JP2001316980A - Resin composition for bundling fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for bundling fibers, capable of satisfying both of reduction of yarn break and fluff in a finishing step of the fibers usable for a fiber-reinforced composite material, and having good opening properties. SOLUTION: This resin composition for the bundling is characterized in that the penetrating rate (Pe) of a wool felt having the resin composition for the bundling impregnated therein, into a methyl ethyl ketone solution of a matrix resin (65 wt.% concentration) is regulated so as to be 1-40 sec.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for bundling fibers. More specifically, the present invention relates to a resin composition for bundling fibers used in a composite material.

[0002]

2. Description of the Related Art Fiber-reinforced composite materials obtained by combining fibers with a matrix resin such as an epoxy resin, an unsaturated polyester resin, or a polyamide resin are widely used in the fields of sports, leisure, aerospace, and the like. The fibers used in the composite material include polyamide fibers, aramid fibers, Kevlar fibers, polyethylene fibers, polyester fibers, glass fibers, carbon fibers, and other inorganic fibers. These fibers are usually manufactured in the form of filaments or tows, and further processed into unidirectionally aligned sheets, tapes, filament windings, woven fabrics, chopped fibers, and the like. By the way, in the processing of such fibers, it is required that the fibers repeatedly come into contact with various guides during the processing step and do not generate fluff or breakage even when subjected to friction. Usually, a fiber sizing agent is applied to the filament or tow to prevent fluff or yarn breakage (abrasion resistance). In addition, in order to obtain a high-quality processed product, a property (opening property) in which the fiber is easily thinned with a weak contact pressure and the fiber is spread without gaps is required.

As the resin composition used for the fiber sizing agent, those comprising various epoxy resins (JP-A-3-76872) and polyurethane resins (JP-A-1-314786) are known. .

[0004]

However, the conventional sizing agent for fibers made of a resin composition reduces fiber breakage and fluff during the processing step (scratch resistance) and has good openability. Nothing satisfies both.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, the present invention relates to a resin composition for sizing a composite material reinforcing fiber, the penetration rate of a wool felt impregnated with the resin composition for sizing into a methyl ethyl ketone solution (concentration 65% by weight) of a matrix resin ( Pe) is 1 to 40
a fiber sizing resin composition comprising: a fiber sizing agent containing the resin composition; a fiber treated with the fiber sizing agent or the fiber sizing agent; a fiber and a matrix resin And a molded article comprising the prepreg.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The resin contained in the sizing resin composition of the present invention is selected from the group consisting of a ring-opening polymerization resin, a polyaddition resin, a polycondensation resin, and an addition condensation resin.
Species or combinations thereof.

Epoxy resins and polyacetal resins as ring-opening polymerization resins, polyurethane resins as polyaddition resins, polyester resins, polyamide resins and polycarbonate resins as polycondensation resins, phenol resins and urea as addition condensation resins Resins, xylene resins and the like. Among these, preferred are an epoxy resin (A), a polyurethane resin (B), a polyester resin (C), a phenol resin (D) or a combination thereof.

[0008] The epoxy resin (A) in the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule, and can be appropriately selected depending on the purpose and required performance. Preferably, two epoxy groups are present in the molecule.
It has up to six. The epoxy equivalent (weight average molecular weight per epoxy group) of the epoxy resin (A) is
Usually 65-2000 g / eq, preferably 90
-1000 g / eq, more preferably 100-70
0 g / eq. Specific examples of the epoxy resin (A) include the following (A-1) to (A-3).

(A-1) Glycidyl ether type epoxy resin (i) Diglycidyl ether of dihydric phenol: weight average molecular weight 200 to 2,000 (hereinafter, all molecular weights represent weight average molecular weights and are measured by GPC) Diglycidyl ethers of dihydric phenols such as, for example, bisphenol A diglycidyl ether and bisphenol A such as diglycidyl ether obtained from the reaction of 1 to 3 mol of bisphenol A with 3 mol of epichlorohydrin
Epoxy resin, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro -4,4'-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9,9'-bis (4-hydroxyphenyl) fluoro orange glycidyl ether and the like.

(Ii) Polyglycidyl ethers of trihydric to hexavalent or higher polyhydric phenols: trihydric to hexavalent or higher polyhydric phenols (molecular weight: 200 to 500)
0) polyglycidyl ethers such as pyrogallol triglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, bis (Dihydroxynaphthalene) tetraglycidyl ether, polyglycidyl ether of phenol or cresol novolak resin (molecular weight 400 to 5000), limonenephenol novolak resin (molecular weight 400 to 50)
00), a polyglycidyl ether of polyphenol (molecular weight: 400 to 5,000) obtained by a condensation reaction of phenol and glyoxal, glutaraldehyde or formaldehyde, and a molecular weight of 4 obtained by a condensation reaction of resorcinol and acetone.
Polyglycidyl ethers of polyphenols having a molecular weight of 00 to 5000, diglycidyl ethers of (poly) alkylene glycol ether of bisphenol A [(poly) ethylene glycol ether or (poly) propylene glycol ether (number of oxyalkylene units is 1 to 20)], and the like.

(Iii) Diglycidyl ether of a dihydric aliphatic alcohol: a diglycidyl ether of a diol (molecular weight 62 to 500), for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether,
1,6-hexanediol diglycidyl ether, polyethylene glycol (molecular weight 150 to 4000) diglycidyl ether, polypropylene glycol (molecular weight 1
80-5000) diglycidyl ether, polytetramethylene glycol (molecular weight 200-5000) diglycidyl ether, neopentyl glycol diglycidyl ether and the like.

