリルアルコール、トリデシルアルコール、ミリスチルアルコール、セチルアルコール、ヘプタデシルアルコール、ステアリルアルコール、オレイルアルコール、ノナデシルアルコール及びそれらの分岐のアルコール等が挙げられる。
R9-COOR10 (9)
一般式(9)において、R9は炭素数9~23のアルキル基、アルケニル基又は、アルキニル基である。R9はアルケニル基が好ましい。R9は直鎖であっても分岐であってもよい。R9の炭素数は、12~22が好ましく、14~20がより好ましく、16~20がさらに好ましい。
一般式(9)において、R10は炭素数8~20のアルキル基、アルケニル基又は、アルキニル基である。R10は直鎖であっても分岐であってもよい。R10の炭素数は、10~20が好ましく、12~20がより好ましく、14~20がさらに好ましい。
本発明の強化繊維用サイジング剤は、前述のエポキシ樹脂(A)、不飽和ポリエステル(B)及び脂肪酸エステル(C)を必須に含有するものである。
不飽和ポリエステル(B)は、エポキシ樹脂(A)100重量部に対して、30~300重量部であることが好ましく、35~250重量部がより好ましく、40~200重量部がさらに好ましい。30重量部未満の場合、ラジカル重合系のマトリックス樹脂に対して、強化繊維の接着性が低下することがある。一方、300重量部超の場合、強化繊維ストランドの風合いが硬くなり、加工工程での擦過毛羽が発生し易くなることがある。
なお、本発明でいう平均粒子径とは、レーザー回折/散乱式粒度分布測定装置(堀場製LA-910)で測定された粒度分布より算出された平均値をいう。
界面活性剤としては、特に限定されず、非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤及び両性界面活性剤から、公知のものを適宜選択して使用することができる。界面活性剤は、1種又は2種以上を併用してもよい。
また、サイジング剤全体に占める水と不揮発分の合計の重量割合は、90重量%以上が好ましく、95重量%以上がより好ましく、99重量%以上がさらに好ましく、100重量%が特に好ましい。90重量%未満の場合、すなわち、熱処理時に不揮発分として残存しない前述の有機溶剤やその他低沸点化合物を10重量%以上含有する場合、取扱い時の人体への安全性や、自然環境の汚染防止の観点で好ましくないことがある。
本発明の強化繊維ストランドは、原料強化繊維ストランドに対して、上記の強化繊維用サイジング剤を付着させたものであり、マトリックス樹脂を補強するための強化繊維である。本発明の強化繊維ストランドは、マトリックス樹脂との接着性に優れる。マトリックス樹脂は、本発明のサイジング剤による接着性向上効果がより高い点から、熱硬化性マトリックス樹脂が好ましい。本発明の強化繊維ストランドは、毛羽発生が少ないので工程通過性に優れ、強化繊維用サイジング剤の経時的な変化がない又は少ないため、長期保管性に優れる。
サイジング剤の付着量が少ないと、耐熱性、樹脂含浸性、接着性に関する本発明の効果が得られにくく、また、強化繊維ストランドの集束性が不足し、取扱い性が悪くなることがある。また、サイジング剤の付着量が多過ぎると、強化繊維ストランドが剛直になり過ぎて、かえって取扱い性が悪くなったり、コンポジット成型の際に樹脂含浸性が悪くなったりすることがあり好ましくない。
調製工程において、処理液に占める不揮発分の重量割合は、0.5~10重量%がより好ましく、1~5重量%がさらに好ましい。水と不揮発分の合計の重量割合は、95重量%以上であることがより好ましく、99重量%以上であることがさらに好ましく、100重量%が特に好ましい。
付着工程において、好ましい不揮発分の付着量については、前段落の通りである。サイジング剤を原料強化繊維ストランドに付着させる方法については、特に限定はないが、サイジング剤をキスローラー法、ローラー浸漬法、スプレー法その他公知の方法で、原料強化繊維ストランドに付着させる方法であればよい。これらの方法のうちでも、ローラー浸漬法が、サイジング剤を原料強化繊維ストランドに均一付着できるので好ましい。
得られた付着物の乾燥方法については、特に限定はなく、例えば、加熱ローラー、熱風、熱板等で加熱乾燥することができる。
本発明の繊維強化複合材料は、マトリックス樹脂と前述の強化繊維ストランドを含むものである。強化繊維ストランドは本発明のサイジング剤により処理されて、サイジング剤が均一に付着しており、強化繊維ストランド及びマトリックス樹脂との親和性が良好となり、接着性に優れた繊維強化複合材料となる。ここで、マトリックス樹脂とは、熱硬化性樹脂又は熱可塑性樹脂からなるマトリックス樹脂をいい、1種又は2種以上含んでいてもよい。熱硬化性樹脂としては、特に制限はなく、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、アクリル樹脂、シアネートエステル樹脂、ポリイミド樹脂等が挙げられる。