Fiber sizing agents, fiber bundles, composite intermediates, and fiber-reinforced composite materials

Abstract

To provide a fiber sizing agent having an excellent bundling property.SOLUTION: There is provided a fiber sizing agent comprising a polyurethane resin (U). The polyurethane resin (U) is a polyurethane resin formed by reacting an active hydrogen-containing compound component (A) and an isocyanate component (B). The active hydrogen containing compound component (A) comprises a hydroxyl group-containing polyolefin (A1). The hydroxyl group-containing polyolefin (A1) comprises as constituent monomers ethylene and a C3-8 α-olefin(s). A weight ratio [ethylene / α-olefin(s)] of ethylene and C3-8 α-olefin(s), the constituent monomers of the hydroxyl group-containing polyolefin (A1), is 3 / 97-65 / 35.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fiber sizing agent, a fiber bundle, a composite intermediate, and a fiber-reinforced composite material. [Background technology]

[0002] Known conventional fiber sizing agents include, for example, those described in Patent Document 1. Patent Document 1 discloses a fiber sizing agent that contains an acid-modified polyolefin aqueous emulsion. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2015-131889 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, even the technology of Patent Document 1 above is not fully satisfactory in terms of sizing ability, and improvements have been required. An object of the present invention is to provide a fiber sizing agent having excellent sizing ability. [Means for solving the problem]

[0005] As a result of investigations aimed at achieving the above object, the present inventors arrived at the present invention. That is, the present invention relates to a fiber sizing agent containing a polyurethane resin (U), the polyurethane resin (U) being a polyurethane resin obtained by reacting an active hydrogen-containing compound component (A) with an isocyanate component (B), the active hydrogen-containing compound component (A) containing a hydroxyl group-containing polyolefin (A1) containing, as constituent monomers, ethylene and an α-olefin having 3 to 8 carbon atoms, the weight ratio of ethylene to the α-olefin having 3 to 8 carbon atoms, [ethylene / α-olefin], being 3 / 97 to 65 / 35; a fiber bundle obtained by treating at least one type of fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers and slug fibers with the fiber sizing agent; a composite intermediate containing the fiber bundle and a matrix resin; and a fiber-reinforced composite material obtained by molding the composite intermediate. Effect of the Invention

[0006] The fiber sizing agent of the present invention has the following effects. (1) The fiber sizing agent of the present invention has excellent fiber bundling properties. (2) Fiber bundles obtained using the fiber sizing agent of the present invention have little fuzz. (3) It gives excellent mechanical strength to fiber-reinforced composite materials. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The fiber sizing agent of the present invention is a fiber sizing agent containing a polyurethane resin (U), the polyurethane resin (U) being a polyurethane resin obtained by reacting an active hydrogen-containing compound component (A) with an isocyanate component (B), the active hydrogen-containing compound component (A) containing a hydroxyl group-containing polyolefin (A1), the hydroxyl group-containing polyolefin (A1) containing, as constituent monomers, ethylene and an α-olefin having 3 to 8 carbon atoms, and a weight ratio [ethylene / α-olefin] of the constituent monomers of the hydroxyl group-containing polyolefin (A1) to the α-olefin having 3 to 8 carbon atoms is 3 / 97 to 65 / 35. In the present invention, the fiber sizing agent is used to improve the handleability of the fibers, improve the quality of the fibers, and strengthen the bond between the fibers and the matrix resin by applying it to the surface of the fibers.

[0008] <Polyurethane resin (U)> The polyurethane resin (U) in the present invention is a polyurethane resin obtained by reacting an active hydrogen-containing compound component (A) with an isocyanate component (B). The polyurethane resin (U) may have a urea group, and in that case, the polyurethane resin (U) is a polyurethane urea resin.

[0009] <Active hydrogen-containing compound component (A)> The active hydrogen-containing compound component (A) contains a hydroxyl group-containing polyolefin (A1). In the present invention, active hydrogen refers to a hydrogen atom that reacts with an isocyanate group of the isocyanate component (B), and examples of such active hydrogen include hydrogen atoms in hydroxyl groups, mercapto groups, amino groups, etc., and among these, hydrogen atoms in hydroxyl groups and amino groups are preferred.

