CN105378176A - Sizing agent for reinforcing fiber and application therefor - Google Patents

Sizing agent for reinforcing fiber and application therefor Download PDF

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Publication number
CN105378176A
CN105378176A CN201480039921.7A CN201480039921A CN105378176A CN 105378176 A CN105378176 A CN 105378176A CN 201480039921 A CN201480039921 A CN 201480039921A CN 105378176 A CN105378176 A CN 105378176A
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Prior art keywords
reinforcing fiber
sizing agent
acid
weight
ester
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CN105378176B (en
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桥本善夫
中川干生
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Matsumoto Yushi Seiyaku Co Ltd
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Matsumoto Yushi Seiyaku Co Ltd
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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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)
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Abstract

The purpose of the present invention is to provide: a sizing agent capable of applying, to reinforcing fiber, properties of excellent adhesion to matrix resin, said sizing agent being capable of suppressing fluff generation and hardening over time of reinforcing fiber strands and also having excellent long-term storage stability; and reinforcing fiber strands and a fiber reinforced composite material that use same. This sizing agent for reinforcing fiber contains an epoxy resin (A), an unsaturated polyester (B) having an acid value of less than 5, and a fatty acid ester (C). The aforementioned problems can be solved by using this sizing agent for reinforcing fiber.

Description

Reinforcing fiber sizing agent and uses thereof
Technical field
The present invention relates to reinforcing fiber sizing agent and uses thereof.Specifically, reinforcing fiber sizing agent, the reinforcing fiber bundle employing this sizing agent and fiber reinforced composite material that matrix resin uses is related to strengthening.
Background technology
The fiber reinforced composite material enhancing plastic material (being called as matrix resin) with various synthetic fiber is widely used at mobile applications, aerospace purposes, Sport & Casual purposes, general industrial applications etc.As the fiber that can be used in these composites, the various organic fibers such as the various inorfil such as carbon fiber, glass fibre, ceramic fibre, aramid fiber, polyamide fiber, polyethylene fiber can be enumerated.These various synthetic fiber normally manufacture long filament shape, the sheet intermediate materials of so-called one direction preimpregnation thing is processed into afterwards by hot melt or cylinder winding method etc., or process with filament winding method, optionally be processed into textiles or staple fiber shape etc., be used as reinforcing fiber through various high accuracy manufacturing procedure.
As the matrix resin of reinforced fiber composite, widely use epoxy resin.Except epoxy resin, also use unsaturated polyester resin, vinylester resin, acrylic resin etc. as the matrix resin of radical polymerization syzygy.
For improving the mechanical strength of reinforced fiber composite, the cementability of matrix resin and reinforcing fiber becomes important, for the matrix resin of above-mentioned epoxy resin, radical polymerization syzygy, the sizing agent (such as, patent document 1,2 etc.) that the cementability having proposed reinforcing fiber improves.
But, although the sizing agent recorded in patent document 1 or patent document 2 can improve the cementability of reinforcing fiber to the matrix resin of epoxy resin or radical polymerization syzygy, but the attached reinforcing fiber giving sizing agent along with the time can be hardening, the problem sometimes causing fluffing or the cementability of matrix resin is reduced.Further, the problem of the long-term storing stability of sizing agent is sometimes caused.
In addition, according to the difference of reinforcing fiber, also have and there is the little and reinforcing fiber of fragile character of percentage elongation.Give these reinforcing fibers of sizing agent in the past sometimes because of the mechanical friction etc. in manufacturing procedure, and cause the problems such as fluffing, fibre cutting.
Therefore, in the field of fiber reinforced composite material, expect to develop a kind of sizing agent, it can make the compatibility between reinforcing fiber and matrix resin improve, and bonding securely, and the fluffing of reinforcing fiber bundle can be suppressed, suppress along with time hardening, and long-term storing stability is excellent.
Prior art document
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 53-52796 publication
Patent document 2: Japanese Laid-Open Patent Publication 57-173150 publication
Summary of the invention
The problem that invention will solve
In view of this technical background in the past, the object of the present invention is to provide a kind of sizing agent, it can give cementability excellent between matrix resin for reinforcing fiber, can suppress the fluffing of reinforcing fiber bundle and harden in time, and long-term storing stability is excellent; And use reinforcing fiber bundle and the fiber reinforced composite material of this sizing agent.
The means of dealing with problems
The present inventor etc. are for solving the problem and further investigated, found that, by using epoxy resin (A) and specific unsaturated polyester (UP) (B), re-using fatty acid ester (C), problem of the present invention can be solved, thus complete the present invention.
That is, reinforcing fiber sizing agent of the present invention contain epoxy resin (A), acid number lower than 5 unsaturated polyester (UP) (B) and fatty acid ester (C).
Relative to above-mentioned epoxy resin (A) 100 weight portion, above-mentioned unsaturated polyester (UP) (B) is preferably 30 ~ 300 weight portions, relative to total 100 weight portion of above-mentioned epoxy resin (A) with above-mentioned unsaturated polyester (UP) (B), above-mentioned fatty acid ester (C) is preferably 1 ~ 15 weight portion.
The weight average molecular weight (Mw) of above-mentioned unsaturated polyester (UP) (B) is preferably 1.2 ~ 2.1 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
Above-mentioned unsaturated polyester (UP) (B) is preferably containing the condensation product of unsaturated dibasic acid (B1) with the alkylene oxide addition product (B2) of bisphenols.
The reactive ingredients that the ratio that above-mentioned unsaturated polyester (UP) (B) preferably makes to meet following formula (I) contains the alkylene oxide addition product (b2) of unsaturated dibasic acid (b1) and bisphenols reacts and obtains.
The molal quantity (I) of the alkylene oxide addition product (b2) of the molal quantity < bisphenols of unsaturated dibasic acid (b1)
The acid number of above-mentioned unsaturated polyester (UP) (B) is preferably less than 4.5.
The fusing point of above-mentioned fatty acid ester (C) is preferably less than 5 DEG C.
Above-mentioned fatty acid ester (C) preferably has the ester of the structure after the unrighted acid of carbon number 10 ~ 24 and the monohydric alcohol ester bond bonding of carbon number 8 ~ 20.
The ratio that above-mentioned epoxy resin (A), above-mentioned unsaturated polyester (UP) (B) account for the nonvolatile component of sizing agent with the total weight of above-mentioned fatty acid ester (C) is preferably more than 70 % by weight.
Reinforcing fiber bundle of the present invention adheres to above-mentioned reinforcing fiber sizing agent to raw material reinforcing fiber bundle to form.
Fiber reinforced composite material of the present invention contains matrix resin and above-mentioned reinforcing fiber bundle.
Above-mentioned matrix resin is preferably thermosetting resin.
The effect of invention
Reinforcing fiber sizing agent of the present invention can invest cementability excellent between matrix resin to reinforcing fiber.In addition, can suppress reinforcing fiber bundle fluffing and along with time hardening.Further, long-term storing stability is excellent.
Reinforcing fiber bundle of the present invention can not to change or few over time in time due to sizing agent, even if therefore long-term preservation also can suppress to rub fluffing property and and matrix resin between the reduction of cementability.The reinforcing fiber bundle of the application of the invention, can obtain the reinforced fiber composite with excellent physical property.
Detailed description of the invention
The present invention is the reinforcing fiber sizing agent used for strengthening matrix resin, containing epoxy resin (A), specific unsaturated polyester (UP) (B) and fatty acid ester (C).Below, describe in detail.