熱可塑性マトリックス樹脂としては、特に制限はなく、ポリオレフィン系樹脂、ポリアミド系樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアセタール樹脂、ABS樹脂、フェノキシ樹脂、ポリメチルメタクリレート樹脂、ポリフェニレンサルフィド樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂等が挙げられる。これらの中でも本発明のサイジング剤による接着性向上効果がより高い点から、熱硬化性マトリックス樹脂が好ましく、エポキシ樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂がさらに好ましく、エポキシ樹脂が最も好ましい。ここで、エポキシ樹脂とは、分子構造内に反応性のエポキシ基を有する化合物であり、硬化剤を混合して加熱することによりエポキシ基が架橋ネットワーク化することで硬化する。エポキシ樹脂としては、サイジング剤の必須成分である前述のエポキシ樹脂(A)と同様なものを挙げることができる。これらマトリックス樹脂は、強化繊維ストランドとの接着性をさらに向上させるなどの目的で、その一部又は全部が変性したものであっても差し支えない。
熱硬化性マトリックス樹脂と強化繊維ストランドを混練する際には、硬化剤を混合して加圧または常圧下で加熱して繊維強化複合材料を製造する方法や、硬化剤、硬化促進剤を混合して常温で繊維強化複合材料を製造する方法がある。
繊維強化複合材料中の強化繊維ストランドの含有量についても特に限定はなく、繊維の種類、形態、マトリックス樹脂の種類などにより適宜選択すればよいが、得られる繊維強化複合材料に対して、5~70重量%が好ましく、20~60重量%がより好ましい。
不揮発分濃度が3.0重量%である各処理剤エマルジョンを50℃に調節された恒温槽で保管し、溶液の外観を目視で確認し、下記の評価基準で溶液安定性を判定した。
◎ :60日間分離無し。
○ :30日間分離無し、60日以内には分離。
△ :7日間分離無し、30日以内に分離。
× :7日間以内に分離。
××:乳化当日に分離、または乳化できない。
複合材料界面特性評価装置HM410(東栄産業株式会社製)を使用し、マイクロドロップレット法により接着性を評価した。
実施例及び比較例で得られた炭素繊維ストランドより、炭素繊維フィラメントを取り出し、試料ホルダーにセッティングする。硬化剤や硬化促進剤を混合した各マトリックス樹脂のドロップを炭素繊維フィラメント上に形成させ、下記の硬化方法によりドロップを硬化させ、測定用の試料を得た。測定試料を装置にセッティングし、ドロップを装置ブレードで挟み、炭素繊維フィラメントを装置上で0.06mm/分の速度で走行させ、炭素繊維フィラメントからドロップを引き抜く際の最大引き抜き荷重Fを測定した。
次式により界面剪断強度τを算出し、炭素繊維フィラメントとマトリックス樹脂との接着性を評価した。
界面剪断強度τ(単位:MPa)=F/πdl
(F:最大引き抜き荷重 d:炭素繊維フィラメント直径 l:ドロップの引き抜き方向の粒子径)
マトリックス樹脂は、実施例1~10及び比較例1~4、7~9ではエポキシ樹脂を、実施例11~14及び比較例5では不飽和ポリエステル樹脂を、実施例15~18及び比較例6ではビニルエステル樹脂を用いた。
エポキシ樹脂:エポキシ樹脂JER828(三菱化学株式会社製)100重量部、DICY(三菱化学株式会社製)3重量部に調整されたマトリックス樹脂のドロップを80℃×1時間、150℃×3時間加熱し硬化させた。
不飽和ポリエステル樹脂:不飽和ポリエステル樹脂リゴラックM540(昭和電工株式会社製)100重量部、パーメックN(日油株式会社製)2重量部に調整されたマトリックス樹脂のドロップを80℃×1時間、150℃×3時間加熱し硬化させた。
ビニルエステル樹脂:ビニルエステル樹脂リポキシR-806(昭和電工株式会社製)100重量部、パーキュアーO(日油株式会社製)2重量部に調整されたマトリックス樹脂のドロップを80℃×1時間、150℃×3時間加熱し硬化させた。
TM式摩擦抱合力試験機TM-200(大栄科学精器製作所(株)製)を用い、ジグザグに配置した鏡面クロムメッキステンレス針3本を介して50gの張力で、実施例及び比較例で得られた炭素繊維ストランドを1000回擦過させ(往復運動速度300回/分)、炭素繊維ストランドの毛羽たちの状態を下記基準で目視判定した。
◎:擦過前と同じく毛羽発生が全く見られなかった。
○:数本の毛羽は見られたものの、実用上全く問題ないレベルであった。
△:毛羽立ちが多くみられ、糸切れも若干確認できた。
×:毛羽立ち及び単糸の糸切れが非常に多く確認できた。
実施例及び比較例で得られた炭素繊維ストランドを100℃で10日間保管し、保管後の炭素繊維ストランドの硬度と保管前の炭素繊維ストランドの硬度の差を求め、差が小さいほど経時硬化が少ないと判断した。炭素繊維ストランド(長さ:約50cm)の硬度は、風合い試験機(HANDLE-O-METERHOM-2 大栄科学精器製作所(株)製、スリット幅10mm)で測定した。
JER1001:三菱化学株式会社製、固形ビスフェノールA型エポキシ樹脂、エポキシ当量450~500
JER834:三菱化学株式会社製、半固形ビスフェノールA型エポキシ樹脂、エポキシ当量230~270
