TW201525233A - Sizing agent for reinforced fiber and its use - Google Patents

Abstract

This invention provides a sizing agent which contributes excellent adhesiveness to a reinforced fiber with respect to matrix resin, and which is capable of suppressing reinforced fiber stands from becoming loose and hardening with time, and also exhibits excellent stability for prolonged storage. This invention also provides a reinforced fiber strand and fiber reinforced composite material. The sizing agent for reinforced fiber of this invention contains an epoxy resin (A), an unsaturated polyester (B), and a fatty acid ester (C). By using the sizing agent of this invention the abovesaid problems can be solved.

Description

Sizing pulp for reinforcing fibers and use thereof

The present invention relates to an upper slurry for reinforcing fibers and uses thereof. Specifically, it relates to an upper slurry for reinforcing fibers used for reinforcing a matrix resin, a reinforcing fiber strand using the above slurry, and a fiber-reinforced composite material.

Fiber-reinforced composite materials made of various synthetic fiber-reinforced plastic materials (called matrix resins) have been widely used in automotive applications, aerospace applications, sports and leisure applications, and general industrial applications. Examples of the fibers of the composite material include various inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and various organic fibers such as linaloamide fibers, polyamide fibers, and polyethylene fibers. These various synthetic fibers are usually produced into a long filament shape, and then processed into a sheet-like intermediate material of a so-called unidirectional prepreg by a hot melt method or a drum winding method, or processed by a filament winding method, and processed as appropriate. The woven fabric or chopped fiber shape or the like is used as a reinforcing fiber through various high-order processing steps.

Epoxy resins have been widely used as matrix resins for reinforcing fiber composites. In addition to the epoxy resin, a radical polyester resin, a vinyl ester resin, an acrylic resin or the like may be used as the radical polymerization-based matrix resin.

In order to improve the mechanical strength of the reinforced fiber composite, the matrix resin is strong In the above-mentioned epoxy resin or radically polymerized matrix resin, it has been proposed to improve the adhesion of the reinforcing fibers to the above-mentioned epoxy resin (for example, Patent Documents 1 and 2).

However, the above-mentioned slurry described in Patent Document 1 or Patent Document 2 can improve the adhesion of the reinforcing fiber to the epoxy resin or the radical polymerization-based matrix resin, but the chemical fiber to which the upper slurry has been attached is The time becomes hard, sometimes causing problems of fuzzing or adhesion to the matrix resin. Moreover, there is a problem that the long-term storage stability of the slurry is sometimes caused.

At the same time, the reinforcing fibers also have a small elongation and fragile properties. These reinforcing fibers which have been imparted with the conventional sizing may cause problems such as fuzzing or fiber cutting due to mechanical friction or the like in the processing step.

Therefore, in the field of fiber-reinforced composite materials, it is desired to develop an upper slurry which can improve the affinity between the reinforcing fibers and the matrix resin, and firmly adhere thereto, and can prevent the raising of the reinforcing fiber strands, It inhibits hardening with time and is excellent in long-term storage stability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-53-52796

[Patent Document 2] Japanese Laid-Open Patent Publication No. SHO 57-173150

In view of such a technical background, it is an object of the present invention to provide an upper slurry which can be imparted to a matrix tree for reinforcing fibers. The excellent adhesion between the fats inhibits the raising of the reinforcing fiber strands and hardening with time, and is excellent in long-term storage stability; and the reinforcing fiber strands and the fiber-reinforced composite material using the upper slurry.

The present inventors have found in order to solve the above problems, and have found that the present invention can be solved by using an epoxy resin (A) and a specific unsaturated polyester (B) and then using a fatty acid polyester (C). The problem while completing the invention.

That is, the sizing slurry for reinforcing fibers of the present invention contains an epoxy resin (A), an unsaturated polyester (B) having an acid value of less than 5, and a fatty acid ester (C).

The unsaturated polyester (B) is preferably 30 to 300 parts by weight, based on 100 parts by weight of the epoxy resin (A), based on the total of the epoxy resin (A) and the unsaturated polyester (B). The fatty acid ester (C) is preferably 1 to 15 parts by weight per 100 parts by weight.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the unsaturated polyester (B) is preferably from 1.2 to 2.1.

The unsaturated polyester (B) is preferably a condensate containing an alkylene oxide adduct (B2) of an unsaturated diprotonic acid (B1) and a bisphenol.

The unsaturated polyester (B) is reacted with a reactive component contained in a ratio of the unsaturated diproton acid (b1) and the bisphenol-based alkylene oxide adduct (b2) to satisfy the following formula (I). The winner is better.

Moir number of unsaturated diprotonic acid (b1) <Molar number of alkylene oxide adduct (b2) of bisphenol (I)

The acid value of the aforementioned unsaturated polyester (B) is preferably 4.5 or less.

The melting point of the fatty acid polyester (C) is preferably 5 ° C or less.

The aforementioned fatty acid polyester (C) is preferably an ester having an ester-bonded structure of an unsaturated fatty acid having 10 to 24 carbon atoms and a monovalent alcohol having 8 to 20 carbon atoms.

The ratio of the total weight of the epoxy resin (A), the unsaturated polyester (B) and the fatty acid polyester (C) to the nonvolatile content of the upper slurry is preferably 70% by weight or more.

In the reinforcing fiber strand of the present invention, the above-mentioned sizing slurry for reinforcing fibers is adhered to the raw material reinforcing fiber strand.

The fiber-reinforced composite material of the present invention contains a matrix resin and the above-mentioned reinforcing fiber strand.

The matrix resin is preferably a thermosetting resin.

The sizing slurry for reinforcing fibers of the present invention imparts excellent adhesion to the matrix resin to the reinforcing fibers. At the same time, the raising of the reinforcing fiber strands and the hardening with time can be prevented. Moreover, it has excellent long-term preservation stability.

Since the reinforced fiber strand of the present invention has little or no change with time in the sizing agent, it is possible to prevent the frictional fluffing property and the adhesion to the matrix resin from being lowered even after long-term storage. By using the reinforcing fiber strand of the present invention, a reinforced fiber composite material having excellent physical properties can be obtained.

The present invention relates to a sizing slurry for reinforcing fibers used for reinforcing a matrix resin, comprising an epoxy resin (A), a specific unsaturated polyester (B), and a fat. Acid ester (C). The details will be described below.

[Epoxy Resin (A)]

The epoxy resin (A) is an essential component of the upper slurry of the present invention. The epoxy resin (A) means a compound having two or more reactive epoxy groups in its molecular structure. The epoxy resin (A) is represented by a glycidyl ether type which can be obtained from epichlorohydrin and an active hydrogen compound, and examples thereof include a glycidyl ester type, a glycidylamine type, and an alicyclic type. One type of the epoxy resin (A) may be used, or two or more types may be used in combination.