[0010] <Hydroxyl group-containing polyolefin (A1)> The hydroxyl group-containing polyolefin (A1) in the present invention can be obtained, for example, by reacting an acid-modified polyolefin (X) in which a polyolefin (A01) having a carbon-carbon double bond described below is modified with an unsaturated (poly)carboxylic acid (anhydride) (E) with an amino alcohol (G), or by reacting the acid-modified polyolefin (X) with an alkylene oxide (hereinafter abbreviated as AO).

[0011] The constituent monomers constituting the polyolefin (A01) having a carbon-carbon double bond include ethylene and an α-olefin having a carbon number of 3 to 8. Hereinafter, the "polyolefin (A01) having a carbon-carbon double bond" may be referred to as "polyolefin (A01)". The α-olefin having 3 to 8 carbon atoms may be a linear α-olefin or a branched α-olefin. Examples of the α-olefin having 3 to 8 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. The α-olefins may be used alone or in combination of two or more kinds, but it is preferable to use one kind. Of the above α-olefins, from the viewpoints of mechanical strength and industrial applicability, preferred are linear α-olefins, more preferred are linear α-olefins having 3 to 6 carbon atoms, and particularly preferred is propylene.

[0012] The weight ratio of ethylene, which is a constituent monomer of the polyolefin (A01) having a carbon-carbon double bond, to an α-olefin having 3 to 8 carbon atoms [ethylene / α-olefin] is 5 / 95 to 65 / 35, preferably 10 / 90 to 60 / 40, and more preferably 15 / 85 to 40 / 60. The weight ratio of ethylene in the polyolefin having a carbon-carbon double bond (A01) to an α-olefin having 3 to 8 carbon atoms is directly reflected in the weight ratio of ethylene in the hydroxyl group-containing polyolefin (A1) to an α-olefin having 3 to 8 carbon atoms. If the weight ratio [ethylene / α-olefin] is less than 3 / 97, the bundling ability is poor, and if it exceeds 65 / 35, the mechanical strength is poor. The weight ratio [ethylene / α-olefin] is, for example, 1 It can be calculated by H-NMR. The weight ratio of ethylene to α-olefin having 3 to 8 carbon atoms in the polyolefin (A01) having a carbon-carbon double bond can be adjusted by the weight ratio of ethylene to α-olefin having 3 to 8 carbon atoms in the high molecular weight polyolefin (A00) which is the raw material of the polyolefin (A01). The high molecular weight polyolefin (A00) will be described later.

[0013] The polyolefin (A01) having a carbon-carbon double bond may contain, as a constituent monomer, another monomer other than ethylene and an α-olefin having 3 to 8 carbon atoms. In this case, the weight ratio of the other monomer based on the weight of all monomers constituting the polyolefin (A01) is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less. Examples of the other monomers include α-olefins having a carbon number [sometimes abbreviated as C] of 9 to 30 (e.g., 1-decene, 1-dodecene, etc.), and unsaturated monomers having a carbon number of 4 to 30 other than α-olefins (e.g., olefins such as 2-butene and isobutene, and vinyl monomers such as styrene, acrylonitrile, acrylamide, and vinyl acetate).

[0014] The number average molecular weight (Mn) of the polyolefin (A01) having a carbon-carbon double bond is preferably 800 to 5,800, more preferably 900 to 4,800, and particularly preferably 1,000 to 3,800, from the viewpoints of mechanical strength and storage stability of the aqueous polyurethane dispersion (Q) described below.

[0015] In the present invention, the conditions for measuring Mn and weight average molecular weight (Mw) of the hydroxyl group-containing polyolefin (A1), polyolefin (A01), and high molecular weight polyolefin (A00) described below by GPC (gel permeation chromatography) are as follows. Apparatus: High temperature gel permeation chromatograph ["Alliance GPC V2000", Waters, Inc.] Detector: Refractive index detector Solvent: orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3mg / ml Column stationary phase: PLgel 10μm, MIXED-B 2 columns in series [Manufactured by Polymer Laboratories, Inc.] Column temperature: 135℃