JER828:三菱化学株式会社製、液状ビスフェノールA型エポキシ樹脂、エポキシ当量184~194
JER807:三菱化学株式会社製、液状ビスフェノールF型エポキシ樹脂、エポキシ当量160~175
JER157S65:三菱化学株式会社製、ビスフェノールAノボラック型エポキシ樹脂、エポキシ当量200~220
(合成例B-1)
無水マレイン酸0.9モルとビスフェノールAのエチレンオキサイド4モル付加物1.0モルを140℃で5時間反応させて、酸価2.5の不飽和ポリエステル(B-1)を得た。重量平均分子量(Mw)は3051であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は1.6であった。
無水マレイン酸0.8モルとビスフェノールAのエチレンオキサイド2モル付加物1.0モルを140℃で3時間反応させて、酸価3.5の不飽和ポリエステル(B-2)を得た。重量平均分子量(Mw)は1626であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は1.7であった。
フマル酸0.85モルとビスフェノールAのエチレンオキサイド3モル付加物1.0モルを170℃で8時間反応させて、酸価4.5の不飽和ポリエステル(B-3)を得た。重量平均分子量(Mw)は3444であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は1.9であった。
無水マレイン酸0.9モルとビスフェノールAのプロピレンオキサイド3モル付加物1.0モルを150℃で5時間反応させて、酸価2.0の不飽和ポリエステル(B-4)を得た。重量平均分子量(Mw)は2903であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は1.7であった。
(合成例b-1)
無水マレイン酸1.0モルとビスフェノールAのエチレンオキサイド2モル付加物1.0モルを135℃で2時間反応させて、酸価60の不飽和ポリエステル(b-1)を得た。重量平均分子量(Mw)は3872であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は2.0であった。
無水マレイン酸1.0モルとビスフェノールAのエチレンオキサイド2モル付加物1.0モルを135℃で5時間反応させて、更に170℃で5時間反応させて、酸価6.3の不飽和ポリエステル(b-2)を得た。重量平均分子量(Mw)は5736であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は2.3であった。
無水マレイン酸1.0モルとビスフェノールAのエチレンオキサイド4モル付加物1.0モルを160℃で5時間反応させて、酸価10の不飽和ポリエステル(b-3)を得た。重量平均分子量(Mw)は4860であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は2.0であった。
無水マレイン酸1.0モルとビスフェノールAのエチレンオキサイド3モル付加物1.0モルを140℃で4時間反応させて、酸価30の不飽和ポリエステル(b-4)を得た。重量平均分子量(Mw)は4860であり、重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)は2.1であった。
オレイン酸オレイル:融点4℃
オレイン酸ラウリル:融点11℃
ステアリン酸イソオクチル:融点10℃
表1に示す処理剤の不揮発分組成になるように、JER1001、不飽和ポリエステル(B-1)、オレイン酸オレイル、POE(150)硬化ヒマシ油エーテル、PO/EO(25/75)ポリエーテル(分子量16000)を乳化装置に仕込み、撹拌下水を序々に加え転相乳化させ、不揮発分濃度30重量%のサイジング剤水分散体を得た。得られたサイジング剤水分散体を水で希釈して、不揮発分濃度3重量%のサイジング剤エマルジョンを調製し、サイジング剤未処理炭素繊維ストランド(繊度800tex、フィラメント数12000本)を浸漬・含浸させた後、105℃で15分間熱風乾燥させて、理論付着量が1.0%であるサイジング剤処理炭素繊維ストランドを得た。本サイジング剤及び本ストランドについて、前述の方法により各特性値を評価した。接着性と擦過毛羽性については、繊維保管性評価前の炭素繊維ストランドと繊維保管性評価後の炭素繊維ストランドを用いて、それぞれ評価した。その結果を表1に示した。
実施例1において、表1~3に示す処理剤の不揮発分組成になるようにサイジング剤エマルジョンを調整した以外は実施例1と同様にして、サイジング剤処理炭素繊維ストランドを得て、各特性値を評価した。各特性値の評価結果を表1~3に示す。
Claims (12)
- エポキシ樹脂(A)、酸価5未満の不飽和ポリエステル(B)及び脂肪酸エステル(C)を含有する、強化繊維用サイジング剤。
- 前記エポキシ樹脂(A)100重量部に対して、前記不飽和ポリエステル(B)が30~300重量部であり、前記エポキシ樹脂(A)と前記不飽和ポリエステル(B)との合計100重量部に対して、前記脂肪酸エステル(C)が1~15重量部である、請求項1に記載の強化繊維用サイジング剤。