Examples of the glycidyl ether type epoxy resin (A) include an epoxy resin having a functional group represented by the following formula (1) produced by using an alcohol as a raw material, and a phenol resin as a raw material. An epoxy resin or the like having a functional group represented by the formula (2). The epoxy resin (A) of the glycidyl ester type, for example, an epoxy resin having a functional group represented by the following formula (3), which is produced by using a carboxylic acid such as a terephthalic acid derivative or a synthetic resin fatty acid as a raw material Wait. The glycidylamine type epoxy resin (A) may, for example, be an epoxy resin having a functional group represented by the following formula (4) or an epoxy resin having a functional group represented by the following formula (5). The alicyclic epoxy resin (A) may, for example, be an epoxy resin having a functional group represented by the following formula (6). Among these epoxy resins, an epoxy resin having a functional group represented by the general formula (2) is preferred for the purpose of improving the adhesion between the fibers and the matrix resin.

The epoxy resin (A) preferably has an epoxy equivalent of from 100 to 1,500 g/eq, more preferably from 120 to 1,000 g/eq, still more preferably from 150 to 800 g/eq. When the epoxy equivalent is less than 100 g/eq, the hardening of the reinforcing fiber strands over time is sometimes promoted. When the epoxy equivalent exceeds 1,500 g/eq, sometimes with matrix resin The adhesion between them is reduced. Further, the epoxy equivalent is based on the definition of JIS-K7236.

The weight average molecular weight of the epoxy resin (A) is preferably from 100 to 10,000, more preferably from 100 to 8,000, still more preferably from 150 to 7,000. When the weight average molecular weight is less than 100, the heat resistance such as the drying step of the reinforcing fiber strand may be insufficient to volatilize. When the weight average molecular weight exceeds 10,000, the long-term storage stability of the upper slurry may be lowered.

The epoxy resin (A) is preferably an aromatic epoxy resin having an aromatic ring in its molecular structure in order to improve the adhesion between the reinforcing fiber and the matrix resin.

Examples of the aromatic epoxy resin include a polyglycidyl ether compound of a mononuclear polyvalent phenol compound such as hydroquinone, resorcin or catechol; dihydroxynaphthalene, bisphenol, bisphenol F, and a double Phenol A, phenol phenolic, o-cresol novolac, resorcinol phenolic, bisphenol F phenolic, bisphenol A phenolic, dicyclopentadiene modified phenol, triphenylmethane, tetraphenylethane, etc. A polyglycidyl ether compound of a phenol compound or the like.

Among these aromatic epoxy resins, a compound represented by the following formula (7) and a compound represented by the following formula (8) are preferred, and a compound represented by the following formula (7) is more preferable.

In the formula (7), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a methyl group. n is an integer of 0 to 30, preferably 0 to 20, and more preferably 0 to 10.

In the formula (8), m is an integer of 0 to 10, preferably 0 to 8, more preferably 0 to 5.

The method for producing the epoxy resin (A) is not particularly limited, and a known method can be employed. Meanwhile, the above-mentioned epoxy resin (A) is a general commercial product, and those commercially available epoxy resins (A) can be used in the above-mentioned carbon fiber upper slurry.

[Unsaturated Polyester (B)]

The unsaturated polyester (B) having an acid value of less than 5 is an essential component of the upper slurry of the present invention. When the acid value is 5 or more, the reinforcing fiber strands are hardened with time, and the long-term storage stability of the sizing slurry is lowered. The acid value is preferably 4.5 or less, more preferably 4 or less, and even more preferably 3.5 or less. The acid value herein is expressed by the number of mg of potassium hydroxide necessary for neutralizing the sample 1 g, and is measured in accordance with JIS K 2501:2003.

The unsaturated polyester means a polyester compound having one or more unsaturated bonds in its molecular structure. Examples of the unsaturated polyester include: 1) a condensate of an acid having one or more unsaturated bonds and an alcohol alone; 2) a mixture of an acid having one or more unsaturated bonds and an acid having no unsaturated bond, and an alcohol; Condensate; 3) A condensate of an acid and an alcohol having one or more unsaturated bonds, and the like. Among these, a condensate of an unsaturated diproton acid and a divalent alcohol is particularly preferred.

The unsaturated diproton acid is a compound having an unsaturated double bond and two carboxylic acid groups, or an acid anhydride thereof, and examples thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like. Itaconic anhydride, mesaconic acid, citraconic acid, allyl malonic acid, and the like. Among these acids, in particular, an aliphatic unsaturated diprotonic acid having a carbon number of 4 to 6 and an aliphatic group is preferred.

Examples of the divalent alcohol include alkylene oxides such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, bisphenols, and bisphenols. Additives, etc. Among these alcohols, an alkylene oxide adduct of bisphenols is preferred. The alkylene oxide adducts of bisphenols and bisphenols will be described later.

The unsaturated polyester (B) is an epoxy containing the above unsaturated diprotonic acid (hereinafter referred to as unsaturated diprotonic acid (b1)) and bisphenol in terms of adhesion of the reinforcing fiber to the matrix resin. The condensate of the alkane adduct (b2) is preferred.

The bisphenols are compounds having two hydroxyphenyl groups, and examples thereof include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, and bisphenol F. Bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, and the like.

The bisphenol-based alkylene oxide adduct (b2) is a compound obtained by addition polymerization of an alkylene oxide to the above bisphenol. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The addition mole number of alkylene oxide is preferably 10 moles or less, and more preferably 5 moles or less, and 2 to 4 moles. The following is the best. If the addition exceeds 10 moles, the rigidity of the bisphenols may be lost, and the adhesion to the matrix resin may be lowered.

The unsaturated polyester (B) contains an unsaturated diprotonic acid (b1) in such a ratio as to satisfy the following formula (I) in terms of preventing the hardening of the reinforcing fiber strands over time and the storage stability of the syrup. It is preferred that the reactive component of the bisphenol-based alkylene oxide adduct (b2) is reacted.

Moir number of unsaturated diprotonic acid (b1) <Molar number of bisphenolic alkylene oxide adduct (b2) (I)

The Mohr ratio (b1/nb2) of the molar number of the unsaturated diprotonic acid (b1) and the alkylene oxide adduct (b2) of the bisphenol is preferably 70/100 to 99/100, and 75/100 to 90/100 is better, and 80/100 to 85/100 is better.

In terms of the adhesion of the reinforcing fiber to the matrix resin, the total ratio of the unsaturated diprotonic acid (b1) and the bisphenol-based alkylene oxide adduct (b2) to the reactive component is 90% by mole or more. Preferably, it is preferably more than 95% by mole, and more preferably 100% by mole or more.

Meanwhile, in terms of adhesion enhancement of the reinforcing fiber to the matrix resin, the reactive component is preferably an ester product substantially free of the unsaturated diproton acid. Specifically, the proportion of the esterified product of the unsaturated diprotic acid in the reactive component is preferably 2 mol% or less, more preferably 1 mol% or less, and still more preferably 0 mol%.

