CN105378176B - Sizing agent for reinforcing fiber and application therefor - Google Patents
Sizing agent for reinforcing fiber and application therefor Download PDFInfo
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- CN105378176B CN105378176B CN201480039921.7A CN201480039921A CN105378176B CN 105378176 B CN105378176 B CN 105378176B CN 201480039921 A CN201480039921 A CN 201480039921A CN 105378176 B CN105378176 B CN 105378176B
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- 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
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- 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
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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- 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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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
Technical field
The present invention relates to reinforcing fiber sizing agent and application thereof.Specifically, being related to strengthen matrix resin is made
Reinforcing fiber sizing agent, the reinforcing fiber beam and fiber reinforced composite material that have used this sizing agent.
Background technology
It is extensive with the fiber reinforced composite material that various synthetic fibers enhance plastic material (being referred to as matrix resin)
Using in mobile applications, aerospace purposes, CRUX purposes, general industrial applications etc..Answer as these can be used in
The fiber of condensation material, can enumerate the various inorfils such as carbon fiber, glass fibre, ceramic fibre, aramid fiber, polyamide fine
The various organic fibers such as dimension, polyethylene fibre.These various synthetic fibers are typically manufactured into long filament shape, afterwards by hot melt
Method or cylinder winding method etc. are processed into the sheet intermediate materials of so-called one direction prepreg, or with the processing of filament winding method,
Textile or chopped strand shape etc. are optionally processed into, are used through various high accuracy manufacturing procedures fine as reinforcing
Dimension.
As the matrix resin of reinforced fiber composite, epoxy resin is widely used.In addition to epoxy resin, also make
With unsaturated polyester resin, vinylester resin, acrylic resin etc. as radical polymerization syzygy matrix resin.
To improve the mechanical strength of reinforced fiber composite, matrix resin becomes important with the cementability of reinforcing fiber, right
In above-mentioned epoxy resin, the matrix resin of radical polymerization syzygy, it has been suggested that the sizing agent (example that the cementability of reinforcing fiber is improved
Such as, patent document 1,2 etc.).
Although however, patent document 1 or the sizing agent described in patent document 2 can be to epoxy resin or radical polymerization syzygies
Matrix resin improve reinforcing fiber cementability, but it is attached give the reinforcing fiber of sizing agent to be hardened over time, sometimes
Cause the problem that fluffing or the cementability to matrix resin are reduced.Also, the long-term storing stability of sizing agent is caused sometimes
Problem.
In addition, according to the difference of reinforcing fiber, also there is the reinforcing fiber of and fragile property little with elongation.Given with
Toward sizing agent these reinforcing fibers sometimes because of mechanical friction in manufacturing procedure etc., and cause fluffing, fibre cutting etc. to ask
Topic.
Therefore, in the field of fiber reinforced composite material, it is desirable to develop a kind of sizing agent, it can make reinforcing fiber
Compatibility between matrix resin is improved, and bonding securely, and can be suppressed the fluffing of reinforcing fiber beam, be suppressed over time
Hardening, and long-term storing stability is excellent.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 53-52796 publication
Patent document 2：Japanese Unexamined Patent Application 57-173150 publication
The content of the invention
Problems to be solved by the invention
In view of the conventional technical background, it is an object of the invention to provide a kind of sizing agent, it can for reinforcing fiber
Excellent cementability and matrix resin between is given, the fluffing of reinforcing fiber beam can be suppressed and with time hardening, and protected for a long time
Deposit excellent in stability；And using the reinforcing fiber beam and fiber reinforced composite material of the sizing agent.
The means of solve problem
As a result the present inventor etc. have found to solve the above problems and further investigated, by using epoxy resin (A) with it is specific
Unsaturated polyester (UP) (B), fatty acid ester (C) is reused, you can solve the problems, such as the present invention, so as to complete the present invention.
That is, reinforcing fiber sizing agent of the invention contain the unsaturated polyester (UP) (B) of epoxy resin (A), acid number less than 5 and
Fatty acid ester (C).
Relative to the weight portion of above-mentioned epoxy resin (A) 100, above-mentioned unsaturated polyester (UP) (B) is preferably 30~300 weight portions,
Relative to total 100 weight portions of above-mentioned epoxy resin (A) and 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 with the ratio (Mw/Mn) of number-average molecular weight (Mn)
~2.1.
Above-mentioned unsaturated polyester (UP) (B) preferably comprises unsaturated dibasic acid (B1) with the alkylene oxide addition product (B2) of bisphenols
Condensation product.
Above-mentioned unsaturated polyester (UP) (B) preferably make the ratio to meet following formula (I)s contain unsaturated dibasic acid (b1) with it is double
The reactive ingredients of the alkylene oxide addition product (b2) of phenols react and obtain.
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.
The monohydric alcohol of above-mentioned fatty acid ester (C) the preferably unrighted acid with carbon number 10~24 and carbon number 8~20
The ester of the structure after ester bond bonding.
Above-mentioned epoxy resin (A), above-mentioned unsaturated polyester (UP) (B) and total weight of above-mentioned fatty acid ester (C) account for sizing agent
The ratio of nonvolatile component be preferably more than 70 weight %.
The reinforcing fiber beam of the present invention is to adhere to above-mentioned reinforcing fiber to raw material reinforcing fiber beam to be formed with sizing agent.
The fiber reinforced composite material of the present invention contains matrix resin with above-mentioned reinforcing fiber beam.
Above-mentioned matrix resin is preferably thermosetting resin.
The effect of invention
The reinforcing fiber sizing agent of the present invention can invest excellent cementability between matrix resin to reinforcing fiber.
In addition, the fluffing of reinforcing fiber beam can be suppressed and hardened over time.Also, long-term storing stability is excellent.
The reinforcing fiber beam of the present invention will not be changed over or few over time due to sizing agent, even if therefore long-term
Preservation can also suppress the reduction of friction fluffing property and the cementability between matrix resin.By using the reinforcing fiber of the present invention
Beam, can obtain the reinforced fiber composite with excellent physical property.
Specific embodiment
The present invention be to strengthen the reinforcing fiber sizing agent that used of matrix resin, containing epoxy resin (A), it is specific not
Saturated polyester (B) and fatty acid ester (C).Hereinafter, describe in detail.
[epoxy resin (A)]
Epoxy resin (A) is the neccessary composition of the sizing agent of the present invention.Epoxy resin (A) refers to have in molecular structure
The compound of more than 2 reactive epoxy radicals.As epoxy resin (A), with can be from epoxychloropropane (epichlorohydrin)
The diglycidyl ether type obtained with active dydrogen compounds is representative, and other can enumerate glycidyl ester type, glycidic amine type, fat
It is ring-like etc..Epoxy resin (A) can use a kind, can also be applied in combination two or more.
Can enumerate as diglycidyl ether type epoxy resin (A)：What is for example manufactured with alcohols as raw material leads to following
The epoxy resin of the functional group that formula (1) is represented, the functional group that represents with following formulas (2) manufactured with phenols as raw material
Epoxy resin etc..Can enumerate as the epoxy resin (A) of glycidyl ester type：For example with phthalic acid derivatives or synthesis tree
Epoxy resin of functional group represented with following formulas (3) that the carboxylic acids such as fat aliphatic acid are manufactured for raw material etc..As shrink
Glycerine amine type epoxy resin (A) can be enumerated：For example there is the epoxy resin of the functional group of following formulas (4) expression or with following
Epoxy resin of functional group that formula (5) is represented etc..Can enumerate as alicyclic type epoxy resin (A)：For example there are following formulas
(6) epoxy resin of functional group for representing etc..Among these epoxy resin, to improve the reason of fiber and the cementability of matrix resin
By the epoxy resin of the functional group for preferably representing with formula (2).
[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, more preferably 120~1,000g/eq, further
It is preferred that 150~800g/eq.When epoxide equivalent is less than 100g/eq, the hardening with the time of reinforcing fiber beam is promoted sometimes.Epoxy
When equivalent is more than 1,500g/eq, sometimes the cementability between matrix resin is reduced.It should be noted that epoxide equivalent foundation
The definition of JIS-K7236.