(Vi) Polyglycidyl ethers of trihydric to hexahydric or higher aliphatic alcohols: trihydric to hexahydric or higher polyhydric alcohols or their (poly) alkylene (C2-4) ethers (Molecular weight 92-100
Glycidyl ethers of 0), for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, poly (n = 2 to 5) glycerol polyglycidyl ether;
Triglycidyl ether of trimethylolpropane polyoxyethylene ether (molecular weight: 222 to 1000);

(A-2) Linear aliphatic polyepoxide (non-glycidyl type) Linear aliphatic polyepoxide having a molecular weight of 90 to 2500 and having a valence of 2 to 6 or more, for example, an epoxy equivalent of 130 to
1,000 epoxidized (poly) butadiene (types 1,2 and / or 1,4, molecular weight 260-250
0), epoxidized soybean oil having an epoxy equivalent of 120 to 1000 (molecular weight 240 to 2,500), and the like.

(A-3) Alicyclic polyepoxide (non-glycidyl type): molecular weight 90 to 2500, number of epoxy groups 2
~ 4 or more cycloaliphatic epoxides such as vinylcyclohexene diepoxide, limonene diepoxide, dicyclopentadiene diepoxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, 3,4 epoxy -6-methylcyclohexylmethyl 3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6
Methylcyclohexylmethyl) butylamine and the like. Further, it also includes a nuclear hydrogenated product of the phenol glycidyl ether. In addition, other than (A-1) to (A-3), any epoxy resin having a glycidyl group capable of reacting with active hydrogen can be used. These epoxy resins can be used in combination of two or more. In the case of the combined use, the ratio of (A-1) is usually 40 to 98% by weight, and (A-1), (A-2) and (A-3) are the total weight.
2) is 2 to 60% by weight, and (A-3) is 0 to 60% by weight. Of these, glycidyl ether type (A-1) is preferable, and among (A-1), diglycidyl ether of dihydric phenols is particularly preferable, and bisphenol A type epoxy resin is particularly preferable. is there.

Examples of the polyurethane resin (B) of the present invention include those obtained by a urethanization reaction between a polymer polyol and a polyisocyanate. Examples of the polymer polyol include a polyether polyol and a polyester polyol having at least two active hydrogens, and a polyether polyol is preferable. The average molecular weight of the high molecular polyol is 500 to 50,000.
00, preferably 500 to 30,000, and more preferably 500 to 10,000.

As a polyether polyol, a compound having at least two active hydrogen groups is used as a starting material.
Examples include those obtained by subjecting an alkylene oxide to polyaddition polymerization or polyaddition copolymerization (block and / or random). Examples of the starting material include aliphatic polyhydric alcohols (for example, dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,3-butanediol, and glycerin, trimethylolpropane, pentaerythritol, and shoe). Trihydric alcohols such as close, etc.), polyhydric phenols (for example, bisphenol A, pyrogallol, Japanese Patent 3,
No. 265,641), amines (triethanolamine, N
Polyalkanoic acids such as alkanolamines such as methyldiethanolamine and monoethanolamine; aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine; aromatic polyamines such as tolylenediamine, methylenedianiline and polymethylenepolyphenylamine (for example, Aliphatic carboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid and dimer acid; and aromatic carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid). Of these, aliphatic polyhydric alcohols and amines are preferable, and it is particularly preferable to use aliphatic polyhydric alcohols.

The oxyalkylene units constituting the polyether polyol include oxyethylene units having 2 to 4 carbon atoms (EO; hereinafter abbreviated as EO), oxypropylene units (PO; hereinafter abbreviated as PO), oxy1 units. , 2-
Butylene units (BO; hereinafter abbreviated as BO) and the like. Two or more of these oxyalkylene units can be used in combination. In this case, the bonding mode of the oxyalkylene unit may be either random or block. Preferably, the oxyethylene unit (EO) is composed of an oxyethylene unit (EO) and an oxypropylene unit (PO).
It is preferable to use a block containing 50% or more of the total amount (weight basis).

Examples of the polyester polyol having at least two active hydrogens include a resin synthesized from a polyhydric alcohol and a polycarboxylic acid. Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and polycarbonate diol. , Neopentyl glycol and bisphenols (bisphenol A, bisphenol F). As trihydric polyhydric alcohols, glycerin, trimethylolpropane, trimethylolethane, etc.
Examples of pentavalent or higher polyhydric alcohols such as pentaerythritol and sorbitan include dipentaerythritol and polyglycerin, and (poly) oxyalkylene ethers of these polyhydric alcohols (number of oxyalkylene units of 1
To 25). These may be used alone or in combination of two or more.

Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, azelaic acid and the like having 4 to 12 carbon atoms.
Aliphatic saturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, an aliphatic unsaturated dicarboxylic acid having 4 to 25 carbon atoms such as alkenyl succinic acid, isophthalic acid, terephthalic acid, aromatic dicarboxylic acid such as naphthalenedicarboxylic acid,
Cyclohexene dicarboxylic acid, tetrahydrophthalic acid,
Alicyclic dicarboxylic acids such as hexahydrophthalic acid and trimellitic acid, aromatic tricarboxylic acids such as pyromellitic acid, and acid anhydrides thereof,
Preferred are aromatic dicarboxylic acids.

