TWI696649B - Sizing agent for reinforced fiber and use thereof - Google Patents

Abstract

This invention provides a sizing agent for reinforced fiber having excellent thermal resistance together with high viscosity at high temperature, and a reinforced fiber formed by providing the sizing agent.

This invention provides sizing agent for reinforced fiber containing at least one selected of the following component (I) and the following component (II). Component (I): a compound obtained by bringing a titanium compound (A) and a compound (B) with activated hydrogen group into reaction; Component (II): titanium compound (A) and a compound (B) with activated hydrogen group. The compound (B) is preferably a compound (B1) containing hydroxyl group. The compound (B1) is preferably containing at least one selected from epoxy resin, polyester resin, urethane resin and poletherpolyol resin.

Description

Sizing agent for reinforcing fiber and its use

The present invention relates to a sizing agent for reinforcing fibers and a reinforcing fiber obtained by giving a sizing agent for reinforcing fibers.

By coating a sizing agent on the fiber, the bundling property can be improved and the process can proceed smoothly, the texture of the manufactured fiber can be adjusted, and various functions can be imparted to the fiber. Among these characteristics, bundling is one of the most important performances to improve production efficiency and quality. It is greatly affected by the viscosity of the sizing agent. When the viscosity is low, bad problems such as low bundling and fiber fuzzing may occur. . Therefore, as described in Patent Document 1, it is very important to increase the viscosity of the sizing agent in order to improve the bundling property.

The sizing agent for reinforcing fibers is applied to the surface of the reinforcing fibers. It is responsible for smoothing the process of reinforcing fibers and the like, making the manufactured reinforcing fibers and the like easier to handle, and will be called matrix resin (matrix resin). The role of connecting the reinforcing fiber to the matrix resin when the resin is immersed in the reinforcing fiber, etc. One of the properties required for these sizing agents includes heat resistance. When matrix resin is used for FRP (Fiber-Reinforced Plastics) of sizing carbon fiber, it is mostly in The matrix resin is hardened at a high temperature, or a resin that has been melted at a high temperature is used.

In this case, the sizing agent may be thermally decomposed to reduce the adhesion between the carbon fiber or the like and the matrix resin, or the gasification of the decomposition product may generate pores and FRP may not be able to satisfy the desired physical property value. In addition, since the FRP is exposed to the above-mentioned high-temperature environment, if the viscosity of the sizing agent is low at high temperatures, the carbon fiber may be excessively dispersed and the carbon fiber may break, so that the predetermined performance may not be exhibited.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2013/146024 Brochure

An object of the present invention is to provide a sizing agent for reinforcing fibers that is excellent in heat resistance and at the same time has a high viscosity at high temperature, and reinforced fibers obtained by giving the sizing agent.

The present inventors conducted intensive studies and found that the above problems can be solved by using at least one component selected from the specific component (I) and the specific component (II), and the present invention has been completed.

That is, the present invention is a sizing agent for reinforcing fibers containing at least one component selected from the following components (I) and (II).

Component (I): a compound formed by reacting a titanium compound (A) and a compound (B) having an active hydrogen group

Ingredient (II): Titanium compound (A) and compound with active hydrogen group (B)

The aforementioned compound (B) preferably contains a compound (B1) having a hydroxyl group.

The compound (B1) preferably contains at least one selected from epoxy resins, polyester resins, urethane resins and polyether polyol resins.

The aforementioned component (II) preferably satisfies the following condition 1.

Condition 1: The weight ratio (A/B) of the aforementioned compound (A) to the aforementioned compound (B) is 0.001 to 10% by weight

The aforementioned compound (A) is preferably represented by the following general formula (1).

(式中，R¹至R⁴是有機基，可分別相同也可不同。n是1以上的整數)。

(In the formula, R ¹ to R ⁴ are organic groups and may be the same or different. n is an integer of 1 or more).

Preferably, the aforementioned organic group is an alkyl group having 2 to 8 carbon atoms, and the aforementioned n is 1.

It is better to further contain a smoothing agent (C).

The reinforcing fiber strand of the present invention is obtained by attaching the above reinforcing fiber sizing agent 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 strands.

Since the sizing agent for reinforcing fibers of the present invention is excellent in bundling property and heat resistance, the decomposition at high temperature is reduced, and the viscosity at high temperature is high, so the loss of reinforcing fibers is not likely to occur and the strength of FRP is excellent.

The sizing agent for reinforcing fibers of the present invention contains at least one component selected from the aforementioned component (I) and the aforementioned component (II). Since the component (I) and the above component (II) are components derived from the titanium compound (A) and the compound (B) having an active hydrogen group, the titanium compound (A) and the compound (B) having an active hydrogen group will be explained first.

[Titanium compound (A)]

The titanium compound (A) is a compound containing a titanium atom in the molecule, and by reacting or combining with a compound (B) having an active hydrogen group described later, the active hydrogen group of the compound (B) undergoes crosslinking or interaction to Improve the viscosity or heat resistance of sizing agent for reinforcing fiber.

The compound (A) is not particularly limited as long as it crosslinks with an active hydrogen group, and examples thereof include organic titanium compounds and/or inorganic titanium compounds.

The above-mentioned organic titanium compound is an organometallic compound in which a titanium atom is bonded to an organic group through oxygen (oxygen atom), and examples thereof include alkoxides, chelates, amides, carboxylic acids, and amines. .