[epoxy resin (A)]
Epoxy resin (A) is the neccessary composition of sizing agent of the present invention.Epoxy resin (A) refers to the compound in molecular structure with more than 2 reactive epoxy radicals.As epoxy resin (A), with the diglycidyl ether type that can obtain from epoxychloropropane (epichlorohydrin) and active dydrogen compounds for representative, other can enumerate glycidyl ester type, glycidic amine type, alicyclic ring type etc.Epoxy resin (A) can use a kind, also two or more can be combinationally used.
Can enumerate as diglycidyl ether type epoxy resin (A): with alcohols be such as raw material manufacture the epoxy resin with the functional group that following general formula (1) represents, be the epoxy resin etc. with the functional group that following general formula (2) represents that raw material manufactures with phenols.Epoxy resin (A) as glycidyl ester type can be enumerated: such as with the epoxy resin etc. with the functional group that following general formula (3) represents that the carboxylic acids such as phthalic acid derivatives or synthetic resin aliphatic acid manufacture for raw material.Can enumerate as glycidyl amine type epoxy resin (A): such as there is the epoxy resin of the functional group that following general formula (4) represents or there is the epoxy resin etc. of the functional group that following general formula (5) represents.Can enumerate as alicyclic type epoxy resin (A): the epoxy resin etc. such as with the functional group that following general formula (6) represents.Among these epoxy resin, to improve the reason of the cementability of fiber and matrix resin, preferably there is the epoxy resin of the functional group that general formula (2) represents.
[changing 1]
[changing 2]
[changing 3]
[changing 4]
[changing 5]
[changing 6]
The epoxide equivalent of epoxy resin (A) is preferably 100 ~ 1,500g/eq, and more preferably 120 ~ 1,000g/eq, preferred 150 ~ 800g/eq further.When epoxide equivalent is lower than 100g/eq, sometimes promote the sclerosis in time of reinforcing fiber bundle.When epoxide equivalent is more than 1,500g/eq, the cementability sometimes and between matrix resin reduces.It should be noted that, epoxide equivalent is according to the definition of JIS-K7236.
The weight average molecular weight of epoxy resin (A) preferably 100 ~ 10,000, more preferably 100 ~ 8,000, further preferably 150 ~ 7,000.Weight average molecular weight lower than 100 time, in the drying process etc. of reinforcing fiber bundle, heat resistance is not enough and volatilize sometimes.Weight average molecular weight, more than 10, when 000, may make the long-term storing stability of sizing agent reduce.
With regard to the cementability of reinforcing fiber and matrix resin improves, there is in epoxy resin (A) preferred molecular structure the aromatic epoxy resin of aromatic rings with regard to making.
As above-mentioned aromatic epoxy resin, can enumerate: the poly epihydric alcohol ether compound of the monokaryon polyphenol compounds such as quinhydrones, resorcinol, catechol; The poly epihydric alcohol ether compound etc. of the multinuclear polyphenol compounds such as dihydroxy naphthlene, bis-phenol, Bisphenol F, bisphenol-A, phenol novolac, orthoresol novolac, resorcinol novolac, Bisphenol F novolac, bisphenol A novolak, dicyclopentadiene-modified phenol, triphenyl methane, tetraphenyl ethane.
Among these aromatic epoxy resins, the compound that the compound that preferred following general formula (7) represents, following general formula (8) represent, the more preferably compound that represents of following general formula (7).
[changing 7]
In general formula (7), R 5, R 6, R 7and R 8be separately hydrogen atom or methyl.N is the integer of 0 ~ 30, preferably 0 ~ 20, more preferably 0 ~ 10.
[changing 8]
In general formula (8), m is the integer of 0 ~ 10, preferably 0 ~ 8, more preferably 0 ~ 5.
As the manufacture method of above-mentioned epoxy resin (A), there is no particular limitation, can adopt known method.In addition, above-mentioned epoxy resin (A) is general commercially available product, in carbon fiber sizing agent of the present invention, can use these commercially available epoxy resin (A).
[unsaturated polyester (UP) (B)]
Acid number is neccessary compositions of sizing agent of the present invention lower than the unsaturated polyester (UP) (B) of 5.When this acid number is more than 5, reinforcing fiber bundle along with the time hardening, and the long-term storing stability of sizing agent can reduce.This acid number preferably less than 4.5, more preferably less than 4, further preferably less than 3.5.Acid number herein, with in and sample 1g time required potassium hydroxide mg number represent, measure according to JISK2501:2003.
Unsaturated polyester (UP) refers in molecular structure the petchem with more than 1 unsaturated bond.Can enumerate as unsaturated polyester (UP): the acid 1) with more than 1 unsaturated bond separately and the condensation product of alcohol; 2) mixture of the acid with more than 1 unsaturated bond and the acid without unsaturated bond, the condensation product with alcohol; 3) acid and the condensation product etc. of alcohol with more than 1 unsaturated bond.Among these, the especially preferably condensation product of unsaturated dibasic acid and dihydroxylic alcohols.
Unsaturated dibasic acid is compound or its acid anhydrides with unsaturated double-bond and 2 carboxylic acid groups, can enumerate: such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, mesaconic acid, citraconic acid, allyl malonic acid etc.Among these acid, especially preferably carbon number 4 ~ 6 and aliphatic unsaturated dibasic acid.
Alcohol as binary can be enumerated: the alkylene oxide addition product etc. of such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexylene glycol, bisphenols, bisphenols.Among these alcohol, the alkylene oxide addition product of preferred bisphenols.Describe the alkylene oxide addition product of bisphenols and bisphenols later.
With regard to the cementability of reinforcing fiber and matrix resin improves, unsaturated polyester (UP) (B) is preferably containing the condensation product of above-mentioned unsaturated dibasic acid (hereinafter referred to as unsaturated dibasic acid (b1)) with the alkylene oxide addition product (b2) of bisphenols.
Bisphenols refers to the compound with 2 hydroxy phenyls, can enumerate: such as bisphenol-A, bisphenol-ap, bisphenol AF, bisphenol b, bisphenol b P, bisphenol-c, bis-phenol E, Bisphenol F, bis-phenol G, bis-phenol M, bisphenol S, bis-phenol P, bis-phenol PH, bis-phenol TMC, bisphenol Z etc.
The alkylene oxide addition product (b2) of bisphenols instigates alkylene oxide addition polymerization in the compound of above-mentioned bisphenols.Oxirane, expoxy propane, epoxy butane can be enumerated as alkylene oxide.As the addition molal quantity preferably less than 10 moles of alkylene oxide, more preferably less than 5 moles, most preferably less than 2 ~ 4 moles.As addition more than 10 moles time, the cementability between rigidity and matrix resin that bisphenols has may be lost and reduce.
With regard to suppressing the storage stability of the sclerosis in time of reinforcing fiber bundle and sizing agent, unsaturated polyester (UP) (B) preferably makes to meet the ratio of following formula (I) and reacts containing the reactive ingredients of unsaturated dibasic acid (b1) with the alkylene oxide addition product (b2) of bisphenols and obtain.
The molal quantity (I) of the alkylene oxide addition product (b2) of the molal quantity < bisphenols of unsaturated dibasic acid (b1)
The mol ratio (b1/nb2) of the molal quantity of the alkylene oxide addition product (b2) of unsaturated dibasic acid (b1) and bisphenols preferably 70/100 ~ 99/100, more preferably 75/100 ~ 90/100, further preferably 80/100 ~ 85/100.
With regard to the cementability of reinforcing fiber and matrix resin improves, unsaturated dibasic acid (b1) accounts for the total ratio preferably more than 90 % by mole of reactive ingredients with the alkylene oxide addition product (b2) of bisphenols, more preferably more than 95 % by mole, preferably more than 100 % by mole further.