The polyester polyol can be synthesized according to a known method. Usually, a polyhydric alcohol and a polycarboxylic acid are reacted at 80 to 200 ° C., preferably 100 to 200 ° C.
The reaction is preferably performed at a temperature of 160 ° C.

The polyisocyanate constituting (B) includes a polyisocyanate having 2 to 25 carbon atoms, and the aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene diisocyanate, and the like. Examples of the aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, and 2,2,4-trimethyl. Hexane diisocyanate and the like are mentioned, and as alicyclic polyisocyanates, isophorone diisocyanate, cyclohexane-1,4-methylenebis (cyclohexyl isocyanate) And the like, and two or more of these can be used in combination. Of these, aromatic polyisocyanates are preferred.

The polyurethane resin (B) of the present invention can be synthesized according to a known method. In general, the polymer polyol and the polyisocyanate are preferably reacted at a temperature of 40 to 150C, preferably 60 to 100C. The reaction may be performed in the presence or absence of an organic solvent. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and isobutyl ketone, esters such as ethyl acetate and butyl acetate, ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as toluene and xylene, dimethylformamide and dimethylacetamide. And sulphoxides such as dimethylsulphoxide, and a mixed solvent of two or more of these. Of these, preferably acetone,
It is preferable to use methyl ethyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, xylene and a mixed solvent of two or more thereof. Further, the reaction was carried out at an equivalent ratio (OH / NCO ratio) of the hydroxyl group of the polymer polyol to the isocyanate group of the polyisocyanate of 3/1 to 1/1, preferably 2.2 / 1 to 1.8 / 1. Things are good.

Examples of the polyester resin (C) of the present invention include a condensation reaction product of a polyhydric alcohol and a polycarboxylic acid. The molecular weight of (C) is usually from 500 to 10,0.
00, preferably 800 to 7,000. Examples of the polyhydric alcohol include the same polyhydric alcohols as those constituting the polyester polyol described above. Preferred among these are (poly) oxyalkylene ethers of bisphenol A. The number of moles of oxyalkylene added is usually 1 to 25, preferably 1 to 2
0. When the number of added moles is 25 or less, the adhesiveness between the fiber treated with the sizing agent and the matrix resin is further improved. As oxyalkylene, oxyethylene,
Oxypropylene, oxy 1,2-butylene and the like can be mentioned, and two or more kinds can be used in combination. In this case, the bonding mode of the oxyalkylene unit may be either random or block. Preferably, a block containing 50% or more of the oxyethylene unit (EO) based on the total amount (weight basis) of the oxyethylene unit (EO) and the oxypropylene unit (PO) is good. Examples of the polyvalent carboxylic acid include the same polyvalent carboxylic acids as the above-mentioned polyvalent carboxylic acids constituting the polyester polyol. Of the polycarboxylic acids, unsaturated dicarboxylic acids are preferred. Further, among the polyester resins (C), preferably,
It is a reaction product of an unsaturated divalent carboxylic acid and a (poly) oxyalkylene ether of bisphenol A.

The condensation reaction product of the polyhydric alcohol and the polycarboxylic acid is obtained by a known ester reaction similar to the above-mentioned polyester polyol, and the equivalent ratio is usually polyhydric alcohol / polycarboxylic acid = 0.5. ~ 2.0. When the equivalent ratio is 0.5 or more, the adhesiveness between the fiber treated with the sizing agent and the matrix resin is good, and when the equivalent ratio is 2.0 or less, fluff or Thread breakage is reduced.

Examples of the phenolic resin (D) in the present invention include addition condensation products of phenols such as phenol, cresol and xylenol with aldehydes (formaldehyde, acetaldehyde, furfural and the like).

The addition condensation reaction product of phenols and formaldehydes is obtained by a known reaction, and the equivalent ratio thereof is usually phenols / aldehydes = 3/1 to 1/1,
More preferably, it is 2.5 / 1 to 1/1, and is obtained by reacting at a temperature of 50 to 180 ° C. in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, and paratoluenesulfonic acid.

When the resin contained in the resin composition for convergence of the present invention is a polyacetal resin, a polyamide resin, a polycarbonate resin, a urea resin, a xylene resin, or the like, conventionally known components can be used as the components.

The sizing resin composition of the present invention comprises a bisphenol A ethylene oxide adduct (N1) and / or
Or polyoxyalkylene higher fatty acid ester (N
Preferably, it contains 2). By containing these surfactants, the penetration rate of wool felt can be easily adjusted to a preferable range.

In the bisphenol A ethylene oxide adduct (N1), the number of moles of EO added is preferably 2
４０40 mol, more preferably 2-20 mol. In addition, polyoxyalkylene higher fatty acid ester (N2)
Is an oxyalkylene unit having 2 to 4 carbon atoms described above.
And preferably EO and / or P
O, more preferably EO alone or a combination of EO and PO, and the weight average molecular weight of the polyoxyalkylene unit is preferably 1,000 to 10,000, more preferably 1,300 to 5,000. As higher fatty acids constituting (N2), palm oil, beef tallow, rapeseed oil,
Those derived from natural fats and oils such as rice bran oil and fish oil are usually used, but synthetic higher fatty acids can also be used. Specific examples include lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and the like. Of these, preferred are saturated and unsaturated higher fatty acids having 10 to 30 carbon atoms, more preferably stearic acid.