When the acid value of the unsaturated polyester (B) is to be lowered, although a compound having a monofunctional active hydrogen group can be considered as a reactive component, when a monofunctional active hydrogen group is used, sometimes it is between the matrix resin and the matrix resin. Adhesive The properties are lowered, and the long-term storage stability of the upper slurry may be lowered. Therefore, it is not preferable to use a monofunctional active hydrogen group as a reactive component. More specifically, the ratio of the compound having a monofunctional active hydrogen group to the reactive component is preferably 2 mol% or less, more preferably 1 mol% or less, and still more preferably 0 mol%.

The compound having a monofunctional active hydrogen group may, for example, be a monovalent alcohol, a secondary amine or a monovalent thiol.

The weight average molecular weight of the unsaturated polyester (B) is preferably from 500 to 5,000, more preferably from 800 to 4,500, still more preferably from 1,000 to 3,500. If the molecular weight is less than 500, good adhesion and heat resistance may not be obtained at the same time. On the other hand, if the molecular weight exceeds 5,000, the stability of the solution may be deteriorated.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw/Mn) of the unsaturated polyester (B) is preferably from 1.2 to 2.1, more preferably from 1.4 to 2.0, and from 1.6 to 1.9. Better yet. If the molecular weight ratio is less than 1.2, good adhesion and heat resistance may not be obtained at the same time. On the other hand, if the molecular weight ratio exceeds 2.2, the solution stability may be deteriorated.

Further, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are injected and separated at a sample concentration of 2 mg/mL by a high-speed gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh. In the column (Shodex (registered trademark) KF-G, KF-402HQ, KF-403HQ manufactured by Showa Denko Co., Ltd.), the value was calculated by a chart measured by an RI detector. Using tetrahydrofuran (THF) as the mobile phase, using polyethylene glycol (PEG) as the calibration curve The substance was measured at a separation column temperature of 40 ° C and a flow rate of 0.3 mL / min.

The method for producing the unsaturated polyester (B) is not particularly limited, and a known one can be employed. For example, it can be obtained by polycondensing an unsaturated diprotonic acid (b1) and an alkylene oxide adduct (b2) of a bisphenol. The reaction temperature at the time of polycondensation is preferably from 110 ° C to 180 ° C and more preferably from 130 ° C to 160 ° C in terms of promotion of esterification and reduction in acid value of the reaction product. The reaction time at the time of polycondensation is preferably from 1 to 10 hours, more preferably from 2 to 5 hours, in terms of promotion of esterification and reduction in acid value of the reaction product. An esterification catalyst can also be used in order to promote the polycondensation reaction.

[Fatty acid ester (C)]

The fatty acid ester (C) is an essential component of the upper slurry of the present invention. In addition to the epoxy resin (A) and the epoxy resin (A) and the unsaturated polyester (B), the sizing slurry for reinforcing fibers of the present invention can be imparted to the reinforcing fibers by containing the fatty acid ester (C). Excellent adhesion to matrix resin. At the same time, the raising of the reinforcing fiber strands and the hardening with time can be prevented. Moreover, it is excellent in long-term storage stability.

The fatty acid ester (C) is a compound having an ester bond structure of a fatty acid and a monovalent alcohol.

The fatty acid may be a saturated fatty acid having 10 to 24 carbon atoms or an unsaturated fatty acid having 10 to 24 carbon atoms. In order to prevent the raising of the reinforcing fiber strand, it is preferred to use an unsaturated fatty acid having 10 to 24 carbon atoms. The carbon number of the fatty acid is preferably from 10 to 22, more preferably from 12 to 20, still more preferably from 14 to 20.

Specific examples of the fatty acid include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid, behenic acid, and tetrakisic acid (lignoceric). Acid) and so on.

The monovalent alcohol may be a monovalent alcohol having 8 to 20 carbon atoms. More specifically, a saturated monovalent alcohol having a carbon number of 8 to 20 or an unsaturated monovalent alcohol having a carbon number of 8 to 20 may be mentioned. The carbon number of the monovalent alcohol is preferably from 12 to 22, more preferably from 14 to 20, still more preferably from 16 to 20.

Specific examples of the monovalent alcohol include, for example, octanol, decyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, oleyl alcohol, and nonadecanol And such branched alcohols and the like.

Among these, in terms of preventing the raising of the reinforcing fiber strand, the fatty acid ester (C) is a compound having an ester bond structure of an unsaturated fatty acid having 10 to 24 carbon atoms and a monovalent alcohol having 8 to 20 carbon atoms. good. The unsaturated fatty acid preferably has a carbon number of 10 to 22, more preferably 12 to 20, and still more preferably 14 to 20. The carbon number of the monovalent alcohol is preferably from 12 to 22, more preferably from 14 to 20, still more preferably from 16 to 20.

The fatty acid ester (C) can be represented by the following formula (9).

R ⁹ -COOR ¹⁰ (9)

In the formula (9), R ⁹ is an alkyl group, an alkenyl group or an alkynyl group having 9 to 23 carbon atoms. R ⁹ is preferably an alkenyl group. R ⁹ may be linear or branched. The carbon number of R ⁹ is preferably from 12 to 22, more preferably from 14 to 20, still more preferably from 16 to 20.

In the formula (9), R ¹⁰ is an alkyl group, an alkenyl group or an alkynyl group having 8 to 20 carbon atoms. R ¹⁰ may be linear or branched. The carbon number of R ¹⁰ is preferably from 10 to 20, more preferably from 12 to 20, still more preferably from 14 to 20.

Specific examples of the fatty acid ester (C) include, for example, lauric acid Octyl ester, decyl laurate, lauryl laurate, tridecyl laurate, tetradecyl laurate, hexadecyl laurate, heptadecyl laurate, octadecyl laurate, lauric acid, laurel Acid nineteen ester, octyl myristate, decyl myristate, dodecyl myristate, tridecyl myristate, tetradecyl myristate, cetyl myristate, heptadecyl myristate , octadecyl myristate, myristyl myristate, decyl myristate, octyl palmitate, decyl palmitate, lauryl palmitate, tridecyl palmitate, tetradecyl palmitate, palmitic acid Hexadecyl ester, heptadecyl palmitate, octadecyl palmitate, palmitic acid palmitate, palmitic acid nineteen ester, octyl stearate, decyl stearate, dodecyl stearate, stearic acid thirteen Ester, tetradecyl stearate, hexadecyl stearate, heptadecyl stearate, stearyl stearate, oleyl stearate, decyl stearate, octyl oleate, bismuth oleate Ester, dodecyl oleate, tridecyl oleate, tetradecyl oleate, hexadecyl oleate, heptadecyl oleate, octadecyl oleate, oleic acid ester, oleic acid decyl ester and the like.

Among these esters, in order to prevent the raising of the reinforcing fiber strands, it is octyl oleate, decyl oleate, lauryl oleate, tridecyl oleate, tetradecyl oleate, hexadecyl oleate. , heptadecyl oleate, octadecyl oleate, oleic acid ester, oleic acid decyl ester is preferred, and hexadecanic acid ester, heptadecyl oleate, oleic acid octadecyl ester, oleic acid ester Nine acid oleic acid ester is better.