In addition, with regard to the cementability of reinforcing fiber and matrix resin improves, reactive ingredients is not preferably in fact containing the carboxylate of unsaturated dibasic acid.Particularly, the ratio preferably less than 2 % by mole that the carboxylate of unsaturated dibasic acid is shared in reactive ingredients, more preferably less than 1 % by mole, preferably 0 % by mole further.
When the acid number of unsaturated polyester (UP) (B) is declined, although can consider to use the compound of the reactive hydrogen base with 1 official's energy as reactive ingredients, but when using the reactive hydrogen base of 1 official's energy, sometimes the cementability and between matrix resin can reduce, also the long-term storing stability of sizing agent may be made in addition to reduce, therefore the reactive hydrogen base of 1 official's energy should not be used as reactive ingredients.In detail, have 1 official can the compound of reactive hydrogen base account for the ratio preferably less than 2 % by mole of reactive ingredients, more preferably less than 1 % by mole, preferably 0 % by mole further.
As have 1 official can the compound of reactive hydrogen base, 1 yuan of alcohol, secondary amine, 1 yuan of mercaptan etc. can be enumerated.
The weight average molecular weight of unsaturated polyester (UP) (B) preferably 500 ~ 5,000, more preferably 800 ~ 4,500, further preferably 1,000 ~ 3,500.As this molecular weight lower than 500 time, good cementability, heat resistance may not be obtained simultaneously.On the other hand, if this molecular weight is more than 5, when 000, stability of solution may be made to be deteriorated.
The weight average molecular weight (Mw) of unsaturated polyester (UP) (B) and the ratio (Mw/Mn) of number-average molecular weight (Mn) preferably 1.2 ~ 2.1, more preferably 1.4 ~ 2.0, further preferably 1.6 ~ 1.9.As this molecular weight ratio lower than 1.2 time, good cementability, heat resistance may not be obtained simultaneously.On the other hand, as this molecular weight ratio more than 2.2 time, stability of solution may be made to be deteriorated.
It should be noted that, weight average molecular weight (Mw) in the present invention, number-average molecular weight (Mn) utilize Tosoh (strain) High Performance Gel Permeation chromatogram arrangement processed HLC-8220GPC, splitter (Showa electrician (strain) Shodex processed (registration mark) KF-G, KF-402HQ, KF-403HQ) is injected, the value calculated by the curve map measured with RI detector with sample solution concentration 2mg/mL.Use oxolane (THF) to be mobile phase, use polyethylene glycol (PEG) is the standard substance for production standard curve, measures with splitter temperature 40 DEG C, flow velocity 0.3mL/ minute.
As the manufacture method of unsaturated polyester (UP) (B), there is no particular limitation, can adopt known method.Such as, obtain by making alkylene oxide addition product (b2) polycondensation of unsaturated dibasic acid (b1) and bisphenols.With regard to the promotion of esterification and the acid number of product reduce, reaction temperature during polycondensation preferably 110 DEG C ~ 180 DEG C, more preferably 130 DEG C ~ 160 DEG C.With regard to the promotion of esterification and the acid number of product reduce, preferably 1 ~ 10 hour reaction time during polycondensation, more preferably 2 ~ 5 hours.As for promoting polycondensation reaction, also esterification catalyst can be used.
[fatty acid ester (C)]
Fatty acid ester (C) is the required composition of sizing agent of the present invention.Except epoxy resin (A) and epoxy resin (A) and unsaturated polyester (UP) (B), again by containing fatty acid ester (C), reinforcing fiber sizing agent of the present invention can give cementability excellent between matrix resin for reinforcing fiber.In addition, fluffing and the sclerosis in time of reinforcing fiber bundle can be suppressed.Further, long-term storing stability can be made excellent.
Fatty acid ester (C) is the compound of the structure after having aliphatic acid and monohydric alcohol ester bond bonding.
The saturated fatty acid of carbon number 10 ~ 24 or the unrighted acid of carbon number 10 ~ 24 can be enumerated as aliphatic acid.With regard to suppressing the fluffing of reinforcing fiber bundle, the unrighted acid of preferred carbon number 10 ~ 24.The carbon number of aliphatic acid preferably 10 ~ 22, more preferably 12 ~ 20, further preferably 14 ~ 20.
Concrete example as aliphatic acid can enumerate capric acid, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid, behenic acid, tetracosanoic acid (lignocericacid) etc.
The monohydric alcohol of carbon number 8 ~ 20 can be enumerated as monohydric alcohol.In more detail, the saturated monohydroxy alcohol of carbon number 8 ~ 20 or the unsaturated monohydric alcohol of carbon number 8 ~ 20 can be enumerated.The carbon number of monohydric alcohol preferably 12 ~ 22, more preferably 14 ~ 20, further preferably 16 ~ 20.
Concrete example as monohydric alcohol can be enumerated: the alcohol etc. of octanol, decyl alcohol, laruyl alcohol, tridecanol, tetradecanol, hexadecanol, heptadecanol, stearyl alcohol, oleyl alcohol, nonadecanol and their side chain.
Among these, with regard to suppressing the fluffing of reinforcing fiber bundle, preferably there is as fatty acid ester (C) compound of the structure after the unrighted acid of carbon number 10 ~ 24 and the monohydric alcohol ester bond bonding of carbon number 8 ~ 20.The carbon number of this unrighted acid preferably 10 ~ 22, more preferably 12 ~ 20, further preferably 14 ~ 20.The carbon number of this monohydric alcohol preferably 12 ~ 22, more preferably 14 ~ 20, further preferably 16 ~ 20.
As fatty acid ester (C), represent with following general formula (9).
R 9-COOR 10(9)
In general formula (9), R 9the alkyl of carbon number 9 ~ 23, alkenyl or alkynyl.R 9preferred thiazolinyl.R 9can be straight chain, also can be branched.R 9carbon number preferably 12 ~ 22, more preferably 14 ~ 20, further preferably 16 ~ 20.
In general formula (9), R 10the alkyl of carbon number 8 ~ 20, alkenyl or alkynyl.R 10can be straight chain, also can be branched.R 10carbon number preferably 10 ~ 20, more preferably 12 ~ 20, further preferably 14 ~ 20.
As the concrete example of fatty acid ester (C), can enumerate: such as octyl laurate, laurate ester in the last of the ten Heavenly stems, bay dodecyl gallate, laurate 13 ester, laurate 14 ester, laurate hexadecyl ester, laurate 17 ester, laurate octadecyl ester, lauric acid oil alcohol ester, laurate 19 ester, myristic acid monooctyl ester, myristic acid ester in the last of the ten Heavenly stems, nutmeg dodecyl gallate, myristic acid 13 ester, myristyl myristate, myristic acid hexadecyl ester, myristic acid 17 ester, myristic acid octadecyl ester, myristic acid oleyl alcohol ester, myristic acid 19 ester, octyl palmitate, palmitic acid ester in the last of the ten Heavenly stems, palm dodecyl gallate, palmitic acid 13 ester, palmitic acid 14 ester, cetyl palmitate, palmitic acid 17 ester, stearyl palmitate, palmitic acid oil alcohol ester, palmitic acid 19 ester, octyl stearate, stearic acid ester in the last of the ten Heavenly stems, stearic dodecyl gallate, stearic acid 13 ester, stearic acid 14 ester, hexadecyl stearate, stearic acid 17 ester, stearyl stearate, stearic acid oleyl alcohol ester, stearic acid 19 ester, oleic acid monooctyl ester, decyl oleate, oil dodecyl gallate, oleic acid 13 ester, oleic acid 14 ester, cetyl oleate, oleic acid 17 ester, oleic acid octadecyl ester, oleic acid oleic alcohol ester, oleic acid 19 ester etc.