Examples of alkoxides include: tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra Isobutoxy titanium, tetra-second butoxy titanium, tetra-third butoxy titanium, tetra(2-ethylhexyl) titanate, tetracyclohexyl titanate, tetra(octadecyl) titanate , Tetraphenyl titanate, tetrakis(tyl) titanate, triisopropoxy isopropyl titanium, tri-n-butoxy n-butyl titanium, tri-n-butoxy titanium monostearate, etc.

The alkoxides are preferably cross-linked with hydroxyl groups to improve heat resistance, so those represented by the above general formula (1) are preferred.

In the general formula (1), R ¹ to R ⁴ are organic groups and may be the same or different. n is an integer of 1 or more.

From the viewpoint of improving heat resistance, the aforementioned R ¹ to R ⁴ are at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 3 to 8 carbon atoms, and aryl groups having 6 to 10 carbon atoms. Better. More preferred is an alkyl group having 2 to 4 carbon atoms.

When n is 1, crosslinking reaction is easy to occur and heat resistance can be extremely improved, which is preferable.

The preferred upper limit of n is 4. If it exceeds 4, the compatibility with the compound (B) having an active hydrogen group used together may be reduced, and the stability of the sizing agent for reinforcing fibers may be reduced.

Chelates include: diisopropoxy titanium bis(ethyl acetoacetate), diisopropoxy titanium bis(ethyl acetoacetate), diisopropoxy titanium bis(ethyl acetate) (Propyl acetyl acetate), diisopropoxy titanium bis (ethyl acetyl acetate), diisopropoxy titanium bis (ethyl acetyl acetate), di-n-propoxy titanium bis (ethyl acetyl) Methyl acetate), di-n-propoxy titanium bis (ethyl acetate), di-n-propoxy titanium bis (propyl acetate), di-n-propoxy titanium bis (ethyl acetate) Ester), di-n-propoxytitanium bis(acetoacetate hexyl), di-n-butoxytitanium bis(acetoacetate methyl), di-n-butoxytitanium bis(acetoacetate) Ethyl), di-n-butoxytitanium bis(propyl acetyl acetate), di-n-butoxytitanium bis(butyl acetyl acetate), di-n-butoxytitanium bis(ethyl acetyl acetate) ), 1,3-propanedioxytitanium bis(ethylacetate), diisopropoxytitanium bis(acetylacetate), di-n-propoxytitanium bis(acetylacetate) Ester), di-n-butoxytitanium bis(acetylacetate), titanium tetraethylacetate, titanium tetra(ethylacetate), titanium tetra(propylacetate), Titanium four (butyl acetyl acetate), etc.

Compounds include: tri-n-butoxy titanium monostearate, diisopropoxy titanium distearate, titanium stearate, titanium diisopropoxide, and diisostearic acid (2- N-butoxycarbonylbenzyloxy) tributoxy titanium and so on.

Carboxylic acids include titanium trimellitate, titanium tetraacetate, titanium triacetate, titanium tetrabutyrate, titanium tributyrate, titanium tetralactate, titanium citrate, titanium oxalate, potassium titanium oxalate, sodium titanium oxalate, etc. .

The inorganic titanium compound is not particularly limited as long as it can react with an active hydrogen group, but it may include titanium chloride.

[Compound (B) with active hydrogen group]

The compound (B) having an active hydrogen group can be reacted with or used in combination with the above-mentioned compound (A) to cross-link the active hydrogen groups with each other or interact with the titanium compound to improve the viscosity of the sizing agent.

The compound (B) having an active hydrogen group, although not particularly limited, may include a compound having a hydroxyl group (B1), a compound having an amine group (B2), a compound having a carboxyl group (B3), and a compound having a thiol group Compound (B4), compound with phosphoric acid group (B5), in which The compound (A) is preferably a compound (B1) having a hydroxyl group from the viewpoint that the compound (A) is cross-linked and excellent in improving viscosity and heat resistance at high temperature.

The compound (B1) having a hydroxyl group is not particularly limited as long as it has a hydroxyl group, but examples thereof include a compound containing an aliphatic hydroxyl group, a compound containing an aromatic hydroxyl group, an epoxy resin, a polyester resin, an urethane resin, and a poly Ether polyol resin, polycarbonate polyol resin, polybutadiene polyol resin, polyacrylic polyol resin, polybutadiene polyol resin, hydrogenated polybutadiene resin, castor oil-based polyol resin, poly Hydroxy compounds such as vinyl alcohol or polymers.

Among them, from the viewpoint of improving the viscosity and improving the heat resistance, epoxy resins, polyester resins, urethane resins and polyether polyol resins are preferred. In order to easily react with the compound (A), the viscosity From the viewpoint that the improvement in heat resistance and heat resistance becomes excellent, the epoxy resin is more preferable.

Compounds containing aliphatic hydroxyl groups, although not particularly limited, may include glycerin, trimethylolpropane, isopentitol, diglycerin, α-methyl glucoside (α-methyl glucoside), sorbitol, wood Sugar alcohol, mannitol, diisopentaerythritol, glucose, fructose, sucrose, etc.

Although there are no particular restrictions on the aromatic hydroxyl group-containing compound, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, etc. may be mentioned.

Epoxy resin refers to compounds with more than two reactive epoxy groups in the molecular structure. Epoxy resins are represented by the deglycidyl ether type obtained from epichlorohydrin and active hydrogen compounds. Other examples include deglycidyl ester type, deglycidylamine type, and fat. Ring type, etc. One type of epoxy resin may be used, or two or more types may be used in combination.