The production of (N2) is obtained by adding AO to a higher fatty acid or by directly subjecting a higher fatty acid and a polyalkylene oxide to an esterification reaction. As (N2), a monoester, a diester and a mixture thereof are used. No. Specific examples of (N2) include polyoxyethylene (weight average molecular weight 1,000 to 5,000) stearic acid ester, polyoxyethylene (weight average molecular weight 500 to 4,000) lauric acid ester, and polyoxyethylene (weight Average molecular weight 1,500 to 3,000
0) Distearic acid ester and the like.

When the sizing resin composition of the present invention contains (N1) and / or (N2), the weight ratio% of the resin component to the surfactant in the sizing resin composition is preferably 98-50% / 2-50%, more preferably 8
5 to 50% / 15 to 50%, and the resin component is 98 to 5
When it is 0%, it becomes easy to simultaneously satisfy the abrasion resistance and the opening property.

The composition of the present invention further comprises a known nonionic surfactant (N) other than (N1) and (N2).
3) may be added. Examples of (N3) include polyalkylene glycol-type nonionic surfactant (n1) and polyvalent alcohol-type nonionic surfactant (n2) other than (N1) and (N2). In addition,
When (N3) is added, it is more preferable to add (N1) and / or (N2) to the sizing composition containing (N1) and / or (N2) than to add to the sizing composition not containing (N1) or (N2). preferable.

Examples of the alkylene oxide (AO) constituting the polyalkylene glycol chain of (n1) include the above-mentioned AO, and among these, EO and random or block adducts of EO and PO are preferred. The number of moles of AO added is preferably 2 to 200 moles, and preferably 50 to 100% by weight of the AO is EO. Usually, the number of moles of AO constituting the polyoxyalkylene is preferably 2 to 100 moles.

The following are specific examples of (n1).

(N1-1) Polyoxyalkylene alkyl ether; obtained by adding the above-mentioned AO to a higher alcohol or etherifying a higher alcohol with a polyalkylene glycol, and the higher alcohol having 8 to 18 carbon atoms An aliphatic saturated or unsaturated alcohol,
It may be primary or secondary, may be linear or branched, and may have a fixed number of carbon atoms or a mixture thereof. For example, examples of the aliphatic saturated primary alcohol include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and alcohol synthesized using a Ziegler catalyst (for example, ALFOL 1214: CON).
DEA), alcohol synthesized by the oxo method (for example, dovanol 23, 25, 45: manufactured by Mitsubishi Yuka, tridecanol: manufactured by Kyowa Hakko, oxocol 1213, 121)
5,1415: Diamond Doll 115-L, manufactured by Nissan Chemical
115H, 135: manufactured by Mitsubishi Chemical Corporation). Examples of the aliphatic unsaturated primary alcohol include oleyl alcohol. Examples of the aliphatic secondary alcohol include those obtained by oxidizing n-paraffin, and are described in "Oil Chemistry", Vol. 21, No. 5, pp. 233-242 (197).
Those described in 2) are mentioned.

Specific examples of (n1-1) include octyl alcohol EO (30 mol) adduct, lauryl alcohol EO (10 to 30 mol) adduct, stearyl alcohol EO (20 to 50 mol) adduct, oleyl alcohol EO (10 to 40 mol) adduct, lauryl alcohol E
O (10 to 50 mol) -PO (5 to 20 mol) block adduct and the like.

(N1-2) Polyoxyalkylene ether of a higher fatty acid ester of a polyhydric alcohol; having a structure in which AO is added to an esterified product obtained by reacting a higher fatty acid with a tri- to polyhydric polyhydric alcohol. The polyhydric alcohols constituting these include glycerin and trimethylo-
Examples include lepropane, pentaerythritol, sorbitan, and sorbitol, and higher fatty acids and AO include those described above. Specifically, sorbitan oleic acid monoester EO (10 to 6)
0 mol) adduct, pentaerythritol lauric acid monoester EO (10-60 mol) adduct, and the like.

(N1-3) polyoxyalkylene alkylaryl ether; alkylphenol having at least one alkyl group or alkylnaphthol has A
It has a structure obtained by adding O, and as the alkylphenol, a monoalkyl group having 8 to 12 carbon atoms,
Di-, tri-decaalkylphenols and alkylnaphthols having an alkyl group having 8 to 12 carbon atoms,
Di, tri to decaalkyl naphthols may be mentioned, and AO may be those described above. Specifically, nonylphenol EO (10 to 50 mol) adduct, nonylphenol EO (10 to 50 mol) -PO (5 to 20 mol)
Block adducts, octylphenol EO (8 to 50 mol) adducts, dinonylphenol EO (20 to 60 mol) adducts and the like can be mentioned.

(N1-4) polyoxyalkylene styrenated aryl ether; monocyclic phenol (phenol,
It has a structure in which AO is added to a reaction product of an alkylphenol having an alkyl group having 1 to 12 carbon atoms) or a polycyclic phenol (phenylphenol, cumylphenol, etc.) and 1 to 20 mol of styrene. The foregoing are mentioned. Specifically, a styrenated (3 mol) phenol EO (10 to 40 mol) adduct, a styrenated (7 mol) cumylphenol EO (10 to 50 mol) adduct, and the like can be given.

(N1-5) AO adducts of bisphenols other than bisphenol A; AO adducts such as bisphenol F and bisphenol S; examples of AO include those described above. Specific examples include an EO (2 to 40 mol) adduct of bisphenol A.

(N1-6) polyoxyalkylenealkylamine having a structure in which AO is added to a saturated or unsaturated alkylamine having 10 to 20 carbon atoms, specifically a stearylamine EO (3 to 20 mol) adduct , Lauririmamine EO
(5 to 15 mol) adduct and the like.