The fatty acid ester (C) preferably has a melting point of 5 ° C or less and more preferably 5 ° C to -10 ° C and more preferably 5 ° C to -5 ° C in terms of preventing the raising of the reinforcing fiber strands. When the melting point exceeds 5 ° C, when the reinforcing fiber strands are stored for a long period of time in the winter, the fatty acid ester is solidified, and the effect of preventing fuzzing may be reduced. Further, the melting point in the present invention is measured as follows. take The sample was measured to a height of about 10 mm in a capillary tube (inner diameter 1 mm, outer diameter 2 mm or less, length 50 to 80 mm) which was opened at both ends. This was placed on a melting point measuring device M-565 manufactured by BUCHI, and the temperature was raised at a temperature of 1 ° C/min from the temperature below the melting point. The measurement sample was melted, and the temperature to be transparent was taken as the melting point.

The weight average molecular weight of the fatty acid ester (C) is preferably from 300 to 700, more preferably from 400 to 600, and most preferably from 500 to 600. When the molecular weight is less than 300, the heat resistance of the fatty acid ester may be lowered, and volatilization may be performed in the drying step of the reinforcing strand to reduce the effect of preventing fuzzing. If the molecular weight exceeds 700, the friction may be increased to reduce the effect of preventing fuzzing.

[Slurry for reinforcing fibers]

The sizing slurry for reinforcing fibers of the present invention must contain the above-mentioned epoxy resin (A), unsaturated polyester (B), and fatty acid ester (C).

The unsaturated polyester (B) is preferably 30 to 300 parts by weight, more preferably 35 to 250 parts by weight, still more preferably 40 to 200 parts by weight, based on 100 parts by weight of the epoxy resin (A). If it is less than 30 parts by weight, the adhesion of the reinforcing fibers to the radical polymerization-based matrix resin may be lowered. On the other hand, when it exceeds 300 parts by weight, the texture of the reinforcing fiber strand may be hardened, and frictional fuzzing may easily occur in the processing step.

The fatty acid ester (C) is preferably 1 to 15 parts by weight, and more preferably 3 to 12 parts by weight, and more preferably 5 parts by weight based on 100 parts by weight of the total of the epoxy resin (A) and the unsaturated polyester (B). It is more preferably 10 parts by weight. If it is less than 1 part by weight, the effect of preventing the raising of the reinforcing fiber strands may be reduced. On the other hand, if it exceeds 15 parts by weight, it is possible to reduce the reinforcing fibers for the matrix resin. Adhesiveness.

The ratio of the total weight of the epoxy resin (A), the unsaturated polyester (B) and the fatty acid ester (C) to the non-volatile content of the upper slurry is preferably 70% by weight or more, and 70 to 95% by weight. % is better, and more preferably 75 to 90% by weight. If it is less than 70% by weight, the adhesion of the reinforcing fibers to the matrix resin may be reduced. In addition, the non-volatile content in the present invention refers to a dry component in which the upper slurry is heat-treated at 105 ° C to remove a solvent or the like to a constant amount.

The sizing slurry of the present invention may contain water for safety of the human body during the treatment, prevention of disasters such as fire, prevention of pollution of the natural environment, and the like. An organic solvent such as methanol, ethanol, isopropanol, acetone or methyl ethyl ketone may also be used insofar as the effects of the present invention are not impaired.

The upper slurry of the present invention is obtained by self-emulsification and/or emulsification dispersion in water. The average particle diameter of the upper slurry is not particularly limited, and is preferably 10 μm or less, more preferably 0.01 to 1 μm, still more preferably 0.01 to 0.5 μm. When the average particle diameter exceeds 10 μm, the reinforcing fibers may not be completely uniformly adhered, and the upper slurry may be separated within a few days, and the storage stability may be poor and practical.

Further, the average particle diameter referred to in the present invention means an average value calculated by a particle size distribution measured by a laser diffraction/scattering type particle size distribution measuring apparatus (LA-910, Horiba).

The upper slurry of the present invention may contain other than the epoxy resin (A), the unsaturated polyester (B), and the fatty acid ester (C) described above, insofar as the effects of the present invention are not impaired. Ingredients. Other ingredients include, for example, various surfactants, various smoothing agents, antioxidants, and difficulties. A fuel, an antibacterial agent, a crystal nucleating agent, an antifoaming agent, etc. may be used alone or in combination of two or more.

When the epoxy resin (A) or the unsaturated polyester (B) or the fatty acid ester (C) or other upper slurry contains a water-insoluble or poorly soluble resin, the surfactant can be effectively used as an emulsifier. Perform aqueous emulsification.

The surfactant is not particularly limited, and may be appropriately selected from a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. One type of the surfactant may be used, or two or more types may be used in combination.

Examples of the nonionic surfactant include an alkylene oxide addition nonionic surfactant (in a higher alcohol, a higher fatty acid, an alkylphenol, a styrenated phenol, a benzyl phenol, glycerin, or a pentaerythritol, Addition of alkylene oxide, propylene oxide, etc. to sorbitol, sorbitan, sorbitan ester, castor oil, hardened castor oil, higher aliphatic amines, fatty acid guanamine, oils and fats, etc. Any of the above, a higher fatty acid or the like is added to the polyalkylene glycol, an ethylene oxide/propylene oxide copolymer, an ester of a polyhydric alcohol and a fatty acid, or an aliphatic alkanolamine.

More specifically, examples of the nonionic surfactant include polyoxyethylene hexane ether, polyoxyethylene octyl ether, polyoxyethylene oxime ether, polyoxyethylene lauryl ether, polyoxyethylene hexadecyl ether and the like. Linear alkyl ether; polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isohexadecyl ether, polyoxyethylene isostearyl ether and other polyoxyalkylene branched primary alkyl ether; polyoxyethylene 1-hexyl hexyl ether, a polyoxyalkylene branched branched secondary alkyl ether such as polyoxyethylene 1-octyl hexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentyl heptyl ether, polyoxyethylene 1-heptyl pentyl ether; Polyoxyethylene Polyoxyalkylene ether such as oleyl ether; polyoxyalkylene phenyl ether such as polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyoxyethylene dodecyl phenyl ether; polyoxyethylene tristyrene Phenyl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tristyrylmethyl phenyl ether, polyoxyethylene distyryl methyl phenyl ether, polyoxyethylene Polyoxyalkylene aryl phenyl ethers such as styrylmethyl phenyl ether, polyoxyethylene triphenylmethyl phenyl ether, polyoxyethylene diphenylmethyl phenyl ether, polyoxyethylene phenyl phenyl ether; polyoxyl Ethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxygen Polyoxyethylene alkylene fatty acid ester such as ethylene dimyristate or polyoxyethylene distearate; sorbitan ester such as sorbitan monopalmitate and sorbitan monooleate; polyoxyethylene shrinkage Polyoxyethylene sorbitan fatty acid ester such as sorbitol stearate or polyoxyethylene sorbitan monooleate; glyceryl monostearate , glycerol fatty acid esters such as glycerol monolaurate, glycerol monopalmitate; polyoxyethylene sorbitan fatty acid ester; sucrose fatty acid ester; polyoxyethylene castor oil ether and other polyoxyethylene castor oil ether; polyoxyethylene hardening Polyoxyethylene hardened castor oil ether such as castor oil ether; polyoxyethylene alkylene amino ether such as polyoxyethylene lauryl amine ether or polyoxyethylene stearyl amine ether; oxyethylene-oxypropylene block or a random copolymer; a terminal alkyl ether compound of an oxyethylene-oxypropylene block or a random copolymer; a terminal sucrose etherate of an oxyethylene-oxypropylene block or a random copolymer;

Examples of anionic surfactants include carboxylic acids (salts) and higher alcohols. Higher alcohol ether sulfate, sulfonate, higher alcohol. A phosphate salt of a higher alcohol ether or the like.