The weight average molecular weight preferably 100~10,000, more preferably 100~8,000, further preferred 150 of epoxy resin (A)
~7,000.When weight average molecular weight is less than 100, sometimes heat resistance is not enough and volatilize in the drying process etc. of reinforcing fiber beam.Weight
When average molecular weight is more than 10,000, may make the long-term storing stability of sizing agent reduces.
For reinforcing fiber is improved with the cementability of matrix resin, have in epoxy resin (A) preferred molecular structure
The aromatic epoxy resin of aromatic rings.
As above-mentioned aromatic epoxy resin, can enumerate：The polynary phenolate of the monokaryons such as quinhydrones, resorcinol, catechol
The poly epihydric alcohol ether compound of compound；Dihydroxy naphthlene, bis-phenol, Bisphenol F, bisphenol-A, phenol novolac, the linear phenol of orthoresol
Aldehyde, resorcinol novolac, Bisphenol F novolac, bisphenol A novolak, dicyclopentadiene-modified phenol, triphenyl first
Poly epihydric alcohol ether compounds of multinuclear polyphenol compound such as alkane, tetraphenyl ethane etc..
Among these aromatic epoxy resins, the compound of preferably following formulas (7) expressions, following formulas (8) are represented
Compound, the compound that more preferably following formulas (7) represent.
[changing 7]
In formula (7), R5、R6、R7And R8It is separately hydrogen atom or methyl.N is 0~30 integer, preferably 0~
20, more preferably 0~10.
[changing 8]
In formula (8), m is 0~10 integer, 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, on
The epoxy resin (A) stated is general commercially available product, in the carbon fiber sizing agent of the present invention, can be using the commercially available asphalt mixtures modified by epoxy resin such as this
Fat (A).
[unsaturated polyester (UP) (B)]
Unsaturated polyester (UP) (B) of the acid number less than 5 is the neccessary composition of the sizing agent of the present invention.When the acid number is more than 5, by force
Change fibre bundle to be hardened over time, and the long-term storing stability of sizing agent can be reduced.The acid number preferably less than 4.5, more preferably 4
Hereinafter, further preferred less than 3.5.Acid number herein, is represented, foundation with the mg numbers of potassium hydroxide required during neutralization sample 1g
JIS K 2501：2003 and determine.
Unsaturated polyester (UP) refers to the petchem in molecular structure with more than 1 unsaturated bond.As unsaturated poly-
Ester can be enumerated：1) acid with more than 1 unsaturated bond individually with the condensation product of alcohol；2) with the acid of more than 1 unsaturated bond
And not with unsaturated bond sour mixture and alcohol condensation product；3) acid and the condensation of the alcohol with more than 1 unsaturated bond
Thing etc..Among these, the condensation product of particularly preferred 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 be enumerated：For example
Maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, mesaconic acid, citraconic acid, allyl malonic acid
Deng.Among these acid, particularly preferred carbon number 4~6 and aliphatic unsaturated dibasic acid.
Can enumerate as the alcohol of binary：Such as ethylene glycol, diethylene glycol, triethylene glycol, propane diols, DPG, fourth two
Alcohol, pentanediol, hexylene glycol, bisphenols, alkylene oxide addition product of bisphenols etc..Among these alcohol, the alkylene oxide of preferred bisphenols
Addition product.The alkylene oxide addition product of bisphenols and bisphenols is described below.
For the cementability of reinforcing fiber and matrix resin is improved, unsaturated polyester (UP) (B) preferably comprises above-mentioned insatiable hunger
With binary acid (hereinafter referred to as unsaturated dibasic acid (b1)) and the condensation product of 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, bis-phenol
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 is to instigate alkylene oxide addition polymerization in the compound of above-mentioned bisphenols.As
Alkylene oxide can enumerate oxirane, expoxy propane, epoxy butane.As preferably less than 10 moles of the addition molal quantity of alkylene oxide,
More preferably less than 5 moles, most preferably less than 2~4 moles.During such as addition more than 10 moles, may lose that bisphenols has is firm
Property and matrix resin between cementability reduce.
For reinforcing fiber beam be may refrain from the hardening of time and the storage stability of sizing agent, unsaturated polyester (UP) (B) is excellent
The reaction that choosing makes to meet the ratio of following formula (I)s and contains unsaturated dibasic acid (b1) and the alkylene oxide addition product (b2) of bisphenols
Property composition reaction and obtain.
The molal quantity (I) of the alkylene oxide addition product (b2) of the molal quantity ＜ bisphenols of unsaturated dibasic acid (b1)
Unsaturated dibasic acid (b1) is excellent with the mol ratio (b1/nb2) of the molal quantity of the alkylene oxide addition product (b2) of bisphenols
Select 70/100~99/100, more preferably 75/100~90/100, further preferred 80/100~85/100.
For the cementability of reinforcing fiber and matrix resin is improved, the alkylene oxide of unsaturated dibasic acid (b1) and bisphenols
Addition product (b2) accounts for preferably 90 moles more than % of total ratio, more preferably 95 moles more than the % of reactive ingredients, further excellent
Select 100 moles of more than %.
In addition, for the cementability of reinforcing fiber and matrix resin is improved, reactive ingredients are preferably substantially free of not
The carboxylate of monounsaturated dicarboxylic acid.Specifically, the shared ratio in reactive ingredients of the carboxylate of unsaturated dibasic acid preferably 2 is rubbed
You are below %, more preferably 1 mole below %, further preferred 0 mole of %.
When the acid number of unsaturated polyester (UP) (B) to be made declines, although it is contemplated that using the chemical combination of the active hydrogen-based with 1 sense
Thing as reactive ingredients, but using 1 sense active hydrogen-based when, sometimes the cementability between matrix resin can be reduced, separately
Outward it is also possible that the long-term storing stability of sizing agent is reduced, therefore the active hydrogen-based of 1 sense should not be used as reactive ingredients.
In detail, the compound of the active hydrogen-based with 1 sense accounts for preferably 2 moles below % of ratio of reactive ingredients, and more preferably 1 rubs
You are below %, further preferred 0 mole of %.
As the compound of the active hydrogen-based with 1 sense, 1 yuan of alcohol, secondary amine, 1 yuan of mercaptan etc. can be enumerated.
The weight average molecular weight preferably 500~5 of unsaturated polyester (UP) (B), 000, more preferably 800~4,500, further preferred 1,
000~3,500.When such as the molecular weight is less than 500, it may not be possible to while obtaining good cementability, heat resistance.On the other hand,
When such as the molecular weight is more than 5,000, 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) preferably 1.2~2.1 of number-average molecular weight (Mn),
More preferably 1.4~2.0, further preferred 1.6~1.9.When such as the molecular weight ratio is less than 1.2, it may not be possible to while obtaining good
Cementability, heat resistance.On the other hand, when such as the molecular weight ratio is more than 2.2, stability of solution may be made to be deteriorated.
It should be noted that the weight average molecular weight (Mw), number-average molecular weight (Mn) in the present invention is made using Tosoh (strain)
High Performance Gel Permeation chromatogram arrangement HLC-8220GPC, with sample solution concentration 2mg/mL injections splitter, (Showa electrician (strain) makes
Shodex (registration mark) KF-G, KF-402HQ, KF-403HQ) in, calculated by the curve map determined with RI detectors
Value.The use of tetrahydrofuran (THF) is mobile phase, the use of polyethylene glycol (PEG) is the standard substance for making calibration curve, with
Separate 40 DEG C of column temperature, flow velocity 0.3mL/ minutes to be measured.
Used as the manufacture method of unsaturated polyester (UP) (B), there is no particular limitation, can adopt known method.For example, can lead to
Crossing makes alkylene oxide addition product (b2) polycondensation of unsaturated dibasic acid (b1) and bisphenols and obtains.The promotion being just esterified and product
Acid number reduce for, preferably 110 DEG C~180 DEG C, more preferably 130 DEG C~160 DEG C of reaction temperature during polycondensation.The rush being just esterified
Enter and product acid number reduce for, preferably 1~10 hour, more preferably 2~5 hours reaction time during polycondensation.As being intended to
Promote polycondensation reaction, it is possible to use esterification catalyst.