[0016] The number of double bonds per 1,000 carbon atoms in the polyolefin (A01) having a carbon-carbon double bond [the number of carbon-carbon double bonds at the molecular terminal and / or in the molecular chain of the polyolefin (A01)] is preferably 1 to 30, more preferably 1.5 to 20, and particularly preferably 2 to 15, from the viewpoints of reactivity with the unsaturated (poly)carboxylic acid (anhydride) (E) described below and productivity. Here, the number of double bonds is 1 It can be determined from a spectrum by H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peaks in the spectrum are assigned, and the relative value between the number of double bonds in (A01) and the number of carbon atoms in polyolefin (A01) is determined from the integral value derived from the double bonds at 4.5 to 6 ppm of polyolefin (A01) and the integral value derived from (A01), and the number of double bonds in the molecular terminal and / or molecular chain per 1,000 carbons of polyolefin (A01) is calculated. The number of double bonds in the examples described below was calculated according to this method.

[0017] The isotacticity of the α-olefin portion of the polyolefin (A01) having a carbon-carbon double bond is preferably 1 to 50%, more preferably 5 to 45%, from the viewpoints of fluff and bundling property, as well as the storage stability of the aqueous polyurethane resin dispersion (Q) described below. The isotacticity of the α-olefin unit sequence of polyolefin (A01) tends to be directly reflected in the isotacticity of the α-olefin unit sequence of the acid-modified polyolefin (X) and the hydroxyl-modified polyolefin (A1) described below. In addition, the isotacticity of the α-olefin unit sequence of polyolefin (A01) tends to be reflected by the isotacticity of the α-olefin unit sequence of the high molecular weight polyolefin (A00) that is the raw material of the polyolefin (A01), and therefore can be adjusted by the high molecular weight polyolefin (A00).

[0018] The isotacticity can be, for example, 13It can be calculated using C-NMR (nuclear magnetic resonance spectroscopy). In general, it is known that the side chain methyl group is affected by the configuration (meso or racemo) with the methyl groups on both sides (triad), on both sides of the triad (pentad), and on both sides of the pentad (heptad), and peaks are observed at different chemical shifts, and the stereoregularity is generally evaluated for the pentad. The isotacticity in the present invention can also be calculated based on the evaluation of the pentad. For example, if the α-olefin is propylene, 13 Regarding the carbon peaks derived from the side chain methyl groups in propylene obtained by C-NMR, when each pentad peak (H) and a peak derived from the methyl groups in isotactic propylene in which the pentad is formed only of mesostructure (Ha) are taken as the peaks, isotacticity is calculated by the following formula. Isotacticity (%) = [(Ha) / Σ(H)] × 100 (1) In formula (1), Ha is the peak height of the isotactic signal (pentads are formed only in the mesostructure), and H is the height of each peak of the pentad. The isotacticity of the α-olefin portion of the polyolefin (A01) having a carbon-carbon double bond and the acid-modified polyolefin (X) can also be measured by the same method as above.

[0019] The polyolefin (A01) having a carbon-carbon double bond can be produced, for example, by thermally degrading the high molecular weight polyolefin (A00). The Mn of the high molecular weight polyolefin (A00) is preferably 60,000 to 400,000, and more preferably 80,000 to 250,000.

[0020] Examples of the thermal degradation method include a method in which the high molecular weight polyolefin (A00) is thermally degraded (1) in the absence of an organic peroxide, for example, at 300 to 450°C for 0.5 to 10 hours, and (2) in the presence of an organic peroxide [for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], for example, at 180 to 300°C for 0.5 to 10 hours. Of these, from the industrial viewpoint and from the viewpoint of modification properties, the method (1) is preferred, which is capable of easily obtaining a polymer having a larger number of double bonds at the molecular terminals and / or in the molecular chain.