More specifically, examples of the anionic surfactant include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, and triethanolamine oleate; glycolic acid, potassium hydroxyacetate, and lactic acid. a carboxylic acid (salt) containing a hydroxyl group such as a potassium lactic acid salt; a polyoxyalkylene ether acetate (salt) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); a carboxyl group such as potassium trimellitic acid or potassium pyromelliate; a salt of an aromatic compound; an alkylbenzenesulfonic acid (salt) such as dodecylbenzenesulfonic acid (sodium salt); a polyoxyalkylene oxide such as polyoxyethylene 2-ethylhexyl sulfonic acid (potassium salt) Sulfonic acid (salt); stearic acid methyl taurine (sodium), lauryl methyl taurine (sodium), myristyl methyl taurine (sodium), palmitoyl methyl cattle a higher fatty acid such as sulfonic acid (sodium), guanamine sulfonic acid (salt); succinic acid sarcosine (sodium) and other N-mercaptoic acid sarcosine (salt); octylphosphonate (potassium salt) and other alkane Alkylphosphonic acid (salt); an aromatic phosphonic acid such as phenylphosphonate (potassium salt); an alkylphosphonic acid such as 2-ethylhexylphosphonate mono-2-ethylhexyl ester (potassium hydride) a nitrogen-containing alkylphosphonic acid such as an amino phosphate (salt); an aminoethylphosphonic acid (diethanolamine salt) Alkyl sulfate (salt) such as 2-ethylhexyl sulfate (sodium hydrazine); polyoxyethylene sulfate (salt) such as polyoxyethylene 2-ethylhexyl ether sulfate (sodium hydrazine); Long-chain sulfosuccinate such as sodium ethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium N-lauroyl glutamine, sodium N-stearyl sulfhydryl-L-glutamate Isometric chain N-mercaptoglutamine;

Examples of the cationic surfactant include, for example, lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and oil base three. Methyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, stearic acid Trimethylammonium bromide, Coconut oil alkyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide methyl sulfate, oleyl dimethyl ethyl ammonium sulfate ethyl ester, dioctyl dimethyl ammonium chloride, dilauryl An alkyl quaternary ammonium salt such as dimethyl ammonium chloride, distearyl dimethyl ammonium chloride or octadecyl diethyl methyl ammonium sulfate; (polyoxyethylene) lauryl amine ether lactate, Stearylamine ether lactate, bis(polyoxyethylene) lauryl methylamino ether dimethyl phosphate, oleyl methyl ethyl ammonium sulfate, bis(polyoxyethylene) lauryl ethyl ammonium Ethyl sulfate, bis(polyoxyethylene) hardened tallow alkyl ethylamine ethyl sulfate, di(polyoxyethylene) lauryl methyl ammonium dimethyl phosphate, di(polyoxyethylene) stearylamine lactate Et-(polyoxyethylene)alkylamino ether salt; N-(2-hydroxyethyl)-N,N-dimethyl-N-stearylsulfonyl guanamine propyl ammonium nitrate, lanolin fatty acid guanamine Alkyl decylamine alkyl quaternary ammonium salt such as ethyl ethyl dimethyl ammonium sulfate, lauryl decyl ammonium methyl methyl diethyl ammonium sulfate; dipalmityl polyoxyethylene ethyl ammonium chloride An alkane such as distearyl polyoxyethylene methyl ammonium chloride a quaternary ammonium salt of oxyethylene; an alkylisoquinoline salt such as lauryl isoquinoline chloride; a benzoate such as lauryl dimethyl benzyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride; Salt; benzoxyl salt such as benzyl dimethyl {2-[2-(p--1,1,3,3-tetramethylbutylphenoxy)ethoxy]ethyl}ammonium chloride; Pyridinium salt such as hexaalkylpyridine chloride; oil-based hydroxyethyl imidazoline ethyl sulfate, lauryl hydroxyethyl imidazoline ethyl sulfate and the like imidazoline salt; N-cocoyl arginine ethyl pyrrolidone carboxylic acid Salt, N-lauroyl-ethylamine ethyl chloride chloride, etc.; alkyl basic amino acid alkyl ester; laurylamine chloride, stearylamine bromide, hardened tallow alkylamine chloride, rosin a primary ammonium hydrazine such as an amine acetate; cetylmethylamine sulfate, lauryl methylamine chloride, dilaurylamine acetate, stearylamine bromide, a secondary amine salt such as lauryl propylamine acetate, dioctylamine chloride or octadecylethylamine hydroxide; dilaurylmethylamine sulfate, lauryl diethylamine chloride, laurel Triethylammonium bromide such as ethyl ethyl methylamine bromide, diethanol stearyl decylamine ethylamine trihydroxyethyl phosphate, stearyl decylamine ethylethanolamine urea polycondensate acetate; fatty acid amidoxime a salt; an alkyltrialkyl glycol ammonium salt such as lauryl triethylene glycol ammonium hydroxide or the like.

The amphoteric surfactant can be exemplified by, for example, 2-undecyl-N,N-(hydroxyethylcarboxymethyl)-2-imidazolinium, 2-cocoin-2-imidazolium hydroxide-1 -Imidazoline-based amphoteric surfactant such as carboxyethoxy 2 sodium salt; 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, stearyl dimethyl betaine, laurel Beta-hydroxyethyl betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, guanamine betaine, sulphobetaine and other betaine amphoteric surfactant; N-lauryl glycine, An amino acid type amphoteric surfactant such as N-lauryl β-alanine, N-stearyl β-alanine or sodium lauryl alaninate.

When the surfactant is contained, the proportion of the surfactant in the non-volatile portion of the upper slurry is preferably 5 to 30% by weight, more preferably 10 to 25% by weight, and 15 to 25% by weight. Better.

The non-volatile content of the sizing slurry of the present invention is not particularly limited, and is appropriately selected in consideration of the stability of the aqueous dispersion, the viscosity of the product to be easily handled, and the like. When considering the transportation cost of the product, etc., the proportion by weight of the nonvolatile matter in the entire upper slurry is preferably 10 to 100% by weight, more preferably 15 to 100% by weight, and 20 to 100% by weight. Especially good.