The epoxy resin is not particularly limited as long as it has a hydroxyl group, but examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and phenol novolac ) Type epoxy resin, cresol novolac epoxy resin, alkylphenol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin or amine modified aromatic Various modified epoxy resins such as family epoxy resin.

Among them, from the viewpoint of improving the viscosity and improving the heat resistance, an epoxy resin having a repeating unit represented by the following chemical formula (2) is particularly preferable.

(式(2)中，R¹、R²、R³及R⁴係分別獨立表示氫原子或甲基。n1是1以上的整數)。

(In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. n1 is an integer of 1 or more).

The epoxy equivalent of the epoxy resin is preferably 100 to 1,500 g/eq, more preferably 120 to 1,000 g/eq, and even more preferably 150 to 800 g/eq. When the epoxy equivalent is less than 100g/eq, it may promote the hardening of the reinforcing fiber strands over time. When the epoxy equivalent exceeds 1,500 g/eq, the adhesion to the matrix resin may be reduced. In addition, epoxy equivalent refers to those based on JIS-K7236.

The weight average molecular weight of the epoxy resin is preferably from 100 to 10,000, more preferably from 100 to 8,000, and from 150 to 7,000. Better. When the weight average molecular weight is less than 100, the heat resistance may be insufficient due to the drying step of the reinforcing fiber strands and the like, and may sublime. If the weight average molecular weight exceeds 10,000, the stability of the sizing agent for long-term storage may be reduced.

Although the polyester resin is not particularly limited, it has a structure obtained by dehydrating and condensing a polycarboxylic acid or its anhydride and a polyhydric alcohol, and has at least one hydroxyl group in the molecule.

Examples of the polycarboxylic acid include aromatic dicarboxylic acid, sulfonate-containing aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and trifunctional or higher polycarboxylic acid.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, and diphenyl Oxyethane dicarboxylic acid, phthalic anhydride, etc.

The sulfonate-containing aromatic dicarboxylic acid includes sulfonate terephthalate, 5-sulfonate isophthalate and the like.

Aliphatic dicarboxylic acid or alicyclic dicarboxylic acid, including fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid , 1,4-Cyclohexanedicarboxylic acid, succinic anhydride, maleic anhydride, etc.

Examples of polycarboxylic acids having more than three functions include trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride.

Examples of the above-mentioned polyhydric alcohols include diols and trifunctional polyhydric alcohols.

Examples of glycols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. , Neopentyl glycol, tetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexane di Methanol, resorcinol, hydroquinone, bisphenol A or its alkylene oxide adducts.

The polyhydric alcohol with more than three functions includes trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, di-trimethylolpropane and the like.

In addition, the above-mentioned resin having a hydroxyl group may also be used.

The hydroxyl value of the polyester resin is preferably from 10 to 250 mgKOH/g, more preferably from 15 to 150 mgKOH/g, and even more preferably from 30 to 120 mgKOH/g. In addition, the hydroxyl value is measured in accordance with JIS K1557-1970.

The number average molecular weight of the polyester resin is preferably from 500 to 10,000, more preferably from 700 to 8,000, and even more preferably from 1,000 to 4,000. In addition, the number average molecular weight in the present invention is calculated from the aforementioned hydroxyl value.

The polyester resin can be obtained by dehydrating and condensing the polycarboxylic acid or its anhydride with the polyol and using the same method as the known polyester production method.

The polyurethane resin is not particularly limited as long as it is a reaction product of a known polyisocyanate and a known polyol as a main component.

The polyisocyanate may be an aromatic polyisocyanate compound or an aliphatic polyisocyanate compound.

Aromatic polyisocyanate compounds include, for example, tolyl-2,4-diisocyanate, tolyl-2,6-diisocyanate, xylylene diisocyanate, naphthyl-1,5-diisocyanate, mono Or dichlorophenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyl Diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane-4,4'-diisocyanate, m-phenylene-diisocyanate, p-phenylene-diisocyanate, triphenylmethane Triisocyanate, etc.

In addition, examples of the aliphatic polyisocyanate compound include 1,6-hexamethylene-diisocyanate, propyl diisocyanate, and butyl diisocyanate. As the polyisocyanate compound, one type of polyisocyanate compound exemplified above may be used, or two or more types may be used in combination.

Polyols can be exemplified by polyethylene glycol and polypropylene glycol; polyether polyols such as ethylene oxide and/or propylene oxide adducts of bisphenol A; belong to polyols and succinic acid, adipic acid, o-benzene Polyester polyols such as condensates of polyacids such as dicarboxylic acid; polyols with carboxyl or sulfonic acid groups such as 2,2-dimethylolpropionic acid and 1,4-butanediol-2-sulfonic acid; Polyol compounds etc. exemplified as the constituents of the ester resin.

Polyether polyol resins, although not particularly limited, may include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol, polyethylene glycol/polypropylene glycol block copolymer, poly Random copolymers of ethylene glycol/polypropylene glycol, various polyether adducts of bisphenol A, and various polyether adducts of hardened castor oil.

Polycarbonate polyol resins, although not particularly limited, may include polyethylene glycol diol, polypropylene glycol diol, polybutylene carbonate diol, polypentyl carbonate diol, poly Ethylene carbonate, these copolymers, etc.