[0021] The weight ratio [ethylene / α-olefin] of ethylene, which is a monomer constituting the polyolefin having a carbon-carbon double bond (A01), to an α-olefin tends to be the same as the weight ratio [ethylene / α-olefin] of the high molecular weight polyolefin (A00) used as the raw material. In addition, the higher the thermal degradation temperature of the high molecular weight polyolefin (A00), the greater the number of double bonds per 1,000 carbon atoms in the polyolefin (A01) tends to be, and the longer the thermal degradation time, the greater the number of double bonds per 1,000 carbon atoms in the polyolefin (A01) tends to be. The smaller the Mn of the high molecular weight polyolefin (A00), the smaller the Mn of the polyolefin (A01). The higher the thermal degradation temperature, the smaller the Mn of the polyolefin (A01) tends to be, and the longer the thermal degradation time, the smaller the Mn of the polyolefin (A01) tends to be. Furthermore, there is a tendency that the higher the isotacticity of the high molecular weight polyolefin (A00), the higher the isotacticity of the polyolefin (A01).

[0022] The unsaturated (poly)carboxylic acid (anhydride) (E) includes (poly)carboxylic acid (anhydride) having one polymerizable unsaturated group and having 3 to 30 carbon atoms [hereinafter sometimes abbreviated as C]. In the present invention, the unsaturated (poly)carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride.

[0023] Among the unsaturated (poly)carboxylic acids (anhydrides) (E), examples of the unsaturated monocarboxylic acids include C3-24 aliphatic monocarboxylic acids (e.g., acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and isocrotonic acid), C6-24 alicyclic monocarboxylic acids (e.g., cyclohexene carboxylic acid); examples of the unsaturated poly(2-3 or more) carboxylic acids (anhydrides) include unsaturated dicarboxylic acids (anhydrides) [C4-24 aliphatic dicarboxylic acids (anhydrides) (e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof), and C8-24 alicyclic dicarboxylic acids (anhydrides). unsaturated tricarboxylic acids (anhydrides) [C5 to C24 aliphatic tricarboxylic acids (anhydrides) (for example, aconitic acid, 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid, and anhydrides thereof, etc.), C9 to C24 alicyclic-containing tricarboxylic acids (anhydrides) (for example, 4-cyclohexene-1,2,3-tricarboxylic acid, 4-cycloheptene-1,2,3-tricarboxylic acid, and anhydrides thereof, etc.)]. The unsaturated (poly)carboxylic acid (anhydride) (E) may be used alone or in combination of two or more kinds. Of the above unsaturated (poly)carboxylic acid (anhydrides) (E), from the viewpoints of reactivity with the polyolefin (A01) having a carbon-carbon double bond, and the storage stability and mechanical strength of the aqueous polyurethane dispersion (Q) described below, unsaturated dicarboxylic acid anhydrides are preferred, and maleic anhydride is more preferred.

[0024] <Acid-modified polyolefin (X)> The acid-modified polyolefin (X) in the present invention contains the polyolefin (A01) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (E) as constituent monomers, and is preferably obtained by reacting the polyolefin (A01) having a carbon-carbon double bond with the unsaturated (poly)carboxylic acid (anhydride) (E) in the absence or presence of a radical initiator.

[0025] The weight ratio of the polyolefin (A01) having a carbon-carbon double bond to the unsaturated (poly)carboxylic acid (anhydride) (E) [(A01) / (E)] is preferably 80 / 20 to 99.5 / 0.5, and more preferably 90 / 10 to 99 / 1, from the viewpoint of the balance between the bundling ability and the storage stability of the aqueous polyurethane dispersion (Q) described later.

[0026] The acid-modified polyolefin (X) can be preferably produced by reacting the polyolefin (A01) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (E) with an appropriate organic solvent [C3-18 hydrocarbons (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbons (di-, tri-, or tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)] added as necessary in the presence of a radical initiator (F). The radical initiator (F) may be a known one, for example, an azo initiator (azobisisobutyronitrile, etc.) or a peroxide initiator (dicumyl peroxide, etc.). Of the above radical initiators (F), peroxide initiators are preferred.

[0027] The reaction temperature is preferably 100 to 270°C, more preferably 120 to 250°C, and particularly preferably 130 to 240°C, from the viewpoints of reactivity between the polyolefin (A01) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (E) and productivity.