[fatty acid ester (C)]
Fatty acid ester (C) is the required composition of the sizing agent of the present invention.Except epoxy resin (A) and epoxy resin (A) with
Outside unsaturated polyester (UP) (B), then by the way that containing fatty acid ester (C), the reinforcing fiber sizing agent of the present invention is for reinforcing fiber
Excellent cementability and matrix resin between can be given.In addition, the fluffing and the hardening with the time of reinforcing fiber beam can be suppressed.And
And, long-term storing stability can be made excellent.
Fatty acid ester (C) is the compound of the structure after being bonded with monohydric alcohol ester bond with aliphatic acid.
The saturated fatty acid of carbon number 10~24 or the unrighted acid of carbon number 10~24 can be enumerated as aliphatic acid.Just press down
For the fluffing of reinforcing fiber beam processed, the unrighted acid of preferred carbon number 10~24.The carbon number of aliphatic acid preferably 10~22, more
It is preferred that 12~20, further preferred 14~20.
Capric acid, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, peanut can be enumerated as the concrete example of aliphatic acid
Acid, behenic acid, tetracosanoic acid (lignoceric acid) etc..
The monohydric alcohol of carbon number 8~20 can be enumerated as monohydric alcohol.In more detail, the saturation unitary of carbon number 8~20 can be enumerated
The unsaturated monohydric alcohol of alcohol or carbon number 8~20.The carbon number of monohydric alcohol preferably 12~22, more preferably 14~20, further preferred 16
~20.
Can enumerate as the concrete example of monohydric alcohol：Octanol, decyl alcohol, laruyl alcohol, tridecanol, tetradecanol, hexadecanol,
Alcohol of heptadecanol, stearyl alcohol, oleyl alcohol, nonadecanol and their side chain etc..
Among these, for may refrain from the fluffing of reinforcing fiber beam, preferably there is carbon number 10~24 as fatty acid ester (C)
Unrighted acid be bonded with the monohydric alcohol ester bond of carbon number 8~20 after structure compound.The carbon of the unrighted acid
Number preferably 10~22, more preferably 12~20, further preferred 14~20.The carbon number of the monohydric alcohol preferably 12~22, more preferably 14
~20, further preferred 16~20.
As fatty acid ester (C), represented with following formulas (9).
R9-COOR10 (9)
In formula (9), R9It is alkyl, the alkenyl or alkynyl of carbon number 9~23.R9It is preferred that thiazolinyl.R9Can be straight chain, also may be used
Being branched.R9Carbon number preferably 12~22, more preferably 14~20, further preferred 16~20.
In formula (9), R10It is alkyl, the alkenyl or alkynyl of carbon number 8~20.R10Can be straight chain, or side chain
Shape.R10Carbon number preferably 10~20, more preferably 12~20, further preferred 14~20.
As the concrete example of fatty acid ester (C), can enumerate：Such as octyl laurate, laurate last of the ten Heavenly stems ester, laurate 12
Ester, the ester of laurate 13, the ester of laurate 14, laurate hexadecyl ester, the ester of laurate 17, laurate octadecyl ester, lauric acid oil
Alcohol ester, the ester of laurate 19, myristic acid monooctyl ester, myristic acid last of the ten Heavenly stems ester, nutmeg dodecyl gallate, the ester of myristic acid 13, meat
The ester of myristic acid 14, myristic acid hexadecyl ester, the ester of myristic acid 17, myristic acid octadecyl ester, myristic acid oleyl alcohol ester, Pork and beans
Cool sour 19 ester, octyl palmitate, palmitic acid last of the ten Heavenly stems ester, palm dodecyl gallate, the ester of palmitic acid 13, the ester of palmitic acid 14, palm
Sour hexadecyl ester, the ester of palmitic acid 17, stearyl palmitate, palmitic acid oil alcohol ester, the ester of palmitic acid 19, octyl stearate, tristearin
Sour last of the ten Heavenly stems ester, stearic dodecyl gallate, the ester of stearic acid 13, the ester of stearic acid 14, hexadecyl stearate, the ester of stearic acid 17, tristearin
Sour octadecyl ester, stearic acid oleyl alcohol ester, the ester of stearic acid 19, oleic acid monooctyl ester, decyl oleate, oily dodecyl gallate, the ester of oleic acid 13, oil
Sour 14 esters, cetyl oleate, the ester of oleic acid 17, oleic acid octadecyl ester, oleic acid oleic alcohol ester, the ester of oleic acid 19 etc..
Among these esters, for may refrain from the fluffing of reinforcing fiber beam, the misery ester of preferred oil, decyl oleate, oleic acid 12
Ester, the ester of oleic acid 13, the ester of oleic acid 14, cetyl oleate, the ester of oleic acid 17, oleic acid octadecyl ester, oleic acid oleic alcohol ester, oleic acid 19
Ester, more preferably cetyl oleate, the ester of oleic acid 17, oleic acid octadecyl ester, oleic acid oleic alcohol ester, the ester of oleic acid 19.
For may refrain from the fluffing of reinforcing fiber beam, preferably less than 5 DEG C of the fusing point of fatty acid ester (C), more preferably 5 DEG C~-
10 DEG C, further preferred 5 DEG C~-5 DEG C.During such as fusing point more than 5 DEG C, when in the winter time long-time preserves reinforcing fiber beam, aliphatic acid
Ester becomes solid fraction and may reduce suppressing the effect of fluffing.It should be noted that the following fusing point determined in the present invention.At two ends
Take in the capillary (internal diameter 1mm, below external diameter 2mm, 50~80mm of length) of open pipe and determine sample until the height of about 10mm
Degree.This is placed in into BUCHI melting point apparatus M-565, the temperature from below fusing point is with 1 DEG C/min of intensification.Try measure
Sample is melted, and will become transparent temperature as fusing point.
The weight average molecular weight preferably 300~700, more preferably 400~600, most preferably 500~600 of fatty acid ester (C).Such as
When the molecular weight is less than 300, may make the heat resistance of fatty acid ester reduces, volatilizees in the drying process of reinforcing beam, reduces suppression
The effect of system fluffing.When such as the molecular weight is more than 700, uprise may friction, reduce the effect that the suppression of reinforcing fiber beam is fluffed
Really.
[reinforcing fiber sizing agent]
The reinforcing fiber sizing agent of the present invention must contain above-mentioned epoxy resin (A), unsaturated polyester (UP) (B) and fat
Acid esters (C).
Unsaturated polyester (UP) (B) relative to weight portion preferably 30~300 weight portions of epoxy resin (A) 100, more preferably 35~
250 weight portions, further preferred 40~200 weight portion.When being such as less than 30 weight portion, reinforcing fiber may be made for radical polymerization
The cementability of the matrix resin of syzygy is reduced.When on the other hand, such as more than 300 weight portion, the texture of reinforcing fiber beam may be made
It is hardened, friction fluffing is easily produced in manufacturing procedure.
Relative to epoxy resin (A) and total 100 weight portions of unsaturated polyester (UP) (B), fatty acid ester (C) preferably 1~15
Weight portion, more preferably 3~12 weight portions, further preferred 5~10 weight portion.When being such as less than 1 weight portion, may reduce suppressing strong
Change the hairy effect of fibre bundle.When on the other hand, such as more than 15 weight portion, reinforcing fiber may be reduced viscous for matrix resin
Connecing property.
Epoxy resin (A), unsaturated polyester (UP) (B) account for the nonvolatile component of sizing agent with total weight of fatty acid ester (C)
Ratio preferably 70 weight % more than, more preferably 70~95 weight %, further preferred 75~90 weight %.Such as it is less than 70 weights
During amount %, reinforcing fiber may be reduced for the cementability of matrix resin.It should be noted that the nonvolatile component in the present invention
Refer to and remove solvent etc. so that 105 DEG C are heat-treated sizing agent, when reaching constant composition is parched.