Among these esters, with regard to suppressing the fluffing of reinforcing fiber bundle, the misery ester of preferred oil, decyl oleate, oily dodecyl gallate, oleic acid 13 ester, oleic acid 14 ester, cetyl oleate, oleic acid 17 ester, oleic acid octadecyl ester, oleic acid oleic alcohol ester, oleic acid 19 ester, more preferably cetyl oleate, oleic acid 17 ester, oleic acid octadecyl ester, oleic acid oleic alcohol ester, oleic acid 19 ester.
With regard to suppressing the fluffing of reinforcing fiber bundle, the fusing point of fatty acid ester (C) preferably less than 5 DEG C, more preferably 5 DEG C ~-10 DEG C, preferably 5 DEG C ~-5 DEG C further.As fusing point more than 5 DEG C time, in the winter time for a long time preserve reinforcing fiber bundle time, fatty acid ester become solid fraction and may reduce suppress fluffing effect.It should be noted that, the following fusing point measured in the present invention.Take to measure sample in the capillary (internal diameter 1mm, below external diameter 2mm, length 50 ~ 80mm) of two ends open pipe until the height of about 10mm.This is placed in BUCHI melting point apparatus M-565, the temperature below fusing point is with 1 DEG C/min of intensification.Make the melting of mensuration sample, will transparent temperature be become as fusing point.
The weight average molecular weight of fatty acid ester (C) preferably 300 ~ 700, more preferably 400 ~ 600, most preferably 500 ~ 600.As this molecular weight lower than 300 time, the heat resistance of fatty acid ester may be made to reduce, strengthening bundle drying process in volatilization, reduce suppress fluffing effect.As this molecular weight more than 700 time, friction may be made to uprise, reduce the suppression of reinforcing fiber bundle fluffing effect.
[reinforcing fiber sizing agent]
Reinforcing fiber sizing agent of the present invention must containing above-mentioned epoxy resin (A), unsaturated polyester (UP) (B) and fatty acid ester (C).
Unsaturated polyester (UP) (B) relative to epoxy resin (A) 100 weight portion preferably 30 ~ 300 weight portions, more preferably 35 ~ 250 weight portions, further preferred 40 ~ 200 weight portions.As during lower than 30 weight portion, reinforcing fiber may be made to reduce for the cementability of the matrix resin of radical polymerization syzygy.On the other hand, as during more than 300 weight portion, may make the texture of reinforcing fiber bundle hardening, in manufacturing procedure, easily produce friction fluffing.
Relative to total 100 weight portion of epoxy resin (A) and unsaturated polyester (UP) (B), fatty acid ester (C) preferably 1 ~ 15 weight portion, more preferably 3 ~ 12 weight portions, further preferred 5 ~ 10 weight portions.As during lower than 1 weight portion, the hairy effect suppressing reinforcing fiber bundle may be reduced.On the other hand, as during more than 15 weight portion, the cementability of reinforcing fiber for matrix resin may be reduced.
The ratio that the total weight of epoxy resin (A), unsaturated polyester (UP) (B) and fatty acid ester (C) accounts for the nonvolatile component of sizing agent preferably more than 70 % by weight, more preferably 70 ~ 95 % by weight, further preferably 75 ~ 90 % by weight.As lower than 70 % by weight time, the cementability of reinforcing fiber for matrix resin may be reduced.It should be noted that, the nonvolatile component in the present invention refers to removes solvent etc. with 105 DEG C by sizing agent heat treatment, parches composition when reaching constant.
With regard to during process to the security of human body or prevent the disasters such as fire, prevent the pollution of natural environment etc. with regard to, sizing agent of the present invention also can contain water.In the scope not damaging effect of the present invention, also can use the organic solvents such as methyl alcohol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone.
Sizing agent of the present invention self-emulsifying and/or emulsion dispersion in water form.There is no particular limitation for the average grain diameter of sizing agent, preferably less than 10 μm, more preferably 0.01 ~ 1 μm, preferably 0.01 ~ 0.5 μm further.When this average grain diameter is more than 10 μm, evenly may not adhere to reinforcing fiber, and have the anxiety making this i.e. separations within a few days of sizing agent, storage stability is poor and without practicality.
It should be noted that, average grain diameter alleged in the present invention, refers to the mean value that the size distribution measured by laser diffraction/diffuse transmission type particle size distribution device (hole field LA-910) is calculated.
In the scope not damaging effect of the present invention, sizing agent of the present invention, also can containing other composition except the epoxy resin (A) of above-mentioned middle explanation, unsaturated polyester (UP) (B) and fatty acid ester (C).As other composition, can enumerate: such as various surfactant, various smooth agent, antioxidant, fire retardant, antiseptic, crystal nucleating agent, defoamer etc., a kind or two or more combinationally used can be used.
During resin containing water-insoluble or slightly solubility in epoxy resin (A) or unsaturated polyester (UP) (B) or fatty acid ester (C) or other sizing agents, surfactant carries out aqueous emulsifying effectively by using as emulsifying agent.
As surfactant, there is no particular limitation, can suitably select known material and use in nonionic surfactant, anionic surfactant, cationic surfactant and amphoteric surfactant.Surfactant can use a kind, also two or more can be combinationally used.
Can enumerate as nonionic surfactant: such as alkylene oxide addition nonionic surfactant is (at higher alcohol, higher fatty acids, alkyl phenol, SP styrenated phenol, benzyl phenol, glycerine, pentaerythrite, sorbierite, anhydro sorbitol, Isosorbide Dinitrate, castor oil, hardened castor oil, higher aliphatic amine, fatty acid amide, addition of ethylene oxide in grease etc., the material of the alkylene oxides such as expoxy propane (may be combined with and use two or more)), the material of addition higher fatty acids etc. in poly alkylene glycol, ethylene oxide/propylene oxide copolymer, the ester of polyalcohol and aliphatic acid, aliphatic alkanolamide etc.
In more detail, can enumerate as nonionic surfactant: the polyoxy alkylidene straight chained alkyl ethers such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene ether in the last of the ten Heavenly stems, polyoxyethylenelauryl ether, polyoxyethylene margaron; The polyoxy alkylidene branched primary alkyl moiety ethers such as polyoxyethylene 2-ethyl hexyl ether, the different margaron of polyoxyethylene, the different stearyl ether of polyoxyethylene; The polyoxy alkylidene branched secondary alkyl group ethers such as polyoxyethylene 1-hexyl hexyl ether, polyoxyethylene 1-octyl group hexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-amyl group heptyl ether, polyoxyethylene 1-heptyl amyl ether; The polyoxy alkylidene alkene ethers such as polyoxyethylene oil ether; The polyoxyalkylene alkyl phenylates such as polyoxyethylene octyl group phenylate, polyoxyethylene nonyl phenylate, polyoxyethylene dodecyl phenylate; The polyoxyalkylene alkyl aryl phenylates such as polyoxyethylene tristyryl base phenylate, polyoxyethylene diphenylethyllene phenylate, polyoxyethylene styryl phenylate, polyoxyethylene tristyryl ylmethyl phenylate, polyoxyethylene diphenylethyllene methyl phenylate, polyoxyethylene styrylmethyl phenylate, polyoxyethylene trityl phenylate, polyoxyethylene benzhydryl phenylate, polyoxyethylene benzyl phenylate; The polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monoleate, polyoxyethylene monostearate, polyoxyethylene list myristinate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxyethylene two myristinate, polyoxyethylene distearate; The anhydrosorbitol such as Arlacel-40, Arlacel-80 alcohol ester; The polyoxyalkylene sorbitan alcohol fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monoleate; The fatty acid glycerides such as glyceryl monostearate, glyceryl monolaurate, glycerol monopalmitate; Polyoxyalkylene sorbitan fatty acid ester; Sucrose fatty ester; The polyoxy alkylidene castor oil ethers such as polyoxyethylene castor oil ether; The polyoxy alkylidene hardened castor oil ethers such as polyoxyethylene hardened castor oil ether; The polyoxyalkylene alkyl amino ethers such as polyoxyethylenelauryl base amino ethers, polyoxyethylene stearyl ether; Oxygen ethene-oxypropylene block or random copolymer; The end alkyl etherate of oxygen ethene-oxypropylene block or random copolymer; The end sucrose ether compound of oxygen ethene-oxypropylene block or random copolymer; Deng.