(N1-7) AO adduct of fatty acid amide;
A to a saturated or unsaturated fatty acid amide having 10 to 20 carbon atoms
O-added structure, specifically, lauric amide EO (20 mol) adduct, stearic amide EO
(12 mol) adduct and oleamide EO (16
Mol) adducts and the like.

(N1-8) AO adduct of fats and oils; a polyalkylene glycol is added to the fats and oils and transesterified with an alkali catalyst to form a mixture of polyalkylene glycol fatty acid ester and fatty acid monoglyceride. Examples thereof include a mixture of polyethylene glycol oleic acid monoester and oleic acid monoglyceride produced from olive oil and polyethylene glycol (number of EO molecules: 9).

(N1-9) polyoxyethylene polyoxypropylene polyol, which is called a pluronic surfactant and is obtained by adding EO to polypropylene glycol (average molecular weight: 900 to 2900). Is usually 10 to 80% by mass. Specific examples include polypropylene glycol having an average molecular weight of 1200 to which EO is added so as to be 40% by mass.

The polyhydric alcohol type nonionic surfactant (n2) includes the following.

(N2-1) Fatty acid ester of trihydric or higher polyhydric alcohol; trihydric alcohol (glycerin, trimethylolpropane, trimethylol) Ethane, etc.), tetrahydric alcohols (pentaerythritol, etc.), pentahydric or higher alcohols (dipentaerythritol, sorbit, sugar, etc.) and sorbitan. The fatty acids include the above-mentioned fatty acids. Specific examples include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan dilaurate, sorbitandiolate, and sucrose monostearate.

(N2-2) Alkyl ether of trihydric or higher polyhydric alcohol; having a structure in which the hydroxyl group of the trihydric or higher polyhydric alcohol is partially etherified with a monohydric alcohol. Examples include methylolpropane monobutyl ether, pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glucoside, lauryl glucoside, and the like.

(N2-3) fatty acid alkanolamide;
It is obtained by condensation of an alkanolamine and a fatty acid, wherein dialkanolamine is produced at a ratio of 2 moles to 1 mole of the fatty acid. 1: 2 mole type fatty acid dialkanolamide (for example, ninol type detergent) and fatty acid 1
1: 1 molar fatty acid dialkanolamide in which dialkanolamine is produced in a molar ratio of 1: 1 (for example,
1: 1 molar lauric acid diethanolamide).

Of (N3) in the present invention, (n1) is preferred, and (n1-4) is more preferred.

In the present invention, (N3) is (n1)
-1) to (n1-9) and (n2-1) to (n2-
You may use together 2 or more types of 3). In this case, the weight ratio between (n1) and (n2) is usually (n1) / (n
2) = 98/2 to 50/50.

When the composition of the present invention contains (N1) and / or (N2) and further contains (N3), the addition ratio of (N3) is (N1) and / or (N1).
It is preferably from 20 to 200%, more preferably from 50 to 120%, based on the total weight of 2).

The sizing resin composition of the present invention impregnates the sizing resin composition into wool felt and then penetrates into a methyl ethyl ketone solution (concentration: 65% by weight) of a matrix resin for a composite material. Speed (Pe) is 1 to 40 sec, preferably 1 to 30 sec
It is characterized by being. Permeation speed is 40s
When the value exceeds ec, the fibers are hardly impregnated into the matrix resin, and the physical properties of the composite material deteriorate. As the matrix resin for the composite material, a resin used as a matrix resin of a composite material using a fiber as a reinforcing material includes, for example, an epoxy resin, an unsaturated polyester resin, a polyimide resin, a phenol resin, and the like. Any resin can be used as long as the resin dissolves in 50% by weight or more.
The matrix resin used for measuring the penetration rate may be the same as or different from the matrix resin of the composite material in which the fibers to be treated with the sizing resin composition of the present invention are used, but are preferably different. Of the same kind.

[0053] Among the matrix resins, an epoxy resin is preferred. Examples of the epoxy resin include bisphenol A type epoxy resins (bisphenol A diglycidyl ether and the like), amine polyfunctional epoxy resins such as tetraglycidylamine and triglycidylamine, and phenol novolak type epoxy resins.

The penetration rate can be measured by the following method. [Measurement method of permeation rate] A commercially available wool felt (manufactured by Nippon Kaori Co., Ltd .: thickness: 3.0 mm, white) was cut into a size of 10 mm in length and width, and then immersed and washed in 10 times weight methanol for 30 minutes. A 2% by weight solution of the sizing resin composition (solvent: solvent) such that the amount of the sizing resin composition adhered to that obtained by removing the methanol in a circulating drier at 100 ° C. was 2.0 ± 0.1% by weight. (Acetone or ethyl ether) at 25 ± 1 ° C., and then the solvent was volatilized and removed by a circulating drier at 100 ° C., confirming that the adhesion amount was 2.0 ± 0.1% by weight / wool felt. I do. In a glass beaker having an inner diameter of 50 mm and a depth of 60 mm, 50 g of a methyl ethyl ketone solution (concentration: 65% by weight) of the matrix resin is collected, the wool felt is gently floated on the surface of the liquid, and the time until it starts to sink is measured (measuring temperature: 25 ± 1 ° C). The measurement is repeated five times, and the weighted average value is defined as Pe.