[0028] The acid value of the acid-modified polyolefin (X) is preferably 1 to 130 mgKOH / g, more preferably 3 to 75 mgKOH / g, and particularly preferably 5 to 50 mgKOH / g, from the viewpoints of the storage stability of the aqueous polyurethane dispersion (Q) described below and the productivity of the acid-modified polyolefin (X). In this specification, the acid value is a value measured according to the following procedures (i) to (iii) in accordance with JIS K0070:1992. (i) Dissolve 1 g of (X) in 100 g of xylene adjusted to 100°C. (ii) At the same temperature, titration is performed with 0.1 mol / L potassium hydroxide ethanol solution [product name "0.1 mol / L ethanolic potassium hydroxide solution", manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator. (iii) Convert the amount of potassium hydroxide required for the titration into mg to calculate the acid value (unit: mgKOH / g). In addition, the above measurement gives the result that one acid anhydride group is equivalent to one carboxyl group. In addition, the acid value can be appropriately adjusted by the number of double bonds in the polyolefin having a carbon-carbon double bond (A01), the weight of the polyolefin having a carbon-carbon double bond (A01), the type of the unsaturated (poly)carboxylic acid (anhydride) (E), and the weight of the unsaturated (poly)carboxylic acid (anhydride) (E).

[0029] The Mn of the acid-modified polyolefin (X) is preferably from 900 to 5,900, more preferably from 900 to 5,000, and particularly preferably from 900 to 4,000, from the viewpoints of mechanical strength and bundling ability.

[0030] The isotacticity of the α-olefin unit chain of the acid-modified polyolefin (X) is preferably 1 to 50%, more preferably 5 to 45%, and particularly preferably 10 to 43%, from the viewpoints of fluff, bundling property, and storage stability of the aqueous polyurethane dispersion (Q) described below. Furthermore, the isotacticity of the α-olefin unit sequence of the acid-modified polyolefin (X) can be appropriately adjusted by the isotacticity of the polyolefin (A01) having a carbon-carbon double bond and the high molecular weight polyolefin (A00), as described above.

[0031] Examples of the hydroxyl-modified polyolefin (A1) in the present invention include a reaction product of an acid-modified polyolefin (X) with an aminoalcohol (G) and a reaction product of an acid-modified polyolefin (X) with AO.

[0032] Examples of the amino alcohol (G) include linear alkanolamines, cycloalkanolamines and alkylalkanolamines having 2 to 12 carbon atoms (e.g., 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, diethanolamine, di-n- or isopropanolamine, 3-aminomethyl-3,5,5-trimethylcyclohexanol, methylethanolamine and ethylethanolamine), and the like. From the viewpoint of mechanical strength, 2-aminoethanol is preferred.

[0033] Examples of AO include AOs having 2 to 12 carbon atoms (ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, α-olefin oxide, etc.), and from the viewpoint of the storage stability of the aqueous polyurethane dispersion (Q) described below, those having 2 to 4 carbon atoms are preferred, and ethylene oxide and propylene oxide are more preferred. One type of AO may be used alone, or two or more types may be used in combination. The amount (number of moles) of AO used is preferably 1 to 10 moles or more, more preferably 1 to 5 moles, and particularly preferably 1 mole, per carboxy group of the acid-modified polyolefin (X) from the viewpoint of mechanical strength.

[0034] The modification of the acid-modified polyolefin (X) with the aminoalcohol (G) can be carried out by a known method, for example, by adding an excess (for example, 1.1 to 2 times the molar amount or more) of the aminoalcohol relative to the carboxyl group (carbonyl group in the case of anhydride) of the acid-modified polyolefin (X) and reacting it, and then removing the unreacted aminoalcohol by a method such as distillation. The reaction can be carried out in the presence or absence of an organic solvent. The reaction temperature is preferably 100 to 220°C, more preferably 120 to 200°C, from the viewpoints of reaction rate and reaction stability. The modification of the acid-modified polyolefin (X) with AO is carried out by a known method. For example, the reaction temperature when carrying out ring-opening addition polymerization of AO is preferably 40 to 200°C, more preferably 70 to 160°C, from the viewpoints of reaction rate and reaction stability. The reaction pressure is preferably -0.1 to 0.5 MPa. The reaction is carried out in the presence of a catalyst as necessary.