Can enumerate as anionic surfactant: the phosphate ester salt etc. of the sulfuric acid of such as carboxylic acid (salt), the senior alcohol ether of higher alcohol, sulfonate, the senior alcohol ether of higher alcohol.
In more detail, can enumerate as anionic surfactant: the aliphatic acid (salt) such as such as oleic acid, palmitic acid, Oleic acid sodium salt, palmitic acid sylvite, triethanol amine oleate; The carboxylic acid (salt) containing hydroxyl such as glycolic acid, glycolic acid sylvite, lactic acid, lactic acid sylvite; The polyoxyalkylene alkyl ether acetic acid (salt) such as polyoxyethylene 13 ether acetic acid (sodium salt); The salt of the carboxyl Polysubstituted Aromatic Compounds such as trimellitic acid potassium, pyromellitic acid potassium; The alkyl benzene sulphonates (salt) such as DBSA (sodium salt); The polyoxyalkylene alkyl ether sulfonic acid (salt) such as polyoxyethylene 2-ethyl hexyl ether sulfonic acid (sylvite); The higher fatty acid amides sulfonic acid (salt) such as stearyl N-methyltaurine (sodium), lauroyl N-methyltaurine (sodium), myristoyl N-methyltaurine (sodium), palmityl N-methyltaurine (sodium); The N-acyl group methyl amimoacetic acids (salt) such as lauroyl sarcosine (sodium); The alkyl phosphonic acids (salt) such as octylphosphonate (sylvite); The aromatic series phosphonic acids (salt) such as phenyl phosphonic acid esters (sylvite); The alkyl phosphonic acid alkyl phosphates (salt) such as 2-ethylhexyl phosphonate single 2-ethyl hexyl ester (sylvite); The nitrogenous alkyl phosphonic acids (salt) such as aminoethyl phosphonic acid (diethanolamine salt); The alkyl sulfates (salt) such as 2-ethylhexylsulfate (sodium salt); The polyoxyethylene sulfuric esters (salt) such as polyoxyethylene 2-ethyl hexyl ether sulfuric ester (sodium salt); The long-chain N-acyl glutamates such as the long-chain sulfosuccinates such as two-2-ethylhexylsulfosuccinate sodium, dioctyl sodium sulphosuccinate, N-sodium lauroyl glutamate, N-stearyl-Pidolidone disodium; Deng.
Can enumerate as cationic surfactant: such as lauryl trimethyl ammonium chloride, myristyl trimonium ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oil base trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, mountain Yu base trimethyl ammonium chloride, coco alkyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, Cocoalkyl trimethylammonium bromide, cetyltrimethyl ammonium Methylsulfate, oleyl dimethyl ethyl ammonium ethyl-sulfate, Quaternium 24, dilauryl ammonium chloride, VARISOFT TA100, the alkyl quaternary ammonium saltss such as octadecyl diethylmethyl ammonium sulfate, (polyoxyethylene) lauryl amino ether lactate, stearyl ether lactate, two (polyoxyethylene) lauryl methyl amino ethers Dimethyl phosphate, oleyl methyl ethyl ammonium ethyl-sulfate, two (polyoxyethylene) lauryl ethyl ammonium ethyl-sulfate, two (polyoxyethylene) hardened tallow alkyl ethylamine ethyl-sulfate, two (polyoxyethylene) lauryl methyl ammonium Dimethyl phosphate, (polyoxy alkylidene) alkyl amino ether salt such as two (polyoxyethylene) stearic amine lactate, the acylamide alkyl quaternary ammonium saltss such as N-(2-hydroxyethyl)-N, N-dimethyl-N-stearyl amido propyl ammonium nitrate, lanolin fatty acid amido propyl ethosulfate ethyl-sulfate, lauroyl acid amides ethyl-methyl diethyl ammonium Methylsulfate, the alkyl oxygen ethylidene quaternary ammonium salts such as two palmityl polyoxyethylene ethyl ammonium chlorides, distearyl polyoxyethylene ammonio methacrylate, the alkyl isoquinolinium salts such as lauryl isoquinolin chloride, the zephiran salt such as lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, the Benzethonium salt such as benzyl dimethyl { 2-[2-(p-1,1,3,3-tetramethyl butyl phenoxy group) ethyoxyl] ethyl } ammonium chloride, the pyridiniujms such as pyrisept, the imidazoline salts such as oil base hydroxyethyl imidazolines ethyl-sulfate, C 100L ethyl-sulfate, the acyl group basic amino acid alkane ester salt such as N-cocoyl arginine ethyl ester pyrrolidone carboxylic acid salt, N-lauroyl lysine diethyl acetamidomalonate chloride, the uncle such as lauryl amine chloride, stearic amine bromide, hardened tallow alkyl amine chloride, rosin amine acetate ammonium salt, the secondary amine salt such as cetyl methyl amine sulfuric ester, lauryl methyl amine chloride, dilauryl amine acetate, stearic amine bromide, lauryl propyl group amine acetate, dioctylamine chloride, octadecyl ethylamine hydroxide, the tertiary amine salt such as dilauryl methyl amine sulfuric ester, lauryl diethylamide chloride, lauryl ethylmethylamine bromide, diethanol stearyl amido-propyl ethylamine trihydroxy ethyl phosphate, stearyl amido-propyl ehtylethanolamine urea polycondensation thing acetate, fatty acid amide guanidinesalt, the alkyl three aklylene glycol ammonium salts etc. such as lauryl triethylene glycol ammonium hydroxide.
Can enumerate as amphoteric surfactant: the imidazoline system amphoteric surfactantes such as such as 2-undecyl-N, N-(hydroxyethyl carboxymethyl group)-2-imidazoline sodium, 2-cocoyl-2-imidazoline hydroxide-1-Carboxyethoxy 2 sodium salt; The betaine system amphoteric surfactantes such as 2-heptadecyl-N-carboxymethyl group-N-hydroxyethyl imidazolines betaine, stearyl dimethyl betaine, lauryl dihydroxy ethyl betaine, lauryl dimethyl oxyneurine, alkyl betaine, amide betaine, sulfobetaines; The amino acid type amphoteric surfactants etc. such as N-lauryl Gly, N-lauryl β-alanine, N-stearyl β-alanine, lauryl amino propionic acid sodium.
Containing the part by weight shared in the nonvolatile component of sizing agent of surfactant during surfactant preferably 5 ~ 30 % by weight, more preferably 10 ~ 25 % by weight, further preferably 15 ~ 25 % by weight.