To the security of human body or for preventing the disasters such as fire, preventing pollution of natural environment etc. when just processing, this
Bright sizing agent can also contain water.Do not damaging the present invention effect in the range of, it is possible to use methyl alcohol, ethanol, isopropanol, third
The organic solvents such as ketone, methyl ethyl ketone.
The sizing agent of the present invention self-emulsifying and/or emulsion dispersion in water are formed.The average grain diameter of sizing agent has no especially
Restriction, preferably less than 10 μm, more preferably 0.01~1 μm, further preferred 0.01~0.5 μm.The average grain diameter is more than 10 μm
When, it may not be possible to the uniform attachment of reinforcing fiber, and make sizing agent sheet i.e. anxiety of separation within a few days, storage stability
Difference and without practicality.
It should be noted that average grain diameter alleged in the present invention, is referred to and is surveyed by laser diffraction/scattering formula size distribution
Determine the mean value that the size distribution of device (hole field LA-910) measure is calculated.
In the range of the effect for not damaging the present invention, the sizing agent of the present invention is except the epoxy resin of above-mentioned middle explanation
(A), beyond unsaturated polyester (UP) (B) and fatty acid ester (C), also can be containing other compositions.As other compositions, can enumerate：
Such as various surfactants, various smooth agents, antioxidant, fire retardant, antiseptic, crystal nucleating agent, defoamer etc., can make
It is applied in combination with a kind or by two or more.
In epoxy resin (A) or unsaturated polyester (UP) (B) or fatty acid ester (C) or other sizing agents containing water-insoluble or
During the resin of slightly solubility, surfactant can effectively carry out aqueous emulsifying by using as emulsifying agent.
As surfactant, there is no particular limitation, can be from nonionic surfactant, Anionic surfactants
It is appropriate in agent, cationic surfactant and amphoteric surfactant to select known material and use.Surfactant can
Using a kind, also two or more can be applied in combination.
Can enumerate as nonionic surfactant：For example alkylene oxide addition nonionic surfactant is (senior
Alcohol, higher fatty acids, alkyl phenol, SP styrenated phenol, benzyl phenol, glycerine, pentaerythrite, sorbierite, anhydro sorbitol, dehydration
Addition of ethylene oxide, epoxy in sorbitol ester, castor oil, hardened castor oil, higher aliphatic amine, fatty acid amide, grease etc.
The material of the alkylene oxides such as propane (can be combined use two or more)), in PAG addition higher fatty acids etc. and
Into material, ethylene oxide/propylene oxide copolymer, ester, the aliphatic alkanolamide of polyalcohol and aliphatic acid etc..
In more detail, can enumerate as nonionic surfactant：Polyoxyethylene hexyl ether, polyoxyethylene octyl ether,
The polyoxy alkylidene straight chained alkyl ether such as polyoxyethylene last of the ten Heavenly stems ether, polyoxyethylenelauryl ether, polyoxyethylene margaron；Polyoxy is sub-
The polyoxy alkylidene branched primary alkyl moiety ethers such as ethyl 2- ethyl hexyl ethers, the different margaron of polyoxyethylene, the different stearyl ether of polyoxyethylene；
Polyoxyethylene 1- hexyl hexyl ether, polyoxyethylene 1- octyl group hexyl ether, polyoxyethylene 1- hexyl octyl ether, polyoxyethylene 1- penta
The polyoxy alkylidene branched secondary alkyl group ethers such as base heptyl ether, polyoxyethylene 1- heptyl amyl ether；The poly (oxyalkylene)s such as polyoxyethylene oil ether
Base alkene ether；The poly (oxyalkylene)s such as polyoxyethylene octyl group phenylate, polyoxyethylene nonyl phenylate, polyoxyethylene dodecyl phenylate
Base alkyl phenylate；Polyoxyethylene tristyryl base phenylate, polyoxyethylene diphenylethyllene phenylate, polyoxyethylene styrene
Base phenylate, polyoxyethylene tristyryl ylmethyl phenylate, polyoxyethylene diphenylethyllene methyl phenylate, polyoxyethylene benzene
Vinyl methyl phenylate, polyoxyethylene trityl phenylate, polyoxyethylene benzhydryl phenylate, polyoxyethylene benzyl
The polyoxyalkylene alkyl aryl phenylate such as phenylate；Polyoxyethylene monolaurate, polyoxyethylene monoleate, polyoxy Asia second
Base monostearate, polyoxyethylene list myristinate, polyoxyethylene dilaurate, polyoxyethylene dioleate,
The polyoxyalkylene fatty acid esters such as the myristinate of polyoxyethylene two, polyoxyethylene distearate；Anhydro sorbitol list
The anhydrosorbitol alcohol ester such as palmitate, Arlacel-80；Polyoxyethylene sorbitan monostearate, polyoxy
The polyoxyalkylene sorbitan alcohol fatty acid ester such as ethylidene Arlacel-80；Glyceryl monostearate, glycerine list
The fatty acid glycerides such as laurate, glycerol monopalmitate；Polyoxyalkylene sorbitan fatty acid ester；Sucrose fatty ester；
The polyoxy alkylidene castor oil ether such as polyoxyethylene castor oil ether；The polyoxy alkylidenes such as polyoxyethylene hardened castor oil ether are hardened
Castor oil ether；The polyoxyalkylene alkyl amino ethers such as polyoxyethylenelauryl base amino ethers, polyoxyethylene stearyl ether；
Oxyethylene-oxypropylene block or random copolymer；The end alkyl etherate of oxyethylene-oxypropylene block or random copolymer；
The end sucrose etherate of oxyethylene-oxypropylene block or random copolymer；Deng.
Can enumerate as anionic surfactant：For example carboxylic acid (salt), the sulfuric acid of the senior alcohol ether of higher alcohol,
Phosphate ester salt of the senior alcohol ether of sulfonate, higher alcohol etc..
In more detail, can enumerate as anionic surfactant：Such as oleic acid, palmitic acid, Oleic acid sodium salt, palmitic acid
The aliphatic acid such as sylvite, triethanol amine oleate (salt)；Hydroxyacetic acid, hydroxyacetic acid sylvite, lactic acid, lactic acid sylvite etc. contain hydroxyl
Carboxylic acid (salt)；The polyoxyalkylene alkyl ether acetic acid such as the ether acetic acid of polyoxyethylene 13 (sodium salt) (salt)；Trimellitic acid potassium,
The salt of the carboxyl Polysubstituted Aromatic Compounds such as benzenetetracarboxylic acid potassium；The alkyl benzene sulphonate such as DBSA (sodium salt) (salt)；It is poly-
The polyoxyalkylene alkyl ether sulfonic acid such as oxygen ethylidene 2- ethyl hexyl ether sulfonic acids (sylvite) (salt)；Stearyl N-methyltaurine
(sodium), lauroyl N-methyltaurine (sodium), myristoyl N-methyltaurine (sodium), palmityl N-methyltaurine (sodium) etc.
Higher fatty acid amides sulfonic acid (salt)；N- acyl group methyl amimoacetic acids such as lauroyl sarcosine (sodium) (salt)；Octylphosphonate (sylvite)
Deng alkyl phosphonic acid (salt)；The aromatic series phosphonic acids such as phenyl phosphonic acid esters (sylvite) (salt)；2- ethylhexyl phosphonate single 2-ethyl hexyls
The alkyl phosphonic acid alkyl phosphate such as ester (sylvite) (salt)；The nitrogenous alkyl phosphonic acid such as aminoethyl phosphonic acid (diethanolamine salt) (salt)；
The alkyl sulfate such as 2- ethylhexylsulfates (sodium salt) (salt)；The polyoxies such as polyoxyethylene 2- ethyl hexyl ether sulfuric ester (sodium salt)
Ethidene sulfate (salt)；The long-chain sulfosuccinic acids such as two -2- ethylhexylsulfosuccinate sodium, dioctyl sodium sulphosuccinate
The long-chain N- acyl glutamates such as salt, N- sodium lauroyl glutamates, N- stearyls-Pidolidone disodium；Deng.