The sizing resin composition of the present invention has an interfacial tension (T) (unit: mN / m) at 50 ° C. between the sizing resin composition and a matrix resin solution of methyl ethyl ketone (concentration: 50% by weight). Preferably -20 to -2
mN / m, more preferably -20 to -5 mN / m, and particularly preferably -20 to -10 mN / m. When the interfacial tension is in the range of −20 to −2 mN / m, the fibers are more easily impregnated into the matrix resin, and the physical properties of the composite material are further improved.

The interfacial tension can be measured by the following method. [Measurement Method of Interfacial Tension] A solution of a matrix resin in methyl ethyl ketone (concentration: 50% by weight) and a sizing resin composition were adjusted to 50 ± 1 ° C., and the inner diameter was 50 mm and the depth was 60 mm.
Pour 30 g each of the matrix resin methyl ethyl ketone solution and the sizing resin composition in this order into a glass beaker and adjust the temperature of the solution in a hot water bath at 50 ± 1 ° C., and measure the tension at the liquid interface with an automatic surface tensiometer (Kyowa Co., Ltd.). Interface Science; Model CB-A
3, Wilhelmy method).

In the present invention, the fiber sizing agent may be, if necessary, a softener (eg, polyoxystearic acid amide) and a diluent (eg, styrene, vinyltoluene, divinylbenzene) in addition to the sizing resin composition. , Reactive diluents such as phenylglycidyl ether, and non-reactive diluents such as nonylphenol and tricresyl phosphate), antioxidants (hindered amines, hydroquinones, hindered phenols, sulfur-containing compounds, etc.),
UV absorbers (benzophenones, benzotriazoles, salicylic esters, metal complex salts, etc.), waxes (eg, paraffin wax, microcrystalline wax, polymerized wax, beeswax, low molecular weight polyolefin, etc.), plasticizers ( For example, phthalic acid esters, phosphate esters, fatty acid esters, castor oil, plasticizers such as liquid paraffin alkyl polycyclic aromatic hydrocarbons, etc.), thermoplastic resins (polypropylene resins, polystyrene resins, acrylic resins, etc.), defoamers, Leveling agents (for example,
Silicone-based leveling agents, polyethylene glycol, etc.), antistatic agents, antibacterial agents, fungicides, viscosity modifiers, fragrances, flame retardants and the like. From the viewpoint of physical properties of the composite (composite material), these additives are added in an amount of 1 to 20% by weight for the softener, 0.1 to 10% by weight for the antioxidant, The agent is 0.1-1
0% by weight, waxes 1-20% by weight, plasticizers 1-
20% by weight, 1-60% of thermoplastic resin, 0.1% of defoamer.
1-5% by weight, 1-20% by weight of a smoothing agent, 0.1-5% by weight of an antistatic agent, 0.01-5% by weight of an antibacterial agent, 0.01-5% by weight of a fungicide, 0.1 to 5% by weight of viscosity modifier, 0.1 to 5% by weight of fragrance, 0.1 to 10% of flame retardant
% By weight is preferred.

When the sizing resin composition or sizing agent for fibers of the present invention is applied to the fiber, an aqueous dispersion (solid content concentration of 1 to 70% by weight) of the sizing resin composition or sizing agent for fibers, or The application can be carried out by applying an organic solvent solution (solid content concentration: 1 to 70% by weight) and then drying. In consideration of safety and the like, it is preferable to use an aqueous dispersion.

For preparing an aqueous dispersion, a surfactant can be used as a dispersant. As a surfactant,
Nonionic, cationic, anionic and amphoteric surfactants. When a nonionic surfactant is used to form a water emulsion, the same nonionic surfactants (N1) to (N3) as described above in the present invention can be used. In this case, wool canvas is used. The measured values of the penetration rate (Pe) and the interfacial tension (T) were measured in advance for (N1) to (N3) and for the resin composition to which a nonionic surfactant was added in order to further form a water emulsion. Thing is each 1-40se
c, -20 to -2 mN / m. Examples of the cationic surfactant include a quaternary ammonium salt type and an amine salt type. Examples of the anionic surfactant include a carboxylate type anionic surfactant, a sulfate ester type anionic surfactant, a sulfonate type anionic surfactant, and a phosphate ester type anionic surfactant. Examples of the amphoteric surfactant include a carboxylate-type amphoteric surfactant, a sulfate ester-type amphoteric surfactant, a sulfonate-type amphoteric surfactant, and a phosphate-type amphoteric surfactant. The amount of the surfactant is from the viewpoint of the emulsifying property of the fiber sizing agent and the physical properties of the composite composite material, and is usually expressed by weight ratio, and the sizing resin composition of the present invention / surfactant = 95/5 to 40/60. preferable.

For forming the solution, an organic solvent can be used. Examples of the organic solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethyl cellosolve acetate, etc.), and ethers (dioxane,
Tetrahydrofuran, etc., hydrocarbons (n-hexane, n-heptane, cyclohexane, tetralin, toluene, xylene, etc.), chlorinated hydrocarbons (dichloroethane, trichloroethane, trichloroethylene, perchloroethylene, etc.), amides (dimethylformamide) ,
Dimethylacetamide, etc.), N-methylpyrrolidone, etc.].

A resin component in the sizing resin composition of the present invention,
The method of mixing the surfactant added as necessary, and other additives is not particularly limited. For example, a method of heating and melting and mixing the resin component and the surfactant to form an aqueous dispersion or a solution, Examples thereof include a method of dissolving and mixing in an appropriate organic solvent to obtain an aqueous dispersion.