Meanwhile, the total weight ratio of water and non-volatile matter in the entire upper slurry is preferably 90% by weight or more, more preferably 95% by weight or more, and still more preferably 99% by weight or more, and 100% by weight. Weight% is especially good. If it is less than 90% by weight, that is, when the organic solvent or other low-boiling compound which does not remain in a non-volatile content at the time of heat treatment contains 10% by weight or more, the safety of the human body during the treatment or the prevention of the pollution to the natural environment is prevented. In terms of, the system is not good.

Further, in the above aqueous dispersion or aqueous solution, in addition to the safety to the human body or the prevention of contamination to the natural environment, it is prevented that the water dispersion or the aqueous solution is thickened/solidified over time, even if it does not contain When the solvent other than water such as an organic solvent is contained, it is preferably 10% by weight or less based on the total amount of the upper slurry, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

The method of preparing the upper slurry of the present invention into an aqueous dispersion is not particularly limited, and a known method can be employed. As described above, a method of mixing the components as a water dispersion when each component in the upper slurry is formed, and mixing the components constituting the upper slurry into warm water under stirring to emulsify and disperse a method of mixing emulsified dispersions in which the components of the upper slurry are pre-emulsified and dispersed; mixing the components constituting the upper slurry, and heating the obtained mixture to a softening point or higher, and then using a homogenizer or a ball mill A method in which a mechanical shearing force is applied to a water phase to gradually convert the emulsification.

[Strengthened fiber strands and their manufacturing methods]

The reinforcing fiber strand of the present invention adheres to the above-mentioned sizing filler for reinforcing fibers to the raw material reinforcing fiber strands, and is used for reinforcing the reinforcing fibers of the matrix resin. The reinforcing fiber strand of the present invention is excellent in adhesion to a matrix resin. The matrix resin is preferably a thermosetting matrix resin in terms of improving the adhesion improving effect by the sizing agent of the present invention. Since the reinforcing fiber strand of the present invention causes less fuzzing, it is excellent in the passability of the step, and since the sizing slurry for reinforcing fibers has little or no change with time, it is excellent in long-term storage stability.

The amount of non-volatile matter of the upper slurry to the raw material reinforcing fiber strands may be appropriately selected as long as the reinforcing fiber strands have the necessary amount for the desired function, but the adhesion amount is 0.1 to 0.1 relative to the raw material reinforcing fiber strands. 20% by weight is preferred. In the reinforcing fiber strand of the long fiber form, the adhesion amount is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the raw material reinforcing fiber strand. Meanwhile, in the strand of the chopped fiber form (cut to a predetermined length), it is preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight.

When the amount of the slurry to be applied is too small, it is difficult to obtain the heat resistance, the resin impregnation property, and the adhesion of the effect of the present invention, and the bunching property of the reinforcing fiber strand may be insufficient to deteriorate the handleability. At the same time, when the amount of the slurry adhered is too large, the reinforcing fiber strands are too rigid, and the handleability is poor, and the resin impregnation property is deteriorated during the composite molding, which is not preferable.

The method for producing a reinforcing fiber strand, comprising the above-mentioned upper slurry, preparing a treatment liquid in which the weight ratio of the nonvolatile matter is 0.5 to 10% by weight, and the total weight ratio of water to the nonvolatile matter is 90% by weight or more; Further, in order to make the adhesion amount of the nonvolatile matter to the raw material reinforcing fiber strands to be 0.1 to 20% by weight, the treatment liquid adheres to the raw material reinforcing fiber strands.

In the preparation step, the proportion by weight of the non-volatile matter in the treatment liquid is preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by weight. The total weight ratio of water to non-volatile matter is preferably 95% by weight or more, more preferably 99% by weight or more, and still more preferably 100% by weight.

In the attaching step, it is preferred that the amount of non-volatiles adhered as in the previous stage. The method of attaching the upper slurry to the raw material reinforcing fiber strand is not particularly limited, and any method may be employed in which the upper slurry is adhered to the raw material reinforcing fiber strand by another known method such as a kiss roll method, a roll impregnation method, or a spray method. Among these methods, the roller dipping method is preferable because the upper slurry can be uniformly adhered to the raw material reinforcing fiber strand.

The method for drying the obtained deposit is not particularly limited, and for example, it can be heated and dried by heating a roller, a hot air, a hot plate or the like.

Further, the upper slurry of the present invention is allowed to adhere to the raw material reinforcing fiber strand, and the constituent components of the upper slurry can be all mixed and adhered, and the constituent components can be attached to each of the two or more stages. In addition, in addition to the epoxy resin (A), the unsaturated polyester (B), and the fatty acid ester (C), a thermosetting resin such as a vinyl ester resin or a phenol resin may be used as long as the effect of the present invention is not inhibited. And/or a thermoplastic resin such as a polyolefin resin, a polyester resin, a nylon resin, or an acrylic resin adheres to the raw material reinforcing fiber strand.

The reinforcing fiber strand of the present invention can be used as a reinforcing fiber of a composite material using various resins as a matrix resin, and may be in the form of a long fiber or a chopped fiber.

The (raw material) reinforcing fiber strand of the upper slurry to which the present invention is applicable, and various inorganic fibers of carbon fiber, glass fiber, and ceramic fiber, Amidamide fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, PBO fiber , such as polyphenylene sulfide fiber, polyketone fiber and other organic fibers. In terms of the physical properties of the obtained fiber-reinforced composite material, the (raw material) reinforcing fiber strand is selected from the group consisting of carbon fiber, guanamine fiber, polyethylene fiber, polyethylene terephthalate fiber, and polybutylene terephthalate. Preferably, at least one of ester fibers, polyethylene naphthalate fibers, polyarylate fibers, polyacetal fibers, PBO fibers, polyphenylene sulfide fibers, and polyketone fibers is preferred, and carbon fiber strands are preferred. .

[Fiber reinforced composite material]

The fiber-reinforced composite material of the present invention is a material comprising a matrix resin and the aforementioned reinforcing fiber strands. The reinforcing fiber strands are uniformly treated by the sizing treatment of the present invention, and the affinity between the reinforcing fiber strands and the matrix resin is good, and the fiber-reinforced composite material having excellent adhesion is obtained. Here, the matrix resin refers to a matrix resin composed of a thermosetting resin or a thermoplastic resin, and may contain one type or two or more types. The thermosetting resin is not particularly limited, and examples thereof include an epoxy resin, a phenol resin, an unsaturated polyester resin, a vinyl ester resin, an acrylic resin, a cyanate resin, and a polyimide resin. The thermoplastic matrix resin is not particularly limited, and examples thereof include a polyolefin resin, a polyamide resin, a polycarbonate resin, a polyester resin, a polyacetal resin, an ABS resin, a phenoxy resin, and a polymethacrylic acid. A methyl ester resin, a polyphenylene sulfide resin, a polyether phthalimide resin, a polyether ketone resin, or the like. Among these resins, it is preferred to use a thermosetting matrix resin for the adhesion improving effect of the sizing agent of the present invention, and to use an epoxy resin or not. Saturated polyester resin, vinyl ester resin is better, and epoxy resin is the best. Here, the epoxy resin means a compound having a reactive epoxy group in a molecular structure, and by heating with a curing agent and heating, the epoxy group can be crosslinked and networked to be hardened. The essential component of the epoxy resin-based slurry may be the same as the epoxy resin (A) described above. These matrix resins are used for the purpose of improving the adhesion to the reinforcing fiber strands, and it is also possible to modify some or all of them.