The polyacrylic polyol resin is not particularly limited as long as it is synthesized from known acrylic monomers and polymerization initiators However, those having hydroxyl groups in the side chain of the polyacrylic resin or those having hydroxyl groups introduced at both ends can be mentioned.

The compound (B2) having an amine group, although not particularly limited, may include polyamide compounds, polyoxyalkylene amines, ethylenediamine, diethylenediamine, trimethylenetetramine, tetramethylenepentamine, Propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, isophoronediamine, m-xylenediamine, norbornanediamine, etc.

The compound (B3) having a carboxyl group may be the same as the above-mentioned polycarboxylic acid.

The compound (B4) having a thiol group is not particularly limited, but a polysulfide polymer and the like can be mentioned.

Examples of the compound (B5) having a phosphate group include organic phosphates. Specific examples are not particularly limited, but they include lauryl phosphate, cetyl phosphate, oleyl phosphate, POE lauryl phosphate, and POE phosphate deca Hexane esters, POE phosphate oil, etc.

〔Sizing agent for reinforcing fiber〕

The sizing agent for reinforcing fibers of the present invention contains at least one selected from the following components (I) and (II).

Component (I): a compound formed by reacting a titanium compound (A) and a compound (B) having an active hydrogen group

Ingredient (II): Titanium compound (A) and compound with active hydrogen group (B)

The component (I) reacts with the titanium compound (A) and the compound (B) having an active hydrogen group to increase the molecular weight, so that the viscosity of the sizing agent can be increased and the heat resistance can be improved. The component (II) is based on the titanium compound (A) and has activity The interaction of the hydrogen-based compound (B) increases the viscosity of the sizing agent and improves the heat resistance.

The components (I) and (II) are obtained by mixing the titanium compound (A) and the compound (B) having an active hydrogen group, and the ratio of the titanium compound (A) and the compound (B) having an active hydrogen group (A /B) Although there is no particular limitation, from the viewpoint of exerting the effect of the present application, it is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, and 0.2 to 3% by weight. Better.

The weight ratio of titanium atoms in the non-volatile components of the sizing agent for reinforcing fibers, although not particularly limited, is preferably 0.00004 to 3% by weight, and more preferably 0.0004 to 2.7% by weight, and 0.004 to 2.4% by weight % Is even better, and 0.02 to 2.1% by weight is particularly preferred. If it is less than 0.00004% by weight, the effect of this application may not be achieved. On the other hand, if it exceeds 3% by weight, the effect of this application may not be exerted.

The weight ratio of titanium atoms in the nonvolatile components of the sizing agent for reinforcing fibers refers to the value measured by the ICP method.

The weight ratio of the above-mentioned compound (A) in the non-volatile components of component (II) is preferably 0.001 to 10% by weight, more preferably 0.01 to 9% by weight, and even more preferably 0.1 to 8% by weight. 0.5 to 7% by weight is particularly preferred. When it is less than 0.001% by weight, the effect of this application may not be exerted. When it exceeds 10% by weight, the viscosity-increasing effect caused by the cross-linking reaction may be too high to mix.

The weight ratio of the above-mentioned compound (B) among the non-volatile components of component (II) is preferably 20 to 99.999% by weight, more preferably 40 to 99.99% by weight, and even more preferably 50 to 99.9% by weight. And 60 To 99.5% by weight is particularly preferred. When it is less than 20% by weight, the effect of this application may not be exerted, and when it exceeds 99.999% by weight, the effect of this application may not be exerted.

In the component (II), the weight ratio (A/B) of the compound (A) to the compound (B) is preferably 0.001 to 10% by weight, more preferably 0.01 to 9% by weight, and 0.1 to 8% by weight is even better, and 0.5 to 7% by weight is particularly preferable. When it is less than 0.001% by weight, the application may not be able to be exerted. When it exceeds 10% by weight, the viscosity-increasing effect caused by the cross-linking reaction may be too high to mix.

Although the sizing agent for reinforcing fibers of the present invention can be used in a state dispersed or dissolved in an organic solvent such as acetone, methyl ethyl ketone, etc., it is safe for the human body at the time of treatment, prevention of fire and other disasters, and From the standpoint of prevention of natural environmental pollution, etc., it is in a state of further containing water and dispersing the neutralized substance or the polymer component (A) in water (aqueous dispersion) or dissolved in water (aqueous solution) ) Is better.

The method for producing the sizing agent for reinforcing fibers of the present invention as an aqueous dispersion or an aqueous solution is not particularly limited, and a known method can be adopted. Examples include: a method of putting the components constituting the sizing agent for reinforcing fibers into warm water under stirring to emulsify, disperse or dissolve it; or mixing the components constituting the sizing agent for reinforcing fibers and mixing the resulting After the mixture is heated to above the softening point, a method such as homogenizer, homomixer, ball mill, etc. is used to apply mechanical shearing force, while water is gradually injected to invert the phase emulsification method.

In addition, in the above aqueous dispersion or aqueous solution, in order to achieve For the purpose of improving the operability at the time of manufacture or the stability of the water dispersion over time, it may contain solvents other than water, such as organic solvents, to the extent that the advantages of the above-mentioned water dispersion or aqueous solution are not impaired.