There is no particular limitation for the nonvolatile component concentration of sizing agent of the present invention, considers to be made the stability of aqueous dispersion, suitably selects as goods easy to handle viscosity etc.If when considering the conveying cost etc. of goods, the part by weight shared in sizing agent entirety of nonvolatile component preferably 10 ~ 100 % by weight, further preferably 15 ~ 100 % by weight, particularly preferably 20 ~ 100 % by weight.
In addition, the total part by weight shared in sizing agent entirety of water and nonvolatile component preferably more than 90 % by weight, more preferably more than 95 % by weight, further preferably more than 99 % by weight, especially preferably 100 % by weight.As lower than 90 % by weight time, namely containing when heat treatment not as the residual above-mentioned organic solvent of nonvolatile component, other low-boiling compound more than 10 % by weight time, with regard to during process to regard to the security of human body, preventing to natural environment pollution, sometimes not preferred.
It should be noted that, in above-mentioned aqueous dispersion or the aqueous solution, except the above-mentioned security for human body, preventing to natural environment pollution, with regard to the thickening/solidification in time preventing aqueous dispersion, the aqueous solution, even if not containing or be preferably relative to less than 10 % by weight of sizing agent entirety containing during solvent beyond the water of organic solvent etc., be more preferably less than 5 % by weight, more preferably less than 1 % by weight.
There is no particular limitation sizing agent of the present invention to be made into the method for aqueous dispersion, can adopt known method.As above-mentioned, can enumerate: when manufacturing each composition forming sizing agent, make aqueous dispersion respectively, by the method that these compositions mix; The each composition forming sizing agent is dropped into the method making its emulsion dispersion in the warm water under stirring; By the method for the emulsified dispersed liquid mixing after each composition of formation sizing agent in advance emulsion dispersion; To each composition mixing of sizing agent be formed, and the mixture of gained be heated after to softening point, utilizes homogenizer, homogenizer, ball mill etc. to apply mechanical shear stress and gently devote the method etc. of carrying out Phase inversion emulsification in water.
[reinforcing fiber bundle and manufacture method thereof]
Reinforcing fiber bundle of the present invention adheres to above-mentioned reinforcing fiber sizing agent to raw material reinforcing fiber bundle to form, and be the reinforcing fiber in order to strengthen matrix resin.Excellent in adhesion between reinforcing fiber bundle of the present invention and matrix resin.Just made cementability improve effect more Gao Eryan, the preferred thermoset matrix resin of matrix resin by sizing agent of the present invention.Reinforcing fiber bundle of the present invention is few because fluffing, therefore operation is excellent by property, because reinforcing fiber sizing agent will along with the change of time or the lacking of change along with the time, therefore can make long-term preservability excellent.
Can suitably select the nonvolatile component of sizing agent to the adhesion amount of raw material reinforcing fiber bundle, as long as be set to make reinforcing fiber harness have the necessary amount of required function, but this adhesion amount is relative to raw material reinforcing fiber Shu Youxuan 0.1 ~ 20 % by weight.The reinforcing fiber of long fiber form is intrafascicular, relative to its adhesion amount of raw material reinforcing fiber bundle more preferably 0.1 ~ 10 % by weight, and further preferably 0.5 ~ 5 % by weight.In addition, staple fiber form (cutting into the state of specific length) intrafascicular, is more preferably 0.5 ~ 20 % by weight, and more preferably 1 ~ 10 % by weight.
When adhesion amount as sizing agent is few, be difficult to obtain heat resistance, resin impregnated, effect of the present invention involved by cementability, in addition, may make the pack of reinforcing fiber bundle not enough, treatability is deteriorated.In addition, when the adhesion amount as sizing agent is too much, reinforcing fiber bundle will be made too upright and outspoken, and make treatability be deteriorated on the contrary, during composite molding, make resin impregnated be deteriorated, thus not preferred.
The manufacture method of reinforcing fiber bundle comprises: preparation is containing above-mentioned sizing agent, and the part by weight of nonvolatile component is 0.5 ~ 10 % by weight, and the total part by weight of water and nonvolatile component is the preparation section of the treatment fluid of more than 90 % by weight; And, be 0.1 ~ 20 % by weight for making nonvolatile component relative to the adhesion amount of raw material reinforcing fiber bundle and make this treatment fluid be attached to the attachment operation of raw material reinforcing fiber bundle.
In preparation section, the part by weight in treatment fluid shared by nonvolatile component preferably 0.5 ~ 10 % by weight, more preferably 1 ~ 5 % by weight.The total part by weight of water and nonvolatile component is preferably more than 95 % by weight, and more preferably more than 99 % by weight, be particularly preferably 100 % by weight.
In attachment operation, the adhesion amount of preferred nonvolatile component as in the previous paragraph.The method making sizing agent be attached to raw material reinforcing fiber bundle is not particularly limited, and makes sizing agent be attached to the method for raw material reinforcing fiber bundle as long as lick method, roller infusion process, spray-on process and other known methods with roller.Among these methods, roller infusion process is attached to raw material reinforcing fiber bundle equably because making sizing agent, therefore preferably.
There is no particular limitation for the drying means of the attachment of gained, such as, can carry out heat drying with warm-up mill, hot blast, hot plate etc.
It should be noted that, when making sizing agent of the present invention be attached to raw material reinforcing fiber bundle, the constituent of sizing agent can be made all to mix rear attachment, constituent also can be made to be divided into the two-stage more than to adhere to respectively.In addition, in the scope not hindering effect of the present invention, except epoxy resin (A), unsaturated polyester (UP) (B) and fatty acid ester (C), the thermoplastic resin such as the thermosetting resin such as vinylester resin, phenolic resins and/or vistanex, mylar, nylon resin, acrylic resin also can be made to be attached to raw material reinforcing fiber bundle.
Reinforcing fiber bundle of the present invention can be used as and uses with the reinforcing fiber of the various resin composite that is matrix resin, as the form used, can be long fiber form, also can be staple fiber form.
As (raw material) reinforcing fiber bundle of applicable sizing agent of the present invention, the bundle of the various organic fibers such as carbon fiber, glass fibre, the various inorfil of ceramic fibre, aramid fibre, polyethylene fiber, dacron fibre, poly fiber, PEN fiber, polyarylate fiber, polyacetal fibre, pbo fiber, polyphenylene sulfide fibre, polyketone fiber etc. can be enumerated.With regard to the physical property of the fiber reinforced composite material as gained, the bundle of at least one in carbon fiber, aramid fibre, polyethylene fiber, dacron fibre, poly fiber, PEN fiber, polyarylate fiber, polyacetal fibre, pbo fiber, polyphenylene sulfide fibre and polyketone fiber is preferably selected from, more preferably carbon fiber bundle as (raw material) reinforcing fiber bundle.