The method for producing the fiber-reinforced composite material is not particularly limited, and a known method such as composite injection molding of chopped fibers, long fibers, or the like, UD sheet, press forming of a fabric sheet, or other fiber winding molding may be employed.

When the thermosetting matrix resin and the reinforcing fiber strand are kneaded, a method of producing a fiber-reinforced composite material by mixing a curing agent and heating under pressure or normal pressure; or mixing a curing agent and a hardening accelerator at room temperature A method of making a fiber reinforced composite material.

The content of the reinforcing fiber strands in the fiber-reinforced composite material is not particularly limited, and may be appropriately selected depending on the type, form, and type of the matrix resin, but for the fiber-reinforced composite material available, 5 to 70% by weight is preferred, and more preferably 20 to 60% by weight.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples described herein. In addition, the percentage (%) shown in the following examples is not particularly limited, and may represent "% by weight" or "parts by weight". The measurement of each characteristic value was carried out in accordance with the method shown below.

<solution stability>

Each of the treated emulsions having a nonvolatile content of 3.0% by weight was stored in a thermostat adjusted to 50 ° C, and the appearance of the solution was visually confirmed, and the solution stability was determined by the following evaluation criteria.

◎: No separation for 60 days.

○: No separation for 30 days, and separation within 60 days.

△: No separation in 7 days, and separation within 30 days.

×: Separated within 7 days.

××: Separation on the day of emulsification, or failure to emulsify.

<adhesiveness>

Adhesive evaluation was performed by the microdroplet method using a composite interface property evaluation device HM410 (manufactured by Toray Industries Co., Ltd.).

The carbon fiber strands were taken out from the carbon fiber strands obtained in the examples and the comparative examples, and placed on a sample holder. A droplet of each matrix resin to which the curing agent or the curing accelerator has been mixed is formed on the carbon fiber yarn, and the droplet is cured by the following curing method to obtain a sample for measurement. The measurement sample was placed on the apparatus, the droplets were clamped by the device blade, and the carbon fiber filament was moved at a speed of 0.06 mm/min on the apparatus, and the maximum extraction tensile force F when the droplet was extracted from the carbon fiber was measured.

The adhesion strength τ was calculated by the following formula, and the adhesion between the carbon fiber filament and the matrix resin was evaluated.

Interfacial shear strength τ (unit: MPa) = F / π dl (F: maximum pull-out force d: carbon fiber wire diameter l: particle size in the direction in which the droplets are pulled out)

(hardening method of droplets of each matrix resin)

Matrix resin in Examples 1 to 10 and Comparative Examples 1 to 4, 7 to 9 An epoxy resin was used, and in Examples 11 to 14 and Comparative Example 5, an unsaturated polyester resin was used, and in Examples 15 to 18 and Comparative Example 6, a vinyl ester resin was used.

Epoxy resin: 100 parts by weight of epoxy resin JER828 (manufactured by Mitsubishi Chemical Corporation) and 3 parts by weight of matrix resin (manufactured by Mitsubishi Chemical Corporation) were adjusted to 80 ° C for 1 hour and 150 ° C for 3 hours. The droplets are heated to harden them.

Unsaturated polyester resin: 100 parts by weight of an unsaturated polyester resin Rigolac M540 (manufactured by Showa Denko Co., Ltd.) and 2 parts by Permek (manufactured by Nippon Oil Co., Ltd.) adjusted to 80 ° C for 1 hour and 150 ° C for 3 hours. The droplets of the matrix resin are heated to harden.

Vinyl ester resin: 100 parts by weight of a vinyl ester resin Repoxy R-806 (manufactured by Showa Denko Co., Ltd.) and Percure-O (manufactured by Nippon Oil Co., Ltd.) 2 at 80 ° C for 1 hour and 150 ° C for 3 hours. The droplets of the part by weight of the matrix resin are heated to harden them.

<friction fluffing>

Using the TM type friction cohesive force tester TM-200 (manufactured by Daiei Scientific Seiki Co., Ltd.), the mirror-plated chrome-plated stainless steel needles arranged in a zigzag pattern were rubbed with a tension of 50 g to rub the examples and comparative examples. The obtained carbon fiber strands were 1,000 times (reciprocating speed 300 times/min), and the raised state of the carbon fiber strands was visually determined on the basis of the following criteria.

◎: No fluffing was observed at all as before the wiping.

○: Although there are several hair liftings, it is practically not a problem.

△: A lot of fluffing was observed, and a number of broken wires were also confirmed.

×: It was confirmed that there were a lot of fluffing and filament breakage.

<Fiber preservation>

The carbon fiber strands obtained in the examples and the comparative examples were stored at 100 ° C for 10 days, and the difference between the hardness of the carbon fiber strands after storage and the hardness of the carbon fiber strands before storage was determined, and it was judged that the smaller the difference, the less the hardening with time. The hardness of the carbon fiber strand (length: about 50 cm) was measured by a texture tester (manufactured by HANDLE-O-METERHOM-2, Daiei Scientific Seiki Co., Ltd., with a slit width of 10 mm).

[Epoxy Resin (A)]

JER1001: Made of Mitsubishi Chemical Corporation, solid bisphenol A epoxy resin, epoxy equivalent 450 to 500

JER834: Made of Mitsubishi Chemical Corporation, semi-solid bisphenol A epoxy resin, epoxy equivalent 230 to 270

JER828: Made by Mitsubishi Chemical Corporation, liquid bisphenol A epoxy resin, epoxy equivalent 184 to 194

JER807: Made by Mitsubishi Chemical Corporation, liquid bisphenol F type epoxy resin, epoxy equivalent 160 to 175

JER157S65: bisphenol A phenolic ring made by Mitsubishi Chemical Corporation Oxygen resin, epoxy equivalent 200 to 220

[Synthesis of Unsaturated Polyester (B)]

(Synthesis Example B-1)

The maleic anhydride 0.9 mol and the ethylene oxide 4 molar addition of bisphenol A were reacted at 1.0 ° C for 5 hours to obtain an unsaturated polyester (B-1) having an acid value of 2.5. Weight average molecular weight (Mw) is 3,051, weight average The ratio (Mw/Mn) of the molecular weight (Mw) to the number average molecular weight (Mn) was 1.6.

(Synthesis Example B-2)

An ethylene oxide 2 molar addition of 0.8 moles of maleic anhydride and bisphenol A was reacted at 1.4 ° C for 3 hours to obtain an unsaturated polyester (B-2) having an acid value of 3.5. The weight average molecular weight (Mw) was 1,626, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 1.7.