- 前記不飽和ポリエステル(B)の重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)が1.2~2.1である、請求項1又は2に記載の強化繊維用サイジング剤。
- 前記不飽和ポリエステル(B)が、不飽和二塩基酸(b1)とビスフェノール類のアルキレンオキサイド付加物(b2)との縮合物を含む、請求項1~3のいずれかに記載の強化繊維用サイジング剤。
- 前記不飽和ポリエステル(B)が、不飽和二塩基酸(b1)とビスフェノール類のアルキレンオキサイド付加物(b2)とを下記式(I)を満たす割合で含む反応性成分を反応させて得られたものである、請求項1~4のいずれかに記載の強化繊維用サイジング剤。
不飽和二塩基酸(b1)のモル数<ビスフェノール類のアルキレンオキサイド付加物(b2)のモル数 (I) - 前記不飽和ポリエステル(B)の酸価が4.5以下である、請求項1~5のいずれかに記載の強化繊維用サイジング剤。
- 前記脂肪酸エステル(C)の融点が5℃以下である、請求項1~6のいずれかに記載の強化繊維用サイジング剤。
- 前記脂肪酸エステル(C)が、炭素数10~24の不飽和脂肪酸と炭素数8~20の一価アルコールがエステル結合した構造を持つエステルである、請求項1~7のいずれかに記載の強化繊維用サイジング剤。
- サイジング剤の不揮発分に占める、前記エポキシ樹脂(A)と前記不飽和ポリエステル(B)と前記脂肪酸エステル(C)の合計の重量割合が、70重量%以上である、請求項1~8のいずれかに記載の強化繊維用サイジング剤。
- 原料強化繊維ストランドに対して、請求項1~9のいずれかに記載の強化繊維用サイジング剤を付着させた、強化繊維ストランド。
- マトリックス樹脂と、請求項10に記載の強化繊維ストランドとを含む、繊維強化複合材料。
- 前記マトリックス樹脂が熱硬化性樹脂である、請求項11に記載の繊維強化複合材料。
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Cited By (10)
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WO2020004523A1 (ja) * | 2018-06-29 | 2020-01-02 | 三菱ケミカル株式会社 | サイジング剤、強化繊維束、繊維強化樹脂成形材料及び繊維強化複合材料 |
JP2020002518A (ja) * | 2018-06-26 | 2020-01-09 | 三洋化成工業株式会社 | 繊維用集束剤、繊維束、繊維製品、プリプレグ及び成形体 |
JP2021055200A (ja) * | 2019-09-27 | 2021-04-08 | 竹本油脂株式会社 | 炭素繊維用サイズ剤、及び炭素繊維 |
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JP7281352B2 (ja) | 2018-06-26 | 2023-05-25 | 三洋化成工業株式会社 | 繊維用集束剤、繊維束、繊維製品、プリプレグ及び成形体 |
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CN112292488B (zh) * | 2018-06-29 | 2023-12-29 | 三菱化学株式会社 | 上浆剂、增强纤维束、纤维增强树脂成型材料及纤维增强复合材料 |
CN112292488A (zh) * | 2018-06-29 | 2021-01-29 | 三菱化学株式会社 | 上浆剂、增强纤维束、纤维增强树脂成型材料及纤维增强复合材料 |
US20210108363A1 (en) * | 2018-06-29 | 2021-04-15 | Mitsubishi Chemical Corporation | Sizing agent, reinforcement fiber tow, fiber-reinforced resin-molding material, and fiber-reinforced composite material |
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JP5730457B1 (ja) | 2015-06-10 |
CN105378176B (zh) | 2017-05-17 |
JPWO2015045618A1 (ja) | 2017-03-09 |
TWI648451B (zh) | 2019-01-21 |
KR102190010B1 (ko) | 2020-12-11 |
TW201525233A (zh) | 2015-07-01 |
CN105378176A (zh) | 2016-03-02 |
KR20160061319A (ko) | 2016-05-31 |
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