Organic solvents can be exemplified by alcohols such as methanol, ethanol, isopropanol; glycols or glycol ethers such as ethylene glycol, propylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether; acetone, methyl alcohol Ketones such as ethyl ethyl ketone. Although its content varies depending on the type of solvent, in order not to impair the advantages of the water dispersion or aqueous solution, it is preferably 100% by weight or less relative to the non-volatile component of the sizing agent for reinforcing fibers, and 50 It is better to be less than% by weight.

When the sizing agent for reinforcing fibers of the present invention is an aqueous dispersion or an aqueous solution, the concentration of non-volatile components is not particularly limited, although it is considered as an aqueous dispersion according to the composition of the non-volatile components of the sizing agent for reinforcing fibers The stability of the product or the viscosity when it is easy to operate as a product are suitable for selection, but when considering the transportation cost of the product, it is preferably 10% by weight or more, and preferably 20 to 60% by weight, and 30 to 50% by weight is particularly preferred.

Components other than the above-mentioned components constituting the sizing agent for reinforcing fibers of the present invention include, for example, various surfactants, various antioxidants, flame retardants, antibacterial agents, crystal nucleating agents, defoaming agents, and the like. These ingredients can be used alone or in combination of two or more.

In particular, when the sizing agent for reinforcing fibers of the present invention has a resin component that is water-insoluble or poorly soluble, an aqueous emulsification can be effectively carried out by using a surfactant as an emulsifier. Therefore, the sizing agent for reinforcing fibers can be made into an aqueous dispersion. When using a surfactant, its weight ratio in the entire non-volatile component is 5 to 40% by weight It is better, and 10 to 30% by weight is better, and 15 to 25% by weight is even better.

The surfactant is not particularly limited, and a known one can be suitably selected and used from among nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. The surfactant can be used alone or in combination of two or more.

Examples of nonionic surfactants include, for example, alkylene oxide addition nonionic surfactants (for higher alcohols, higher fatty acids, alkylphenols, styrenated phenols, cresols, sorbitan, and sorbitan) Alcohol esters, castor oil, hardened castor oil, etc. Addition of ethylene oxide, propylene oxide and other alkylene oxides (two or more types can be used in combination); for polyalkylene glycol addition of higher fatty acids, etc.; Ethylene oxide/propylene oxide copolymer, etc.

Examples of the anionic surfactants include carboxylic acids (salts), sulfate ester salts, sulfonate salts of higher alcohols/higher alcohol ethers, and phosphate ester salts of higher alcohols/higher alcohol ethers.

Cationic surfactants include, for example, quaternary ammonium salt type cationic surfactants (lauryl trimethyl ammonium chloride, oleyl methyl ethyl (ethyl sulfate) ammonium, etc.), amine salt type cationic surfactants Surfactant (polyoxyethyl laurylamine lactate, etc.), etc.

Amphoteric surfactants include, for example, amino acid-type amphoteric surfactants (sodium lauryl aminopropionate, etc.), betaine-type amphoteric surfactants (stearyl dimethyl betaine, lauryl dihydroxy ethyl Base betaine, etc.) etc.

The sizing agent for reinforcing fibers of the present invention can be used in combination with resins without hydroxyl groups in a range that does not impair performance. Specifically, we can cite: Polyethylene resin, polypropylene resin, polybutadiene resin, polyamide resin, polyimide resin, acrylic resin, styrene resin, nylon resin, polyester resin, etc.

〔Smoothing agent (C)〕

The sizing agent for reinforcing fibers of the present invention preferably contains a smoothing agent (C), which can improve scratch resistance.

The smoothing agent (C) is not particularly limited as long as it shows smoothness, but examples thereof include ester compounds or thioester-containing compounds having a structure in which an aliphatic alcohol and a fatty acid ester are combined.