The fibers to be used in the present invention include polyamide fibers, aramid fibers, Kevlar fibers, polyethylene fibers,
Polyester fiber, glass fiber, carbon fiber, other inorganic fiber, and the like, and two or more kinds can be used in combination. Particularly preferred for imparting high strength to the composite material are Kevlar fiber, aramid fiber and carbon fiber.

The method of attaching the fiber sizing agent to the fiber is as follows.
Known methods such as a commonly used roller sizing method, roller dipping method, and spray method can be used.
The amount of solids attached to the fibers of the fiber sizing agent is generally 0.1 to 10% by weight, preferably 0.5 to 10% by weight, from the viewpoint of yarn physical properties.
2.5% by weight.

The filaments of the fiber to which the sizing agent has been added; the tow or the strand are dried by a known method (hot air drying, far infrared drying, hot roller drying, etc.).

For producing a composite material from the fiber treated with the fiber sizing agent of the present invention and the matrix resin, a known method may be employed. For example, the fiber is impregnated in the matrix resin in advance, and a tension is applied to the rotating mandrel. Filament wind (PW) molding method to wind while applying
A press molding method in which fibers are preliminarily arranged in one direction or a knitted or woven fabric and a prepreg sheet impregnated with a resin is laminated, or a method in which cut fibers of fibers are appropriately mixed with a matrix resin and then injection molded is used. . Examples of the matrix resin include an epoxy resin, an unsaturated polyester resin, a polyimide resin, and a phenol resin.Among these, an epoxy resin is preferable, and as the epoxy resin,
And diglycidyl ether of bisphenol A. In the injection molding method, the mixing weight ratio of the cut fiber and the matrix resin is usually 5/95 to 90 /.
10, preferably 20/80 to 70/30.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Parts represent parts by weight.

Examples 1 to 5 and Comparative Examples 6 to 8: Each component was charged into a high-viscosity emulsifying apparatus in the following amounts, and
After the mixture was heated to 0 to 90 ° C. and uniformly mixed, water was gradually added, and the mixture was emulsified and phase-inverted to obtain a uniform white emulsion-like sizing agent (solid content: 50% by weight). The sizing agent is diluted with water to prepare an aqueous dispersion having a concentration of 3%, and an untreated carbon fiber (number of filaments: 12,000 filaments, tensile strength: 3530 MPa) yarn bundle is immersed and impregnated in the aqueous dispersion. After drying in hot air at 100 ° C for 20 minutes,
For carbon fiber wound on a bobbin after heat setting for one minute, the deflocculating property,
The abrasion resistance, spreadability, and physical properties of the composite (composite material) were evaluated. The results are shown in Table 1.

Resin composition 1 Bisphenol A diglycidyl ether (epoxy equivalent: 185) 40 parts (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) Bisphenol AEO 10 mol adduct and maleic acid (molar ratio 6/5) Polyester (molecular weight: 3200) 20 parts Bisphenol AEO18 mole adduct 20 parts Polyethylene glycol (molecular weight 3500) monostearate 20 parts Resin composition 2 Bisphenol A diglycidyl ether (epoxy equivalent: 185) 40 parts (Yuika Shell Epoxy Co., Ltd.) "Epicoat 828") Polyester of bisphenol AEO2 mol adduct and maleic acid (molar ratio: 6/5) (molecular weight: 2600) 15 parts Styrenated (7 mol) cumylphenol EO 25 mol adduct 20 parts Polyethylene glycol (molecular weight) 3500) Monostearate 30 parts Resin composition 3 Bisphenol A diglycidyl ether (epoxy equivalent: 470) 40 parts ("Epicoat 1001" manufactured by Yuka Shell Epoxy Co., Ltd.) Bisphenol AEO4 mole adduct and fumaric acid (molar ratio 4) / 3) Polyester (Molecular weight: 3000) 30 parts Styrenated (3 mol) phenol EO 20 mol adduct 20 parts Polyethylene glycol (molecular weight 2500) monostearate 20 parts Resin composition 4 Bisphenol A EO 10 mol adduct and maleic acid Polyester (molecular weight: 3500) with (molar ratio: 6/5) 35 parts Polyether-type urethane resin ("HYDRAN HW-312B" manufactured by Dainippon Ink Co., Ltd.) 20 parts Styrenated (7 mol) cumylphenol EO 25 mol 15 parts polyethylene glycol (Molecular weight 2500) Distearate 30 parts Resin composition 5 Bisphenol A diglycidyl ether (epoxy equivalent: 185) 35 parts ("Epicoat 828" manufactured by Yuka Shell Epoxy Co., Ltd.) Polyether type urethane resin (Dainippon Ink Co., Ltd.) "HYDRAN HW-312B") 20 parts Styrenated (3 mol) phenol EO 25 mol adduct 20 parts Polyethylene glycol (molecular weight 3500) monostearate 25 parts Resin composition 6 Bisphenol A diglycidyl ether (epoxy equivalent: 185) 40 Part ("Epicoat 828" manufactured by Yuka Shell Epoxy Co., Ltd.) Polyester (molecular weight: 2600) of EO2 mole adduct of bisphenol A and maleic acid (molar ratio: 6/5) 35 parts Styrenated (7 mole) phenol PO20 Mol EO 40 mol adduct 25 parts Resin composition 7 Polyester (molecular weight: 2600) of an EO2 mole adduct of bisphenol A and maleic acid (molar ratio: 4/3) 45 parts Polyether-type urethane resin ("HYDRAN HW-" manufactured by Dainippon Ink Co., Ltd.) 312B ") 30 parts Styrenated (7 mol) cumylphenol PO15 mol EO30 mol adduct 25 parts Resin composition 8 bisphenol A diglycidyl ether (epoxy equivalent: 470) 40 parts (Yuika Shell Epoxy Co., Ltd." Epicoat ") 1001 ") 40 parts of polyether type urethane resin (" HYDRAN HW-312B "manufactured by Dainippon Ink and Chemicals, Inc.) 20 parts of styreneated (2 mol) phenol PO15 mol EO30 mol adduct

Performance evaluation method: (1) Removability: Carbon fiber wound on a bobbin was 50 m /
Total test length of 10 ⁵ when the vertical length is disassembled
It is displayed as the number of yarn breaks per m. Number of thread breaks is 1
It is preferably 0 times or less.