[fiber reinforced composite material]
Fiber reinforced composite material of the present invention is the material containing matrix resin and above-mentioned reinforcing fiber bundle.Reinforcing fiber bundle, by sizing agent process of the present invention, makes sizing agent adhere to equably, the compatibility between reinforcing fiber bundle and matrix resin can be made good, become fiber reinforced composite material excellent in adhesion.Herein, matrix resin refers to the matrix resin comprising thermosetting resin or thermoplastic resin, can contain one or two or more kinds.Be not particularly limited as thermosetting resin, epoxy resin, phenolic resins, unsaturated polyester resin, vinylester resin, acrylic resin, cyanate ester resin, polyimide resin etc. can be enumerated.Be not particularly limited as thermoplastic matrix resin, polyolefin-based resins, polyamide series resin, polycarbonate resin, mylar, polyacetal resin, ABS resin, phenoxy resin, plexiglass, polyphenylene sulfide, polyetherimide resin, polyether ketone resin etc. can be enumerated.Among these resins, the cementability just based on sizing agent of the present invention improves effect more Gao Eryan, preferred thermoset matrix resin, more preferably epoxy resin, unsaturated polyester resin, vinylester resin, most preferably epoxy resin.Herein, epoxy resin refers in molecular structure the compound with reactive epoxy radicals, heats, can make epoxy radicals cross-linked network and solidify after mixing with curing agent.As epoxy resin, the epoxy resin identical with the above-mentioned epoxy resin (A) of the neccessary composition as sizing agent can be enumerated.These matrix resins, for objects such as the cementability made between reinforcing fiber bundle more improve, make its a part of or whole modification also harmless.
As the manufacture method of fiber reinforced composite material, there is no particular limitation, can adopt shaping by the composite injection of staple fiber, long fiber particle etc., by the known method such as punch forming, other fiber winding formings of UD sheet, textiles sheet etc.
When thermoset matrix resin and reinforcing fiber bundle being mixed, there is the method heating under pressurization or normal pressure after being mixed by curing agent and manufacture fiber reinforced composite material; Or, curing agent, curing accelerator are mixed and in normal temperature, manufacture the method for fiber reinforced composite material.
The content of the reinforcing fiber bundle in fiber reinforced composite material also limits without special, as long as according to the kind of fiber, form, matrix resin kind etc. and suitably select, but for available fiber reinforced composite material, preferably 5 ~ 70 % by weight, more preferably 20 ~ 60 % by weight.
Embodiment
Below, specifically describe the present invention by embodiment, but the embodiment that the present invention is not limited thereto described in place.It should be noted that, the percentage (%) represented in following embodiment, as long as part just represents " % by weight ", " weight portion " without special restriction.The mensuration of each characteristic value is carried out according to method shown below.
< stability of solution >
Preserve with the thermostat being adjusted to 50 DEG C each process emulsion that nonvolatile component concentration is 3.0 % by weight, with the outward appearance of visual confirmation solution, judge stability of solution with following assessment benchmark.
◎: 60 days without being separated.
Within zero: 30 day, without being separated, be separated within 60 days.
Within △: 7 days, without being separated, be separated within 30 days.
×: be separated within 7 days.
××: emulsification was separated the same day, or cannot emulsification.
< cementability >
Use composite material interface characteristic evaluation apparatus HM410 (Dong Rong industry joint-stock company), carry out cementability assessment by microlayer model method.
Take out carbon fiber wire by the carbon fiber bundle of gained in embodiment and comparative example, be placed in specimen mounting.Make to be mixed with curing agent, the drop of each matrix resin of curing accelerator is formed in carbon fiber wire, by following curing, drop is solidified, obtain the sample measured.Mensuration sample is placed in equipment, clamps drop with device blade, carbon fiber wire is moved with the speed of 0.06mm/ minute on device, measure the maximum pull-out forces F when carbon fiber wire extracts drop.
Calculate interface shear strength τ by following formula, carry out cementability assessment between carbon fiber wire and matrix resin.
Interface shear strength τ (unit: MPa)=F/ π dl
(F: maximumly extract pulling force d: carbon fiber wire diameter 1: the particle diameter extracting direction of drop)
(curing of the drop (drop) of each matrix resin)
Matrix resin is use epoxy resin in embodiment 1 ~ 10 and comparative example 1 ~ 4,7 ~ 9, is use unsaturated polyester resin in embodiment 11 ~ 14 and comparative example 5, is use vinylester resin in embodiment 15 ~ 18 and comparative example 6.
Epoxy resin: with 80 DEG C × 1 hour, 150 DEG C × 3 hours, to be adjusted to epoxy resin JER828 (joint-stock company of Mitsubishi Chemical) 100 weight portions, DICY (joint-stock company of Mitsubishi Chemical) 3 weight portions matrix resin drop heating, make it solidify.
Unsaturated polyester resin: with 80 DEG C × 1 hour, 150 DEG C × 3 hours, to be adjusted to unsaturated polyester resin Rigolac (リ go ラ Star Network) M540 (Showa electrician joint-stock company) 100 weight portions, Permek (パ mono-メ Star Network) N (You joint-stock company) 2 weight portions matrix resin drop heating, make it solidify.
Vinylester resin: with 80 DEG C × 1 hour, 150 DEG C × 3 hours, to be adjusted to vinylester resin Repoxy (リ Port キ シ) R-806 (Showa electrician joint-stock company) 100 weight portions, Percure (パ mono-キ ュ ア mono-)-O (You joint-stock company) 2 weight portions matrix resin drop heating, make it solidify.
< friction fluffing property >
Utilize TM formula friction cohesive force testing machine TM-200 (Daiei science essence device makes institute's (strain) system), utilize the minute surface chromium plating stainless pin 3 being configured to "the" shape, with the tension force of 50g, the carbon fiber bundle 1 that obtains in friction embodiment and comparative example, 000 time (back and forth movement speed 300 beats/min), with the fluffing state of the visual judgement carbon fiber bundle of following benchmark.
◎: do not see fluffing completely in the same manner as before friction.
Zero: although see several Zhi Qimao, practical complete unchallenged degree.
△: can see many fluffings, also can confirm some fracture of wires.
×: can confirm to have very many fluffings and the fracture of wire of monofilament.
< fiber keeping quality >
To preserve in embodiments and comparative example gained carbon fiber bundle 10 days with 100 DEG C, the hardness of trying to achieve the carbon fiber bundle after preservation with preserve before the difference of hardness of carbon fiber bundle, can judge to go on business less, sclerosis is in time fewer.The hardness of carbon fiber bundle (length: approximately 50cm) measures with texture testing machine (HANDLE-O-METERHOM-2 Daiei science essence device makes institute's (strain) system, stitches wide 10mm).