Although the ester compound is not particularly limited, for example, 2-decyl tetradecanoyl ercinate, 2-decyl tetradecanoyl ercinate, 2-decyl tetradecanoyl oleate, and stearic acid (2- Octyl dodecyl) ester, isooctyl palmitate, isooctyl stearate, butyl palmitate, butyl stearate, butyl oleate, isooctyl oleate, lauryl oleate, hard Isotridecyl fatty acid, cetyl stearate, isostearyl oleate, oleic octanoate, oleyl laurate, oleic palmitate, oleyl stearate, oleic oleate, etc. Among these ester compounds, 2-decyltetradecyl oleate, (2-octyldodecyl) stearate, isooctyl palmitate, isooctyl stearate are preferred , Lauryl oleate, isotridecyl stearate, cetyl stearate, isooctadecyl oleate, oleic oleate, trimethylolpropane trioctanoate, trimethylol Propane trihexanoate, trimethylolpropane trilaurate, trimethylolpropane trioleate, trimethylolpropane (laurate, cinnamate, palmitate), trimethylolpropane (Laurate, cinnamate, oleate), trimethylolpropane (tripalmitan Nuclear fatty acid ester), trimethylolpropane (tri-coconut fatty acid ester), coconut oil, rapeseed oil, palm oil, glycerol trilaurate, glycerol trioleate, glycerol triisostearate, Sorbitan trioleate, sorbitan (laurate, cinnamate, oleate), isopentaerythritol tetraoctanoate, isopentaerythritol tetracaproate, isopentaerythritol tetralaurate Ester, erythritol laurate, isopentaerythritol (tetra-palm core fatty acid ester), isopentaerythritol (tetra-coconut fatty acid ester), 1,6-hexanediol dioleate, hexane di Dioctyl acid, dilauryl adipate, dioleic adipate, di(isohexadecyl) adipate, dioctyl sebacate, dilauryl sebacate, disebacate Oil ester, di(isohexadecyl) sebacate, di(n-dodecyl) thiodiacetate, di(n-tridecyl) thiodiacetate, thiodiacetic acid di( N-tetradecyl) ester, thiodiacetic acid di(n-pentadecyl) ester, thiodiacetic acid di(n-hexadecyl) ester, thiodiacetic acid di(oleyl) ester, etc. Acetate dilinear ester; thiodiacetic acid di(isododecyl) ester, thiodiacetic acid di(isotridecyl) ester, thiodiacetic acid di(isotetradecyl) ester, thiodiacetic acid Sulfur such as di(isopentadecyl) ester, thiodiacetic acid di(isohexadecyl) ester, thiodiacetic acid di(2-hexyldecyl) ester, thiodiacetic acid di(isostearyl) ester, etc. Dibranched-chain diacetate; di(n-dodecyl) thiodipropionate, di(n-tridecyl) thiodipropionate, di(n-tetradecane) thiodipropionate ), thiodipropionate di(n-pentadecyl) ester, thiodipropionate di(n-hexadecyl) ester, thiodipropionate di(oleyl) ester, etc. Acid diacid di-chain type ester; thiodipropionate di(isododecyl) ester, thiodipropionate di(isotridecyl) ester, thiodipropionate bis(isotetradecane) ), bis(isopentadecyl)thiodipropionate, bis(isohexadecyl)thiodipropionate, bis(2-hexylethyl)thiodipropionate, sulfur Dipropionate (isostearyl) Thiodipropionic acid dibranched chain ester; thiodibutyric acid di(n-dodecyl) ester, thiodibutyric acid di(n-tridecyl) ester, thiodibutyric acid Di(n-tetradecyl) ester, thiodibutyric acid di(n-pentadecyl) ester, thiodibutyric acid di(n-hexadecyl) ester, thiodibutyric acid di(oleyl) Di-linear thiodibutyrate esters such as esters; thiodibutyric acid (isododecyl) ester, thiodibutyric acid (isotridecyl) ester, thiodibutyric acid (isotetradecyl) Alkyl) ester, thiodibutyric acid (isopentadecyl) ester, thiodibutyric acid (isohexadecyl) ester, thiodibutyric acid di(2-hexyldecyl) ester, thio Dibranched chain esters of thiodibutyric acid such as di(isostearyl) dibutyrate; di(n-dodecyl) thiodivalerate, di(n-tridecyl) thiodivalerate ) Ester, Di(n-tetradecyl) thiodivalerate, Di(n-pentadecyl) thiodivalerate, Di(n-hexadecyl) thiodivalerate, Thio Di(oleyl) divalerate and other straight-chain thiodivalerate diacids; di(isododecyl) thiodivalerate, di(isotridecyl) thiodivalerate ) Ester, thiodivalerate di(isotetradecyl) ester, thiodivalerate di(isopentadecyl) ester, thiodivalerate di(isohexadecyl) ester, thio Di(2-hexyldecyl) divalerate, di(isostearyl) thiodivalerate and other dibranched chain esters of thiodivalerate; hexylene glycol di(octadecyl)thio Propionate, trimethylolpropane tris (dodecyl) thiopropionate, glycerol tris (dodecyl) thiopropionate, isopentaerythritol tetra (octadecyl) thiopropionate Esters of thioether monocarboxylic acids such as acid esters.

The ester compound can be obtained by synthesizing a commercially available fatty acid, aliphatic alcohol, or sulfur-containing compound by a known method.

[Reinforced fiber strands]

The reinforcing fiber strand of the present invention is a sizing agent for the above reinforcing fiber Attached to raw material synthetic fiber strands, it is a reinforcing fiber used to reinforce thermoplastic matrix resin.

The method for manufacturing a reinforcing fiber strand of the present invention includes the steps of attaching the sizing agent for reinforcing fiber to a raw material synthetic fiber strand, and drying the resulting adherent to a sizing treatment step.

The method of attaching the sizing agent for reinforcing fibers to the raw material synthetic fiber strands to obtain attachments is not particularly limited, but as long as the kiss roller method, roller immersion method, spray method and other known methods are used The method of attaching the sizing agent for reinforcing fibers to the raw material synthetic fiber strands may be sufficient. Among these methods, the roller immersion method is preferred, which allows the sizing agent for reinforcing fibers to uniformly adhere to the raw material synthetic fiber strands.

There is no particular limitation on the drying method of the obtained attachments. For example, a heating roller, hot air, a hot plate, etc. can be used for heating and drying.

In addition, when the sizing agent for reinforcing fibers of the present invention is to be attached to raw material synthetic fiber strands, all components of the sizing agent for reinforcing fibers may be mixed and adhered, or the components may be divided into two separately Attachment is carried out above the stage. In addition, thermosetting resins such as epoxy resins, vinyl ester resins, phenol resins, and/or polyolefin-based resins, nylon resins other than the polymer components of the present invention may be used as long as the effects of the present invention are not impaired. Thermoplasticity such as polycarbonate resin, polyester resin, polyacetal resin, ABS resin, phenoxy resin, polymethyl methacrylate resin, polyphenylene sulfide resin, polyether amide imide resin, polyether ketone resin, etc. The resin is attached to the raw material synthetic fiber strands.