Can enumerate as cationic surfactant：Such as lauryl trimethyl ammonium chloride, myristyl trimonium chlorine
Change ammonium, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oil base trimethyl ammonium chloride, cetyl trimethyl chlorine
Change ammonium, behenyl base trimethyl ammonium chloride, coco alkyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, stearyl front three
Base ammonium bromide, Cocoalkyl trimethylammonium bromide, cetyltrimethyl ammonium Methylsulfate, oleyl dimethyl ethyl ammonium sulfuric acid second
Ester, Quaternium 24, dilauryl ammonium chloride, VARISOFT TA100, octadecyl diethyl
The alkyl quaternary ammonium salts such as ammonium methyl sulfate；(polyoxyethylene) lauryl amino ether lactate, stearyl ether lactate, two
(polyoxyethylene) lauryl methyl amino ethers Dimethyl phosphate, oleyl methyl ethyl ammonium ethyl-sulfate, two (polyoxy Asia second
Base) lauryl ethyl ammonium ethyl-sulfate, two (polyoxyethylene) hardened tallow alkyl ethylamine ethyl-sulfates, two (polyoxy Asia second
Base) (polyoxy alkylidene) the alkyl ammonia such as lauryl methyl ammonium Dimethyl phosphate, two (polyoxyethylene) stearic amine lactates
Base ether salt；N- (2- hydroxyethyls)-N, N- dimethyl-N-stearyl amido propyl ammonium nitrate, lanolin fatty acid amido propyl ethyl
The acylamide alkyl quaternary ammonium salts such as Dimethyl Ammonium ethyl-sulfate, lauroyl acid amides ethyl-methyl diethyl ammonium Methylsulfate；Two
The alkyl oxygen ethylidene quaternary ammonium salt such as palmityl polyoxyethylene ethyl ammonium chloride, distearyl polyoxyethylene ammonio methacrylate；
The alkyl isoquinolinium salts such as lauryl isoquinolin chloride；Lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzene
The zephiran salt such as ammonio methacrylate；Benzyl dimethyl { 2- [2- (p- 1,1,3,3- tetramethyl butyl phenoxy group) ethyoxyl] second
Base } the Benzethonium salt such as ammonium chloride；The pyridiniujms such as pyrisept；Oil base hydroxyethyl imidazolines sulfuric acid second
The imidazoline salts such as ester, C 100L ethyl-sulfate；N- cocoyl arginine ethyl ester pyrrolidones carboxylics
The acyl group basic amino acid alkyl ester salt such as hydrochlorate, N- lauroyl lysine diethyl acetamidomalonate chlorides；Lauryl amine chloride, tristearin
The primary ammonium salts such as base amine bromide, hardened tallow alkyl amine chloride, rosin amine acetate；Cetyl methyl amine sulfuric ester, the moon
Osmanthus ylmethyl amine chloride, dilauryl amine acetate, stearic amine bromide, lauryl propyl group amine acetate, dioctylamine
The secondary amine salts such as chloride, octadecyl ethylamine hydroxide；Dilauryl methyl amine sulfuric ester, lauryl diethylamide chlorination
Thing, lauryl ethylmethylamine bromide, diethanol stearyl amido-propyl ethylamine trihydroxy ethyl phosphate, stearyl amido-propyl second
The tertiary amine salt such as ethylethanolamine urea polycondensation thing acetate；Fatty acid amide guanidinesalt；The alkane such as lauryl triethylene glycol ammonium hydroxide
Aklylene glycol ammonium salt of base three etc..
Can enumerate as amphoteric surfactant：Such as 2- undecyls-N, N- (hydroxyethyl carboxymethyl group) -2- imidazoles
The imidazoline system amphoteric surfactantes such as quinoline sodium, the sodium salt of 2- cocoyl -2- imidazoline hydroxide -1- Carboxyethoxies 2；
2- heptadecyl-N- carboxymethyl group-N- hydroxyethyl imidazolines glycine betaines, stearyl dimethyl betaine, lauryl dihydroxy
Base ethyl glycine betaine, lauryl dimethyl oxyneurine, alkyl betaine, amide betaine, sulfobetaines etc. are sweet
Dish alkali system amphoteric surfactant；N- lauryl Glys, N- lauryls β-alanine, N- stearyls β-alanine, lauryl
Amino acid type amphoteric surfactant such as alanine sodium etc..
Containing the shared part by weight in the nonvolatile component of sizing agent of surfactant during surfactant preferably 5~
30 weight %, more preferably 10~25 weight %, further preferred 15~25 weight %.
There is no particular limitation for the nonvolatile component concentration of the sizing agent of the present invention, it is considered to is made stablizing for aqueous dispersion
Property, suitably select as product easy to handle viscosity etc..If consider conveying cost of product etc., nonvolatile component is upper
Shared part by weight preferably 10~100 weight % in slurry agent entirety, further preferred 15~100 weight %, particularly preferred 20
~100 weight %.
In addition, more than water and nonvolatile component preferably 90 weight % of shared total part by weight in sizing agent entirety,
It is more than more preferably 95 weight %, it is more than further preferred 99 weight %, particularly preferred 100 weight %.When being such as less than 90 weight %,
I.e. containing heat treatment when not as nonvolatile component residual above-mentioned organic solvent, other weight % of low-boiling compound 10 with
When upper, when just processing to the security of human body, prevent for the pollution of natural environment, it is sometimes not preferred.
It should be noted that in above-mentioned aqueous dispersion or the aqueous solution, except above-mentioned security to human body, prevent to from
Outside for the pollution of right environment, for preventing the thickening/solidification with the time of aqueous dispersion, the aqueous solution, even if not containing
Or be preferably during solvent beyond the water containing organic solvent etc. relative to below 10 overall weight % of sizing agent, more preferably
Below 5 weight %, below more preferably 1 weight %.
The sizing agent of the present invention is fabricated to into the method for aqueous dispersion, and there is no particular limitation, can adopt known method.
As above-mentioned, can enumerate：Manufacture is respectively prepared aqueous dispersion when constituting each composition of sizing agent, by the side of these composition mixing
Method；The method of its emulsion dispersion will be made in warm water under each composition input stirring for constituting sizing agent；The each of sizing agent will be constituted
The method of the emulsified dispersed liquid mixing after the advance emulsion dispersion of composition；Each composition mixing of sizing agent will be constituted, make the mixed of gained
After compound is heated up to more than softening point, apply mechanical shear stress using homogenizer, homogenizer, ball mill etc. while delaying
Devote slowly in water and carry out method of Phase inversion emulsification etc..
[reinforcing fiber beam and its manufacture method]
The reinforcing fiber beam of the present invention is to adhere to above-mentioned reinforcing fiber to raw material reinforcing fiber beam to be formed with sizing agent, and
It is the reinforcing fiber for strengthening matrix resin.It is excellent in adhesion between the reinforcing fiber beam and matrix resin of the present invention.Just
For making cementability raising effect higher by the sizing agent of the present invention, the preferred thermoset matrix resin of matrix resin.This
Bright reinforcing fiber beam is few because of fluffing, therefore operation is excellent by property, due to reinforcing fiber sizing agent will not be over time change
Change or change over time is lacked, therefore long-term preservability can be made excellent.
Adhesion amount of the nonvolatile component of sizing agent to raw material reinforcing fiber beam can be suitably selected, as long as being set to make
Reinforcing fiber beam has the necessary amount of required function, but the adhesion amount relative to raw material reinforcing fiber Shu Youxuan 0.1
~20 weight %.In the reinforcing fiber beam of long fibre form, relative to raw material reinforcing fiber beam its adhesion amount more preferably 0.1~10
Weight %, further preferred 0.5~5 weight %.In addition, in the beam of chopped strand form (cutting into the state of specific length),
More preferably 0.5~20 weight %, more preferably 1~10 weight %.