(Synthesis Example B-3)

0.85 mol of fumaric acid and 1.0 mol of ethylene oxide 3 molar addition of bisphenol A were reacted at 170 ° C for 8 hours to obtain an unsaturated polyester (B-3) having an acid value of 4.5. The weight average molecular weight (Mw) was 3,444, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 1.9.

(Synthesis Example B-4)

The maleic anhydride 0.9 mol and the propylene oxide 3 molar addition product of bisphenol A were reacted at 150 ° C for 5 hours to obtain an unsaturated polyester (B-4) having an acid value of 2.0. The weight average molecular weight (Mw) was 2,903, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 1.7.

[Synthesis of Unsaturated Polyester]

(Synthesis Example b-1)

1.0 mmol of maleic anhydride and 1.0 mole of ethylene oxide 2 molar addition of bisphenol A were reacted at 135 ° C for 2 hours to obtain an unsaturated polyester (b-1) having an acid value of 60. The weight average molecular weight (Mw) was 3,872, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 2.0.

(Synthesis Example b-2)

Making maleic anhydride 1.0 mole with bisphenol A ethylene oxide 2 mole The adduct 1.0 mole was reacted at 135 ° C for 5 hours, and further reacted at 170 ° C for 5 hours to obtain an unsaturated polyester (b-2) having an acid value of 6.3. The weight average molecular weight (Mw) was 5,736, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 2.3.

(Synthesis Example b-3)

1.0 mmol of maleic anhydride and 1.0 mole of ethylene oxide 4 molar addition of bisphenol A were reacted at 160 ° C for 5 hours to obtain an unsaturated polyester (b-3) having an acid value of 10. The weight average molecular weight (Mw) was 4,860, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 2.0.

(Synthesis Example b-4)

1.0 mmol of maleic anhydride and 1.0 mole of ethylene oxide 3 molar addition of bisphenol A were reacted at 140 ° C for 4 hours to obtain an unsaturated polyester (b-4) having an acid value of 30. The weight average molecular weight (Mw) was 4,860, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 2.1.

[Fatty Acid Polyester (C)]

Oleic acid oil ester: melting point 4 ° C

Lauryl oleate: melting point 11 ° C

Isooctyl stearate: melting point 10 ° C

[Example 1]

JER1001, unsaturated polyester (B-1), oleic acid ester, POE (150) hardened castor oil ether, PO / EO (25 / 75) polyether (molecular weight 16,000) into the emulsifying device, such as the table The nonvolatile content of the treating agent shown in Fig. 1 was gradually added with water under stirring to cause phase inversion and emulsification to obtain an aqueous slurry aqueous dispersion having a nonvolatile content of 30% by weight. Dispersion of upper slurry water diluted with water To prepare a sizing emulsion having a non-volatile content of 3% by weight, and immersing/impregnating the untreated carbon fiber strands (denier 800 tex, number of filaments 12,000) in an upper slurry, and then drying it at 105 ° C for 15 minutes with hot air to obtain a theory. The upper slurry treated carbon fiber strands having an adhesion amount of 1.0%. The evaluation of each characteristic value of the present slurry and the stock was carried out by the aforementioned method. Adhesion and friction fluffing were evaluated using carbon fiber strands before fiber preservative evaluation and carbon fiber stocks after fiber preservative evaluation. The results are shown in Table 1.

[Examples 2 to 18, Comparative Examples 1 to 9]

The same procedure as in Example 1 was carried out except that the upper slurry emulsion was adjusted to the nonvolatile content of the treating agent as shown in Tables 1 to 3, and the upper slurry-treated carbon fiber strand was obtained, and each of the evaluations was evaluated. Characteristic value. The results of the respective characteristic values are shown in Tables 1 to 3.

As is clear from Tables 1 to 3, the sizing slurry of the examples was excellent in long-term stability. At the same time, the fiber strands of the examples were excellent in adhesion to the matrix resin to prevent fuzzing. Further, the fiber is excellent in preservability, and the adhesion after storage of the fiber is also excellent, and fluffing can be prevented.

[Possibility of application in industry]

The fiber-reinforced composite material of the reinforced fiber matrix resin can be used in automotive applications, aerospace applications, sports and leisure applications, general industrial applications, and the like. Examples of the reinforcing fibers include various inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers, and various organic fibers such as melamine fibers, polyamide fibers, and polyethylene fibers. The upper slurry of the present invention can be suitably used for reinforcing reinforcing fibers for a matrix resin.

Claims (12)

A sizing slurry for reinforcing fibers, which comprises an epoxy resin (A), an unsaturated polyester (B) having an acid value of less than 5, and a fatty acid ester (C). The above-mentioned unsaturated polyester (B) is 30 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin (A), as opposed to 100 parts by weight of the epoxy resin (A). 100 parts by weight of the total of the epoxy resin (A) and the unsaturated polyester (B), and the fatty acid ester (C) is 1 to 15 parts by weight. The sizing slurry for reinforcing fibers according to claim 1 or 2, wherein the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the unsaturated polyester (B) (Mw/Mn) It is 1.2 to 2.1. The sizing slurry for reinforcing fibers according to any one of claims 1 to 3, wherein the unsaturated polyester (B) contains an unsaturated diprotonic acid (b1) and a bisphenol-based cycloalkoxide The condensate of the adduct (b2). The sizing slurry for reinforcing fibers according to any one of claims 1 to 4, wherein the pre-unsaturated polyester (B) is a cycloalkane of an unsaturated diprotonic acid (b1) and a bisphenol. The adduct (b2) is obtained by reacting a reactive component contained in the ratio of the following formula (I), and the molar number of the unsaturated diprotonic acid (b1) < the bisphenol-based alkylene oxide adduct ( B2) Molar number (I). The sizing slurry for reinforcing fibers according to any one of claims 1 to 5, wherein the unsaturated polyester (B) has an acid value of 4.5 or less. The sizing slurry for reinforcing fibers according to any one of claims 1 to 6, wherein the fatty acid ester (C) has a melting point of 5 ° C or less. The sizing slurry for reinforcing fibers according to any one of claims 1 to 7, wherein the fatty acid ester (C) has an unsaturated fatty acid having a carbon number of 10 to 24 and a carbon number of 8 to 20. An ester of a structure in which the valent alcohol is ester-bonded. The sizing slurry for reinforcing fibers according to any one of claims 1 to 8, wherein the epoxy resin (A), the unsaturated polyester (B), and the fatty acid ester (C) The ratio of the total weight to the nonvolatile content of the upper slurry is 70% by weight or more. A reinforced fiber strand which is adhered to the sizing slurry for reinforcing fibers described in any one of claims 1 to 9 to the raw material reinforced fiber enthalpy. A fiber reinforced composite material comprising a matrix resin and a reinforcing fiber strand according to claim 10 of the patent application. The fiber-reinforced composite material according to claim 11, wherein the matrix resin is a thermosetting resin.