The reinforcing fiber strand of the present invention can be used as a The plastic resin is used as the reinforcing fiber of the matrix resin composite material, and the form of use may be a state of continuous fiber or a state of being cut to a predetermined length.

The non-volatile component of the sizing agent for reinforcing fibers can be appropriately selected for the adhesion amount of the raw material synthetic fiber strands, although it is sufficient as long as it is necessary to make the synthetic fiber strands have the desired function, but the adhesion amount is relative It is preferably 0.1 to 20% by weight based on raw material synthetic fiber strands. In the continuous fiber state synthetic fiber strands, the adhesion amount is preferably 0.1 to 10% by weight relative to the raw material synthetic fiber strands, and more preferably 0.5 to 5% by weight. In addition, in the string in a state of being cut to a predetermined length, it is preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight.

If the adhesion amount of the sizing agent for reinforcing fibers is small, the effects of the present invention on resin impregnation and adhesiveness are not easily obtained, and the bundling properties of the synthetic fiber strands are insufficient, which may make handling properties poor. In addition, if the amount of the sizing agent for reinforcing fibers is too large, the synthetic fiber strands may become too hard, but the handling may become poor, or the resin impregnability may become poor during composite molding, so Is not good.

Synthetic fibers of (raw materials) synthetic fiber strands to which the sizing agent for reinforcing fibers of the present invention can be applied include various inorganic fibers such as carbon fiber, glass fiber, ceramic fiber; aromatic aramid fiber, poly Ethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polyacetal fiber, PBO fiber, polyphenylene sulfide fiber , Polyketone fiber and other organic fibers. From the viewpoint of the physical properties of the fiber-reinforced composite material obtained, it is selected From carbon fiber, aromatic polyamide fiber, polyethylene fiber, polyethylene terephthalate fiber, polybutylene terephthalate fiber, polyethylene naphthalate fiber, polyarylate fiber, polycondensation At least one of aldehyde fiber, PBO fiber, polyphenylene sulfide fiber and polyketone fiber is preferred.

〔Fiber-reinforced composite materials〕

The fiber-reinforced composite material of the present invention contains a matrix resin and the aforementioned reinforcing fiber strand. Here, the matrix resin refers to a base material of reinforcing fibers that holds the fiber-reinforced composite material. Since the reinforcing fiber strands are processed by the sizing agent for reinforcing fibers of the present invention, the affinity between the reinforcing fiber strands and the matrix resin becomes good, making it a fiber-reinforced composite material excellent in adhesion.

Here, the matrix resin refers to a matrix resin containing a thermosetting resin and/or a thermoplastic resin, and is not particularly limited. Known matrix resins can be appropriately selected and used, and they may contain one kind or two or more kinds.

The thermosetting matrix resin is not particularly limited, and examples thereof include epoxy resin, unsaturated polyester resin, vinyl ester resin, benzoxazine resin, phenol resin, urea resin, melamine resin, and thermosetting resin. Polyimide resin, etc.

The thermoplastic matrix resin is not particularly limited, and examples include polyolefin resins, nylon resins, polycarbonate resins, polyester resins, polyacetal resins, ABS resins, phenoxy resins, and polymethyl methacrylate Resin, polyphenylene sulfide resin, polyether amide imide resin, polyether ketone resin, etc. For these thermoplastic matrix resins, in order to further enhance the connection with the synthetic fiber strands For sexual and other purposes, it can also be partially or completely modified.

The manufacturing method of the fiber-reinforced composite material is not particularly limited, and the following methods can be used: composite injection molding by chopped fiber, long fiber particles, etc.; by UD sheet (UD sheet), fabric sheet Die-casting performed by Etc.; other known methods such as filament winding.

The content of the synthetic fiber strands in the fiber-reinforced composite material is not particularly limited, although it may be appropriately selected according to the type and shape of fibers, the type of thermoplastic matrix, etc., relative to the obtained fiber-reinforced composite material , It is preferably 5 to 70% by weight, and more preferably 20 to 60% by weight.

[Example]

Hereinafter, although the present invention is specifically described based on the embodiments, the present invention is not limited to the scope of the embodiments described herein. In addition, the percentage (%) shown in the following examples means "weight%" unless otherwise limited. The measurement of each characteristic value is performed according to the method shown below.

<viscosity>

The viscosity is measured to investigate the viscosity-increasing effect between compound (A) and compound (B). It was measured at each temperature of 50°C, 75°C, and 100°C using a cone-plate viscometer (manufactured by RESEARCH EQUIPMENT, I.C.I CON & PLATE VISCOMETER). According to the following indexes, ◎ and ○ are considered as passing.

Compared with the sizing agent without added compound (A),

◎: 10 times or more

○: When it exceeds 1.2 times and does not reach 10 times

<cluster>

Each sizing agent (diluted with water to 3%, adhesion rate 1%) was sizing on carbon fiber, and when it was cut into 10 pieces of 5mm length using a cutter, visually evaluate whether it would disintegrate. Judging from the following evaluation criteria, ○ was determined as a pass.