When the adhesion amount of such as sizing agent is few, it is difficult to obtain of the invention involved by heat resistance, resin impregnated, cementability
Effect, additionally, it is possible to make the pack deficiency of reinforcing fiber beam, make treatability be deteriorated.In addition, the adhesion amount such as sizing agent is excessive
When, reinforcing fiber beam will be made too upright and outspoken, make treatability be deteriorated on the contrary, make resin impregnated be deteriorated during composite molding, thus it is unexcellent
Choosing.
The manufacture method of reinforcing fiber beam includes：Prepare and contain above-mentioned sizing agent, the part by weight of nonvolatile component is
0.5~10 weight %, water and the preparation section that total part by weight of nonvolatile component is treatment fluid more than 90 weight %；
And, to make nonvolatile component that the treatment fluid attachment is made for 0.1~20 weight % relative to the adhesion amount of raw material reinforcing fiber beam
In the attachment operation of raw material reinforcing fiber beam.
In preparation section, preferably 0.5~10 weight % of the part by weight in treatment fluid shared by nonvolatile component is more excellent
Select 1~5 weight %.Water is preferably more than 95 weight % with total part by weight of nonvolatile component, more preferably 99 weights
Amount more than %, particularly preferably 100 weight %.
In attachment operation, the adhesion amount of preferred nonvolatile component is as in the previous paragraph.Sizing agent is set to be attached to raw material strong
The method for changing fibre bundle is not particularly limited, as long as method, roller infusion process, spray-on process and other known methods are licked with roller make
The method that sizing agent is attached to raw material reinforcing fiber beam.Among these methods, roller infusion process is because making sizing agent uniform
Be attached to raw material reinforcing fiber beam, therefore it is preferred that.
There is no particular limitation for the drying means of the attachment of gained, for example, can be carried out with heating roller, hot blast, hot plate etc.
Heat drying.
It should be noted that when making the sizing agent of the present invention be attached to raw material reinforcing fiber beam, the composition of sizing agent can be made
Composition adheres to after all mixing, and can also make constituent be respectively divided into the attachment of more than two-stage.In addition, not hindering the present invention's
In the range of effect, in addition to epoxy resin (A), unsaturated polyester (UP) (B) and fatty acid ester (C), also can make vinylester resin,
The thermoplastic resin such as the thermosetting resins such as phenolic resin and/or vistanex, polyester resin, nylon resin, acrylic resin
Fat is attached to raw material reinforcing fiber beam.
The reinforcing fiber beam of the present invention can be used as the reinforcing fiber of the composite with various resins as matrix resin,
Can be long fibre form, alternatively chopped strand form as the form for using.
As (raw material) reinforcing fiber beam of the sizing agent of the applicable present invention, carbon fiber, glass fibre, ceramics can be enumerated
The various inorfils of fiber, aramid fibre, polyethylene fibre, dacron fibre, poly- terephthaldehyde
The ester fiber of sour fourth two, PEN fiber, polyarylate fiber, polyacetal fibre, pbo fiber, polyphenylene sulfide fibre,
The beam of the various organic fibers such as polyketone fiber etc..For the physical property as the fiber reinforced composite material of gained, as (former
Material) reinforcing fiber beam be preferably selected from carbon fiber, aramid fibre, polyethylene fibre, dacron fibre,
It is poly fiber, PEN fiber, polyarylate fiber, polyacetal fibre, pbo fiber, poly-
At least one beam in sulfide fibers and polyketone fiber, more preferably carbon fiber bundle.
[fiber reinforced composite material]
The fiber reinforced composite material of the present invention is the material containing matrix resin with above-mentioned reinforcing fiber beam.Reinforcing is fine
Dimension beam is processed by the sizing agent of the present invention, sizing agent is equably adhered to, and can be made between reinforcing fiber beam and matrix resin
Compatibility is good, becomes fiber reinforced composite material excellent in adhesion.Herein, matrix resin refer to comprising thermosetting resin or
The matrix resin of thermoplastic resin, can contain one or two or more kinds.It is not particularly limited as thermosetting resin, can enumerates
Epoxy resin, phenolic resin, unsaturated polyester resin, vinylester resin, acrylic resin, cyanate ester resin, polyimides
Resin etc..It is not particularly limited as thermoplastic matrix resin, polyolefin-based resins, polyamide series resin, poly- carbon can be enumerated
Acid ester resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, plexiglass, polyphenylene sulfide
Resin, polyetherimide resin, polyether ketone resin etc..Among these resins, the cementability for being based on the sizing agent of the present invention is carried
For high effect is higher, preferred thermoset matrix resin, more preferably epoxy resin, unsaturated polyester resin, vinylester resin, most
Preferred epoxy.Herein, epoxy resin refers to the compound in molecular structure with reactive epoxy radicals, by with curing agent
Heat after mixing, epoxy radicals cross-linked network can be made and solidified.As epoxy resin, can enumerate with the necessity as sizing agent into
Above-mentioned epoxy resin (A) the identical epoxy resin for dividing.These matrix resins are bonding between reinforcing fiber beam for making
Property the purpose such as more improve so as to even a part of or all modified.
As the manufacture method of fiber reinforced composite material, there is no particular limitation, can adopt by chopped strand, long fibre
The known side such as composite injection shaping, the punch forming by UD pieces, textile piece etc., other fiber winding formings of particle etc.
Method.
When thermoset matrix resin and reinforcing fiber beam are kneaded, have after curing agent is mixed and add under pressurization or normal pressure
The method of heat and manufacture fiber reinforced composite material；Or, by curing agent, curing accelerator mixes and manufacture fiber is strong in normal temperature
The method for changing composite.
The content of the reinforcing fiber beam in fiber reinforced composite material also without special restriction, as long as according to the species of fiber,
Form, species of matrix resin etc. and suitably select, but for available fiber reinforced composite material, preferably 5~70 weights
Amount %, more preferably 20~60 weight %.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the invention is not limited in embodiments described herein.Need
It is noted that the percentage (%) represented in below example as long as, part without special restriction mean that " weight % ",
" weight portion ".The measure of each characteristic value is carried out according to method shown below.
<Stability of solution>
Each process emulsion that nonvolatile component concentration is 3.0 weight % is preserved to adjust to 50 DEG C of thermostat, with visual
Confirm the outward appearance of solution, stability of solution is judged with following assessment benchmark.
◎：60 days without separation.
○：Without separation, separated within 60 days within 30 days.
△：Without separation, separated within 30 days within 7 days.
×：Separated within 7 days.
××：The emulsification same day separates, or cannot emulsify.
<Cementability>
Using composite material interface characteristic evaluation apparatus HM410 (Dong Rong industries joint-stock company), entered by microlayer model method
Row cementability is assessed.
Carbon fiber wire is taken out by the carbon fiber bundle of gained in embodiment and comparative example, specimen mounting is placed in.Make to be mixed with admittedly
Agent, the droplet formation of each matrix resin of curing accelerator solidify drop in carbon fiber wire by following curings,
Obtain the sample of measure.Sample will be determined and is placed in equipment, drop is clamped with device blade, make carbon fiber wire on device with
0.06mm/ minutes speed movement, determine from carbon fiber wire extract drop when maximum pull-out forces F.
Interface shear strength τ is calculated by following formula, cementability assessment between carbon fiber wire and matrix resin is carried out.
Interface shear strength τ (units：MPa)=F/ π dl
(F：Maximum extracts pulling force d：Carbon fiber wire diameter 1：The particle diameter for extracting direction of drop)
(curing of the drop (drop) of each matrix resin)
Matrix resin is to use epoxy resin in embodiment 1~10 and comparative example 1~4,7~9, in embodiment 11~14
And in comparative example 5 be to use unsaturated polyester resin, it is to use vinylester resin in embodiment 15~18 and comparative example 6.
Epoxy resin：With 80 DEG C × 1 hour, 150 DEG C × 3 hours, will adjust to epoxy resin JER828 (Mitsubishi Chemical's stocks
Part company system) 100 weight portions, the drop heating of the matrix resin of DICY (joint-stock company of Mitsubishi Chemical) 3 weight portions so as to Gu
Change.