[epoxy resin (A)]
JER1001: joint-stock company of Mitsubishi Chemical, solid bisphenol A type epoxy resin, epoxide equivalent 450 ~ 500
JER834: joint-stock company of Mitsubishi Chemical, half solid bisphenol A type epoxy resin, epoxide equivalent 230 ~ 270
JER828: joint-stock company of Mitsubishi Chemical, aqueous bisphenol A type epoxy resin, epoxide equivalent 184 ~ 194
JER807: joint-stock company of Mitsubishi Chemical, aqueous bisphenol f type epoxy resin, epoxide equivalent 160 ~ 175
JER157S65: joint-stock company of Mitsubishi Chemical, bisphenol A novolak type epoxy resin, epoxide equivalent 200 ~ 220
[synthesis of unsaturated polyester (UP) (B)]
(synthesis example B-1)
Make maleic anhydride 0.9 mole in 140 DEG C, react 5 hours with oxirane 4 moles of addition products 1.0 moles of bisphenol-A, obtain the unsaturated polyester (UP) (B-1) of acid number 2.5.Weight average molecular weight (Mw) is 3,051, and weight average molecular weight (Mw) is 1.6 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
(synthesis example B-2)
Make maleic anhydride 0.8 mole in 140 DEG C, react 3 hours with oxirane 2 moles of addition products 1.0 moles of bisphenol-A, obtain the unsaturated polyester (UP) (B-2) of acid number 3.5.Weight average molecular weight (Mw) is 1,626, and weight average molecular weight (Mw) is 1.7 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
(synthesis example B-3)
Make fumaric acid 0.85 mole in 170 DEG C, react 8 hours with oxirane 3 moles of addition products 1.0 moles of bisphenol-A, obtain the unsaturated polyester (UP) (B-3) of acid number 4.5.Weight average molecular weight (Mw) is 3,444, and weight average molecular weight (Mw) is 1.9 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
(synthesis example B-4)
Make maleic anhydride 0.9 mole in 150 DEG C, react 5 hours with expoxy propane 3 moles of addition products 1.0 moles of bisphenol-A, obtain the unsaturated polyester (UP) (B-4) of acid number 2.0.Weight average molecular weight (Mw) is 2,903, and weight average molecular weight (Mw) is 1.7 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
[synthesis of unsaturated polyester (UP)]
(synthesis example b-1)
Make maleic anhydride 1.0 moles in 135 DEG C, react 2 hours with oxirane 2 moles of addition products 1.0 moles of bisphenol-A, obtain the unsaturated polyester (UP) (b-1) of acid number 60.Weight average molecular weight (Mw) is 3,872, and weight average molecular weight (Mw) is 2.0 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
(synthesis example b-2)
Make maleic anhydride 1.0 moles in 135 DEG C, react 5 hours with oxirane 2 moles of addition products 1.0 moles of bisphenol-A, then make it react 5 hours with 170 DEG C, obtain the unsaturated polyester (UP) (b-2) of acid number 6.3.Weight average molecular weight (Mw) is 5,736, and weight average molecular weight (Mw) is 2.3 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
(synthesis example b-3)
Make maleic anhydride 1.0 moles in 160 DEG C, react 5 hours with oxirane 4 moles of addition products 1.0 moles of bisphenol-A, obtain the unsaturated polyester (UP) (b-3) of acid number 10.Weight average molecular weight (Mw) is 4,860, and weight average molecular weight (Mw) is 2.0 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
(synthesis example b-4)
Make maleic anhydride 1.0 moles in 140 DEG C, react 4 hours with oxirane 3 moles of addition products 1.0 moles of bisphenol-A, obtain the unsaturated polyester (UP) (b-4) of acid number 30.Weight average molecular weight (Mw) is 4,860, and weight average molecular weight (Mw) is 2.1 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
[fatty acid ester (C)]
Oleic acid oleic alcohol ester: fusing point 4 DEG C
Laurel oleate: fusing point 11 DEG C
Ethylhexyl stearate: fusing point 10 DEG C
[embodiment 1]
To become the mode of the nonvolatile component composition of the finishing agent shown in table 1 by JER1001, unsaturated polyester (UP) (B-1), oleic acid oleic alcohol ester, POE (150) hardened castor oil ether, PO/EO (25/75) polyethers (molecular weight 16,000) load in emulsifier unit, low add water under stirring and make its Phase inversion emulsification, obtain the sizing agent aqueous dispersion of nonvolatile component concentration 30 % by weight.With the sizing agent aqueous dispersion of water dilution gained, the sizing agent emulsion of preparation nonvolatile component concentration 3 % by weight, make sizing agent untreated carbon fiber bundle (fiber number 800tex, silk several 12,000) dipping/infiltration after, make its heated-air drying 15 minutes with 105 DEG C, obtain the sizing agent Treatment of Carbon bundle that theoretical adhesion amount is 1.0%.By above-mentioned method, carry out each characteristic value assessment of this sizing agent and this bundle.About cementability and friction fluffing property, the carbon fiber bundle after using the carbon fiber bundle before the assessment of fiber keeping quality and fiber keeping quality to assess, assesses respectively.The results are shown in table 1.
[embodiment 2 ~ 18, comparative example 1 ~ 9]
Except the nonvolatile component of the finishing agent be adjusted to as shown in table 1 ~ 3 except sizing agent emulsion is in embodiment 1 grouped into, all the other obtain sizing agent Treatment of Carbon bundle, assess each characteristic value similarly to Example 1.The evaluation result of each characteristic value is shown in table 1 ~ 3.
[table 1]
[table 2]
[table 3]
From table 1 ~ 3, the long-time stability of the sizing agent of embodiment are excellent.In addition, excellent in adhesion between the fibre bundle of embodiment and matrix resin, also inhibits fluffing.Further, fiber keeping quality is excellent, and the cementability after fiber is preserved is also excellent, inhibits fluffing.
Utilizability in industry
The fiber reinforced composite material strengthening matrix resin through reinforcing fiber can be used in mobile applications, aerospace purposes, Sport & Casual purposes, general industrial applications etc.The various organic fibers such as the various inorfil such as carbon fiber, glass fibre, ceramic fibre, aramid fibre, polyamide fiber, polyethylene fiber can be enumerated as reinforcing fiber.Sizing agent of the present invention is applicable to the reinforcing fiber strengthening matrix resin.

Claims (12)

1. a reinforcing fiber sizing agent, its contain epoxy resin (A), acid number lower than 5 unsaturated polyester (UP) (B) and fatty acid ester (C).
2. reinforcing fiber sizing agent as claimed in claim 1, wherein, relative to described epoxy resin (A) 100 weight portion, described unsaturated polyester (UP) (B) is 30 ~ 300 weight portions, relative to total 100 weight portion of described epoxy resin (A) with described unsaturated polyester (UP) (B), described fatty acid ester (C) is 1 ~ 15 weight portion.
3. reinforcing fiber sizing agent as claimed in claim 1 or 2, wherein, the weight average molecular weight Mw of described unsaturated polyester (UP) (B) is 1.2 ~ 2.1 with the ratio Mw/Mn of number-average molecular weight Mn.
4. the reinforcing fiber sizing agent according to any one of claims 1 to 3, wherein, described unsaturated polyester (UP) (B) is containing the condensation product of unsaturated dibasic acid (b1) with the alkylene oxide addition product (b2) of bisphenols.
5. the reinforcing fiber sizing agent according to any one of Claims 1 to 4, wherein, described unsaturated polyester (UP) (B) is that the reactive ingredients that the ratio making to meet following formula (I) contains the alkylene oxide addition product (b2) of unsaturated dibasic acid (b1) and bisphenols reacts and obtains
The molal quantity (I) of the alkylene oxide addition product (b2) of the molal quantity < bisphenols of unsaturated dibasic acid (b1).
6. the reinforcing fiber sizing agent according to any one of Claims 1 to 5, wherein, the acid number of described unsaturated polyester (UP) (B) is less than 4.5.
7. the reinforcing fiber sizing agent according to any one of claim 1 ~ 6, wherein, the fusing point of described fatty acid ester (C) is less than 5 DEG C.
8. the reinforcing fiber sizing agent according to any one of claim 1 ~ 7, wherein, described fatty acid ester (C) is the ester of the structure after having the unrighted acid of carbon number 10 ~ 24 and the monohydric alcohol ester bond bonding of carbon number 8 ~ 20.
9. the reinforcing fiber sizing agent according to any one of claim 1 ~ 8, wherein, the ratio that the total weight of described epoxy resin (A), described unsaturated polyester (UP) (B) and described fatty acid ester (C) is shared in the nonvolatile component of sizing agent is more than 70 % by weight.
10. a reinforcing fiber bundle, forms arbitrary described reinforcing fiber sizing agent in raw material reinforcing fiber bundle attachment claim 1 ~ 9.
11. 1 kinds of fiber reinforced composite materials, it contains matrix resin and reinforcing fiber bundle according to claim 10.
12. fiber reinforced composite materials as claimed in claim 11, wherein, described matrix resin is thermosetting resin.
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