○: Disintegration of 2 or less

△: 7 to 3 disintegration

×: Disintegration of 8 or more

<heat resistance>

The sizing agent is heat-treated at 105°C to remove the solvent, etc., and the non-volatile components of the sizing agent are obtained when the weight is constant. The nonvolatile content obtained by sampling in an aluminum pan of known weight is about 4 mg, and the weight (W1) is determined. The non-volatile components that had been put in the aluminum pan were placed in a differential thermal balance TG-8120 (manufactured by Rika Co., Ltd.), and the temperature was raised from 25°C to 500°C in the air at a heating rate of 20°C/min, and the temperature was measured at 300°C. Weight at the time point (W2). Then calculate the weight reduction rate according to the following formula. According to the following indexes, ◎ and ○ were considered as pass.

Weight reduction rate (%)=((W1-W2)/W1)×100

index

The weight reduction rate is compared to the weight reduction rate of the sizing agent without added compound (A),

◎: Less than 1/10

○: Less than 8/10 to 1/10

In addition, the non-volatile content in this specification means heating at 105°C. Treatment to remove the solvent etc. and reach a constant amount.

(Examples 1 to 11, Comparative Examples 1 to 4)

The following components (A-1 to D-3) were used and mixed at the ratio (parts by weight) described in Tables 1 to 6, to obtain the reinforcing fibers for Examples 1 to 11 and Comparative Examples 1 to 4, respectively. Slurry. The results are shown in Tables 1 to 4.

A-1 Titanium tetraethoxylate

A-2 Titanium tetraisopropoxide

A-3 Titanium tetrabutoxide

A-4 tetraisopropylglycoxy titanium

A-5 Tetrabutoxy titanium tetramer

B-1 Liquid epoxy resin (JER-828 molecular weight: 380, manufactured by Mitsubishi Chemical Corporation, molecules with hydroxyl groups are contained in 10 molecules at a ratio of 1 molecule)

B-2 Solid epoxy resin (JER-1001 molecular weight: 900, manufactured by Mitsubishi Chemical Corporation)

B-3 Polyester polymerized by 2mol of PEG/maleic anhydride at both ends of Bis-A (acid value: 4.6KOHmg/g)

B-4 Reactor of PTMG (polytetramethylene glycol, molecular weight 2000) and HDI (hexamethylene diisocyanate) in a ratio of 2:1 (molar ratio)

B-5 Use DURANOL T-5652 manufactured by Asahi Kasei Chemical Company

C-1 Oleic acid oleate

D-1 Hardened castor oil ether (polyether polyol) added with 150 mol of ethylene oxide

D-2 Monoisopropyl glycol ether

D-3: Water

As shown in Tables 1 to 4, it can be seen that Examples 1 to 11 The fiber treatment agent contains the above-mentioned component (I) and the above-mentioned component (II) by blending the titanium compound (A) and the compound (B) having an active hydrogen group. The viscosity becomes higher, which solves the problem of this application.

On the other hand, the treatment agents for fibers of Comparative Examples 1 to 4 were prepared with the compound (B) having an active hydrogen group, but the titanium compound (A) was not prepared, so it was not possible to solve any of the problems of the present application.

[Possibility of industrial application]

The fiber-reinforced composite material reinforced with matrix resin reinforced fiber can be used for automotive applications, aerospace applications, sports and leisure applications, general industrial applications, etc. Reinforced fibers include various inorganic fibers such as carbon fiber, glass fiber, ceramic fiber, and various organic fibers such as aromatic polyamide fiber, polyamide fiber, and polyethylene fiber.

Claims (10)

A sizing agent for reinforcing fibers, which contains at least one selected from the following components (I) and the following components (II), component (I): a titanium compound (A) and a compound having an active hydrogen group ( B) A compound resulting from the reaction; component (II): a titanium compound (A) and a compound (B) having an active hydrogen group, wherein the compound (A) is represented by the following general formula (1);

In the formula, R ¹ to R ⁴ are alkyl groups having 1 to 8 carbon atoms, which may be the same or different; n is an integer of 1 or more. The sizing agent for reinforcing fibers as described in item 1 of the patent application range, wherein the compound (B) contains a compound (B1) having a hydroxyl group. The sizing agent for reinforcing fibers as described in item 2 of the patent application range, wherein the compound (B1) contains at least one selected from epoxy resins, polyester resins, urethane resins and polyether polyol resins . The sizing agent for reinforcing fibers according to any one of items 1 to 3 of the patent application range, wherein the compound (II) satisfies the following condition 1, condition 1: the compound (A) is relative to the compound (B ) Has a weight ratio (A/B) of 0.1 to 8% by weight. The sizing agent for reinforcing fibers as described in any one of items 1 to 3 of the patent application range, wherein the weight ratio of titanium atoms in the non-volatile components of the sizing agent for reinforcing fibers is 0.004 to 2.4% by weight. The sizing agent for reinforcing fibers as described in any one of claims 1 to 3, wherein the weight ratio of titanium atoms in the non-volatile components of the sizing agent for reinforcing fibers is 0.02 to 2.1% by weight. The sizing agent for reinforcing fibers according to any one of items 1 to 3 in the patent application range, wherein the alkyl group is an alkyl group having 2 to 8 carbon atoms, and the n is 1. The sizing agent for reinforcing fibers as described in any one of items 1 to 3 of the patent application range further contains a smoothing agent (C). A reinforcing fiber strand obtained by attaching a sizing agent for reinforcing fibers according to any one of claims 1 to 8 to a raw material reinforcing fiber strand. A fiber-reinforced composite material comprising: a matrix resin and the reinforcing fiber strands described in item 9 of the patent application.