Unsaturated polyester resin：With 80 DEG C × 1 hour, 150 DEG C × 3 hours, will adjust to unsaturated polyester resin
(day is oily for Rigolac (リ go ラ Star Network) M540 (Showa electrician joint-stock company) 100 weight portions, Permek (the メ Star Network of パ mono-) N
Joint-stock company) 2 weight portions matrix resin drop heating so as to solidify.
Vinylester resin：With 80 DEG C × 1 hour, 150 DEG C × 3 hours, will adjust to vinylester resin Repoxy (リ Port キ
シ) R-806 (Showa electrician joint-stock company) 100 weight portions, Percure (the キ ュ ア mono- of パ mono-)-O (You joint-stock companies)
The drop heating of the matrix resin of 2 weight portions so as to solidify.
<Friction fluffing property>
Using TM formulas friction obvolvent force tester TM-200 (Daiei science essence device makes institute's (strain) system), using being configured to
The minute surface chromium plating stainless pin 3 of "the" shape, with the tension force of 50g, the carbon fiber bundle obtained in friction embodiment and comparative example
1,000 time (300 beats/min of back and forth movement speed), with the fluffing state that following benchmark visually confirm carbon fiber bundle.
◎：Fluffing is had not seen completely in the same manner as before friction.
○：Although seeing several Zhi Qimao, the upper unchallenged degree completely of practicality.
△：Visible many fluffings, can also confirm some fracture of wires.
×：The fracture of wire of very many fluffing and monofilament can be confirmed to have.
<Fiber keeping quality>
Gained carbon fiber bundle 10 days in embodiment and comparative example are preserved with 100 DEG C, the hard of the carbon fiber bundle after preserving is tried to achieve
The difference of the hardness of the carbon fiber bundle before degree and preservation, can determine whether to go on business less, and the hardening with the time is fewer.Carbon fiber bundle (length：
About 50cm) hardness with texture testing machine, (HANDLE-O-METERHOM-2 Daieis science essence device makes institute's (strain) system, and seam is wide
10mm) it is measured.
[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, liquid bisphenol A type epoxy resin, epoxide equivalent 184~194
JER807：Joint-stock company of Mitsubishi Chemical, liquid 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)
0.9 mole of maleic anhydride is set to react in 140 DEG C with 4 moles of oxirane, 1.0 moles of the addition product of bisphenol-A
5 hours, 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 equal with number
The ratio (Mw/Mn) of molecular weight (Mn) is 1.6.
(synthesis example B-2)
0.8 mole of maleic anhydride is set to react in 140 DEG C with 2 moles of oxirane, 1.0 moles of the addition product of bisphenol-A
3 hours, 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 equal with number
The ratio (Mw/Mn) of molecular weight (Mn) is 1.7.
(synthesis example B-3)
0.85 mole of fumaric acid is set to react 8 in 170 DEG C with 3 moles of oxirane, 1.0 moles of the addition product of bisphenol-A
Hour, 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 equal with number
The ratio (Mw/Mn) of molecular weight (Mn) is 1.9.
(synthesis example B-4)
0.9 mole of maleic anhydride is set to react in 150 DEG C with 3 moles of expoxy propane, 1.0 moles of the addition product of bisphenol-A
5 hours, 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 equal with number
The ratio (Mw/Mn) of molecular weight (Mn) is 1.7.
[synthesis of unsaturated polyester (UP)]
(synthesis example b-1)
1.0 moles of maleic anhydride is set to react in 135 DEG C with 2 moles of oxirane, 1.0 moles of the addition product of bisphenol-A
2 hours, 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 equal with number
The ratio (Mw/Mn) of molecular weight (Mn) is 2.0.
(synthesis example b-2)
1.0 moles of maleic anhydride is set to react in 135 DEG C with 2 moles of oxirane, 1.0 moles of the addition product of bisphenol-A
5 hours, then its reaction 5 hours is made with 170 DEG C, obtain the unsaturated polyester (UP) (b-2) of acid number 6.3.Weight average molecular weight (Mw) is 5,
736, weight average molecular weight (Mw) is 2.3 with the ratio (Mw/Mn) of number-average molecular weight (Mn).
(synthesis example b-3)
1.0 moles of maleic anhydride is set to react in 160 DEG C with 4 moles of oxirane, 1.0 moles of the addition product of bisphenol-A
5 hours, 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 equal with number
The ratio (Mw/Mn) of molecular weight (Mn) is 2.0.
(synthesis example b-4)
1.0 moles of maleic anhydride is set to react in 140 DEG C with 3 moles of oxirane, 1.0 moles of the addition product of bisphenol-A
4 hours, 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 equal with number
The ratio (Mw/Mn) of molecular weight (Mn) is 2.1.
[fatty acid ester (C)]
Oleic acid oleic alcohol ester：4 DEG C of fusing point
Laurel oleate：11 DEG C of fusing point
Ethylhexyl stearate：10 DEG C of fusing point
[embodiment 1]
By JER1001, unsaturated polyester (UP) (B- in the way of the nonvolatile component for becoming the inorganic agent shown in table 1 is constituted
1), oleic acid oleic alcohol ester, POE (150) hardened castor oil ether, PO/EO (25/75) polyethers (molecular weight 16,000) load emulsifier unit
In, low adding water under stirring makes its Phase inversion emulsification, obtains the sizing agent aqueous dispersion of weight % of nonvolatile component concentration 30.With
Sizing agent aqueous dispersion obtained by water dilution, prepares the sizing agent emulsion of weight % of nonvolatile component concentration 3, makes at sizing agent
After reason carbon fiber bundle (fiber number 800tex, silk number 12,000) dipping/infiltration, its heated-air drying is made 15 minutes with 105 DEG C, obtained
Obtain the sizing agent Treatment of Carbon beam that theoretical adhesion amount is 1.0%.By above-mentioned method, each of this sizing agent and this beam is carried out
Characteristic value is assessed.With regard to cementability and friction fluffing property, using carbon fiber bundle and fiber keeping quality before the assessment of fiber keeping quality
Carbon fiber bundle after assessment, is estimated respectively.In the results are shown in table 1.
[embodiment 2~18, comparative example 1~9]
Except in embodiment 1 sizing agent emulsion is adjusted to the nonvolatile component packet of the inorganic agent as shown in table 1~3
Into beyond, remaining obtains sizing agent Treatment of Carbon beam similarly to Example 1, assesses each characteristic value.By commenting for each characteristic value
Valency result 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, the fibre bundle and matrix of embodiment
It is excellent in adhesion between resin, also inhibits fluffing.Also, fiber keeping quality is excellent, the cementability after fiber is preserved is also
It is excellent, it is suppressed that fluffing.
Industrial applicability
Jing reinforcing fibers strengthen the fiber reinforced composite material of matrix resin can be used in mobile applications, aerospace use
On the way, in CRUX purposes, general industrial applications etc..Carbon fiber, glass fibre, ceramic fibre etc. can be enumerated as reinforcing fiber
The various organic fibers such as various inorfils, aramid fibre, Fypro, polyethylene fibre.The starching of the present invention
Agent is applicable to strengthen the reinforcing fiber of matrix resin.
Claims (10)
1. a kind of reinforcing fiber sizing agent, it contains the unsaturated polyester (UP) (B) of epoxy resin (A), acid number less than 5 and aliphatic acid
Ester (C),
Condensation product of the unsaturated polyester (UP) (B) containing unsaturated dibasic acid (b1) with the alkylene oxide addition product (b2) of bisphenols,
Relative to the weight portion of the epoxy resin (A) 100, the unsaturated polyester (UP) (B) is 30~300 weight portions, relative to institute
Total 100 weight portions of epoxy resin (A) and the unsaturated polyester (UP) (B) are stated, the fatty acid ester (C) is 1~15 weight portion.
2. reinforcing fiber sizing agent as claimed in claim 1, wherein, weight average molecular weight Mw of the unsaturated polyester (UP) (B)
It is 1.2~2.1 with the ratio Mw/Mn of number-average molecular weight Mn.