(2) Scratch resistance: smooth surface with a diameter of 10 m
5 stainless steel rods were arranged zigzag at 50 mm intervals in parallel so that the carbon fiber yarns passed therethrough at an angle of 120 °. A 12,000 D-filament-converted carbon fiber yarn is passed through the apparatus at a speed of 10 m / min while applying an initial tension of 300 g to the fiber yarn, and a laser beam is irradiated from a direction perpendicular to the fiber yarn. The number of fluffs generated is counted from the number of times the laser beam is shielded, and the result is displayed in units / 10 m. It is preferable that the number of fluffs is 50/10 m or less.

(3) Spreadability: A container containing a methyl ethyl ketone solution of Epicoat 828 (concentration: 65% by weight) and three stainless steel rods having a smooth surface and a diameter of 10 mm were used for 50 times.
The carbon fiber strips were arranged in a zigzag manner so as to pass in parallel at an interval of mm and while contacting the carbon fiber strips at an angle of 120 °. 12000D-1200 filament count
While impregnating the zero carbon fiber thread with the methyl ethyl ketone solution (concentration 65 wt%) of Epicoat 828 while applying an initial tension of 500 g, the carbon fiber thread is passed through the stainless steel rod at a speed of 50 m / min, and the spread width of the carbon fiber after passing through Was measured.

(4) Physical properties of composite (composite material): Carbon fibers are aligned in one direction and placed in a mold, and a resin mixed with Epicoat 828 (100 parts) / BF ₃ MEA (3 parts) is added thereto. Impregnate with vacuum. At this time, the amount of the carbon fiber is adjusted so that the volume content of the fiber becomes 60%.
After impregnation, it is cured under pressure at 150 ° C. for 1 hour, taken out of the mold, and post-cured at 140 ° C. for 4 hours.

For a test piece having a thickness of 2.5 mm and a width of 6.0 mm, ASTM D-3039 was used.
The tensile strength was measured according to -72-T, and ASTM D-
The interlaminar shear strength (ILSS) was measured according to 2344.

[0074]

[Table 1]

[0075]

The fiber sizing agent containing the fiber sizing resin composition of the present invention can be applied to various organic fibers or inorganic fibers used in the composite material by applying various sizing agents in the fiber processing step. Even if it comes into contact with guides and receives friction, the generation of fluff and breakage of yarn can be suppressed. In addition, since the fiber has a good opening property, the composite material comprising the treated fiber and the matrix resin has high strength and is extremely useful.

Claims (11)

[Claims] The present invention relates to a resin composition for bundling a composite material reinforcing fiber, the penetration rate of wool felt impregnated with the resin composition for bundling into a methyl ethyl ketone solution (concentration of 65% by weight) of a matrix resin (Pe). ) Is 1 to 40 seconds
A resin composition for tying fibers. 2. The resin composition according to claim 1, wherein the matrix resin has an interfacial tension (T) at −50 ° C. of −20 to −2 mN / m with a methyl ethyl ketone solution (concentration: 50% by weight). object. 3. The matrix resin is bisphenol A.
3. The sizing resin composition according to claim 1, which is diglycidyl ether. 4. The sizing resin composition according to claim 1, further comprising a bisphenol A ethylene oxide adduct and / or a polyoxyalkylene higher fatty acid ester. 5. The convergence resin composition comprises a ring-opening polymer resin,
The convergence resin composition according to any one of claims 1 to 4, further comprising at least one member selected from the group consisting of a polyaddition resin, a polycondensation resin, and an addition condensation resin. 6. The ring-opening polymerization type resin is an epoxy resin (A),
The convergence resin composition according to claim 5, wherein the polyaddition resin is a polyurethane resin (B), the polycondensation resin is a polyester resin (C), and the addition condensation resin is a phenol resin (D). (A) is a bisphenol A type epoxy resin, (B) is a reaction product of an aromatic isocyanate and a polyether polyol or a polyester polyol,
7. The sizing resin composition according to claim 6, wherein (C) is a reaction product of an unsaturated dicarboxylic acid and a (poly) oxyalkylene ether of bisphenol A. 8. A sizing agent for fibers, which is an aqueous dispersion or solution of the sizing resin composition according to any one of claims 1 to 7. 9. A polyamide fiber, aramid fiber, Kevlar fiber, polyethylene fiber treated with the sizing resin composition or the fiber sizing agent according to any one of claims 1 to 8,
One or more fibers selected from the group consisting of polyester fibers, glass fibers, carbon fibers and other inorganic fibers. 10. The fiber according to claim 9 as a reinforcing fiber,
A prepreg characterized by using a thermosetting resin or a thermoplastic resin as a matrix. 11. A molded product obtained by molding the prepreg according to claim 10.