3. reinforcing fiber sizing agent as claimed in claim 1 or 2, wherein, the unsaturated polyester (UP) (B) is made with satisfaction
The reactive ingredients reaction of the alkylene oxide addition product (b2) that the ratio for stating formula (I) contains unsaturated dibasic acid (b1) and bisphenols and
,
The molal quantity (I) of the alkylene oxide addition product (b2) of the molal quantity ＜ bisphenols of unsaturated dibasic acid (b1).
4. reinforcing fiber sizing agent as claimed in claim 1 or 2, wherein, the acid number of the unsaturated polyester (UP) (B) is 4.5
Below.
5. reinforcing fiber sizing agent as claimed in claim 1 or 2, wherein, the fusing point of the fatty acid ester (C) be 5 DEG C with
Under.
6. reinforcing fiber sizing agent as claimed in claim 1 or 2, wherein, the fatty acid ester (C) be with carbon number 10~
24 unrighted acid be bonded with the monohydric alcohol ester bond of carbon number 8~20 after structure ester.
7. reinforcing fiber sizing agent as claimed in claim 1 or 2, wherein, it is the epoxy resin (A), described unsaturated poly-
Ester (B) ratio shared in the nonvolatile component of sizing agent with total weight of the fatty acid ester (C) be 70 weight % with
On.
8. a kind of reinforcing fiber beam, arbitrary described reinforcing fiber in claim 1~7 is adhered to raw material reinforcing fiber beam and is used
Slurry agent is formed.
9. a kind of fiber reinforced composite material, it contains matrix resin and the reinforcing fiber beam described in claim 8.
10. fiber reinforced composite material as claimed in claim 9, wherein, the matrix resin is thermosetting resin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2013200699 | 2013-09-27 | ||
| JP2013-200699 | 2013-09-27 | ||
| PCT/JP2014/070302 WO2015045618A1 (en) | 2013-09-27 | 2014-08-01 | Sizing agent for reinforcing fiber and application therefor |
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| CN105378176A CN105378176A (en) | 2016-03-02 |
| CN105378176B true CN105378176B (en) | 2017-05-17 |
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| JP (1) | JP5730457B1 (en) |
| KR (1) | KR102190010B1 (en) |
| CN (1) | CN105378176B (en) |
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| WO (1) | WO2015045618A1 (en) |
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| CN109891021B (en) * | 2016-10-28 | 2022-04-12 | 三菱化学株式会社 | Sizing agent for carbon fiber, aqueous dispersion of sizing agent for carbon fiber, and carbon fiber bundle having sizing agent attached thereto |
| CN108484891B (en) * | 2018-03-12 | 2020-05-08 | 吉林乾仁新材料有限公司 | Preparation of self-assembly self-emulsifying self-stabilizing polyester type high-performance fiber interface modification auxiliary agent, product and application |
| JP7281352B2 (en) * | 2018-06-26 | 2023-05-25 | 三洋化成工業株式会社 | Fiber sizing agents, fiber bundles, textile products, prepregs and moldings |
| CN112292488B (en) * | 2018-06-29 | 2023-12-29 | 三菱化学株式会社 | Sizing agent, reinforcing fiber bundle, fiber-reinforced resin molding material, and fiber-reinforced composite material |
| CN109180476B (en) * | 2018-08-27 | 2020-12-01 | 西南交通大学 | High-carbon alcohol ester and preparation method thereof |
| DE112019005802T5 (en) * | 2018-11-20 | 2021-08-26 | Dic Corporation | Fiber sizing agent, fiber material, molding compound and molding |
| JP6614629B1 (en) * | 2019-09-27 | 2019-12-04 | 竹本油脂株式会社 | Carbon fiber sizing agent and carbon fiber |
| CN111005229B (en) * | 2019-12-27 | 2021-03-02 | 鸿羽腾风材料科技有限公司 | Carbon fiber sizing agent and preparation method thereof |
| EP4239120A1 (en) * | 2020-10-30 | 2023-09-06 | Sanyo Chemical Industries, Ltd. | Fiber sizing agent composition, fiber bundle, fiber product, and composite material |
| CN112679717B (en) * | 2020-12-04 | 2023-06-27 | 吉林乾仁新材料有限公司 | Preparation method of multipurpose self-emulsifying anionic unsaturated polyester carbon fiber sizing agent, product and application thereof |
| TWI797655B (en) | 2021-06-28 | 2023-04-01 | 臺灣塑膠工業股份有限公司 | Sizing agent composition, carbon fiber material and composite material |
| TWI784693B (en) * | 2021-08-27 | 2022-11-21 | 臺灣塑膠工業股份有限公司 | Sizing agent for carbon fiber |
| CN116031184A (en) | 2021-10-25 | 2023-04-28 | 大立钰科技有限公司 | Wafer access assembly, wafer access device and wafer carrier thereof |
| JP7480244B2 (en) | 2021-11-01 | 2024-05-09 | 三洋化成工業株式会社 | Fiber sizing agent composition, fiber bundle, fiber product, and composite material |
| JP7220323B1 (en) * | 2022-05-16 | 2023-02-09 | 三洋化成工業株式会社 | Fiber sizing agent composition and fiber sizing agent solution |
| JP7235925B1 (en) * | 2022-05-16 | 2023-03-08 | 三洋化成工業株式会社 | Fiber sizing agent composition and fiber sizing agent solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0295916A2 (en) * | 1987-06-16 | 1988-12-21 | Takemoto Yushi Kabushiki Kaisha | Sizing agents for carbon fibers |
| CN1745127A (en) * | 2003-01-30 | 2006-03-08 | 东邦泰纳克丝株式会社 | Carbon fiber-reinforced resin composite materials |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5352796A (en) | 1976-10-19 | 1978-05-13 | Sanyo Chemical Ind Ltd | Surface treating resin composition for carbon fiber and composite carbon fiber material containing said treated fiber |
| JPS5943298B2 (en) | 1981-12-16 | 1984-10-20 | 東レ株式会社 | carbon fiber composite material |
| JPS60104578A (en) * | 1983-11-05 | 1985-06-08 | 竹本油脂株式会社 | Sizing agent for carbon fiber |
| JPS6392780A (en) * | 1986-09-30 | 1988-04-23 | 竹本油脂株式会社 | Sizing agent for carbon fiber |
| JPH0718085B2 (en) * | 1987-04-27 | 1995-03-01 | 竹本油脂株式会社 | Sizing agent for carbon fiber |
| US5242958A (en) * | 1991-07-12 | 1993-09-07 | Ppg Industries, Inc. | Chemical treating composition for glass fibers having emulsified epoxy with good stability and the treated glass fibers |
| JP2957406B2 (en) * | 1993-12-28 | 1999-10-04 | 東邦レーヨン株式会社 | Sizing agent for carbon fiber strand, sized carbon fiber strand, and prepreg using carbon fiber strand as reinforcing fiber |
| JPH08120069A (en) * | 1994-09-02 | 1996-05-14 | Mitsui Toatsu Chem Inc | Unsaturated polyester resin |
| JP3156990B2 (en) * | 1995-07-17 | 2001-04-16 | 竹本油脂株式会社 | Sizing method of carbon fiber |
-
2014
- 2014-08-01 KR KR1020167005031A patent/KR102190010B1/en active IP Right Grant
- 2014-08-01 CN CN201480039921.7A patent/CN105378176B/en active Active
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- 2014-08-01 JP JP2015504801A patent/JP5730457B1/en active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0295916A2 (en) * | 1987-06-16 | 1988-12-21 | Takemoto Yushi Kabushiki Kaisha | Sizing agents for carbon fibers |
| CN1745127A (en) * | 2003-01-30 | 2006-03-08 | 东邦泰纳克丝株式会社 | Carbon fiber-reinforced resin composite materials |
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| WO2015045618A1 (en) | 2015-04-02 |
| TWI648451B (en) | 2019-01-21 |
| KR102190010B1 (en) | 2020-12-11 |
| KR20160061319A (en) | 2016-05-31 |
| JPWO2015045618A1 (en) | 2017-03-09 |
| CN105378176A (en) | 2016-03-02 |
| JP5730457B1 (en) | 2015-06-10 |
| TW201525233A (en) | 2015-07-01 |
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