[0035] The hydroxyl-modified polyolefin (A1) contains ethylene and an α-olefin having 3 to 8 carbon atoms as constituent monomers. The weight ratio [ethylene / α-olefin] of the ethylene and α-olefin (having 3 to 8 carbon atoms), which are constituent monomers of the hydroxyl-containing polyolefin (A1), is 3 / 97 to 65 / 35. The weight ratio [ethylene / α-olefin] is preferably 5 / 95 or more, more preferably 9 / 91 or more, even more preferably 15 / 85 or more, and is preferably 60 / 40 or less, more preferably 40 / 60 or less, even more preferably 30 / 70 or less. If the weight ratio [ethylene / α-olefin] is less than 3 / 97, the sizing ability is poor, and if it exceeds 65 / 35, the mechanical strength is poor. The weight ratio of ethylene and α-olefin having 3 to 8 carbon atoms, which are constituent monomers of the hydroxyl-modified polyolefin (A1), can be adjusted by adjusting the ratio of ethylene and α-olefin having 3 to 8 carbon atoms used in the high molecular weight polyolefin (A00). The weight ratio of ethylene and α-olefin having 3 to 8 carbon atoms, which are constituent monomers of the hydroxyl-modified polyolefin (A1), can be adjusted by adjusting the ratio of ethylene and α-olefin having 3 to 8 carbon atoms used in the high molecular weight polyolefin (A00). 1 This can be confirmed by H-NMR.

[0036] The isotacticity of the α-olefin portion of the hydroxyl group-containing polyolefin (A1) is preferably from 1 to 50%, more preferably from 5 to 45%. When the isotacticity of the α-olefin portion of the hydroxyl group-containing polyolefin (A1) is 1% or more, the bundling ability and fuzz tend to be good, and when it is 50% or less, the storage stability of the aqueous polyurethane dispersion (Q) described below tends to be good. The isotacticity of the α-olefin portion of the hydroxyl group-containing polyolefin (A1) can be adjusted by adjusting the isotacticity of (A01).

[0037] The Mn of the hydroxyl group-containing polyolefin (A1) is preferably 500 or more, and from the viewpoints of mechanical strength and storage stability of the aqueous polyurethane dispersion (Q) described below, it is preferably 1,000 to 10,000, more preferably 1,100 to 7,500, and particularly preferably 1,400 to 5,500. The Mn of the hydroxyl group-containing polyolefin (A1) can be adjusted by adjusting the Mn of the polyolefin (A01) having a carbon-carbon double bond, the type and amount of the unsaturated (poly)carboxylic acid (anhydride) (E) used, and by controlling the reaction between the polyolefin (A01) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (E).

[0038] The hydroxyl value (mg KOH / g) of the hydroxyl-containing polyolefin (A1) is preferably 12 or more, more preferably 15 or more, even more preferably 20 or more, from the viewpoints of reaction stability and mechanical strength, and is preferably 120 or less, more preferably 110 or less, particularly preferably 50 or less. The hydroxyl value of the hydroxyl-containing polyolefin (A1) can be adjusted by adjusting the number of double bonds in the polyolefin (A01) having a carbon-carbon double bond, the amount of the polyolefin (A01) having a carbon-carbon double bond used, the type and amount of the unsaturated (poly)carboxylic acid (anhydride) (E) used, and the type and amount of the amino alcohol (G) or AO used. The acid value (mgKOH / g) of the hydroxyl-containing polyolefin (A1) is preferably 0 to 50, more preferably 0 to 30, from the viewpoints of the storage stability and reaction stability of the aqueous polyurethane dispersion (Q) described below. The hydroxyl value and acid value of the hydroxyl-containing polyolefin (A1) are values ​​measured in accordance with JIS K0070-1992.

[0039] In the present invention, the number of hydroxyl groups per molecule of the hydroxyl-modified polyolefin (A1) is preferably 1.5 to 2.0, more preferably 1.6 to 2.0, from the viewpoint of mechanical properties. The number of hydroxyl groups per molecule of the hydroxyl-modified polyolefin (A1) can be calculated by the following mathematical formula (1). Number of hydroxyl groups per molecule = Mn A1 ×OHV / 56100 (1) Mn A1 : (A1) Mn OHV: Hydroxyl value of (A1) (mgKOH / g)

[0040] When the polyurethane resin (U) uses multiple types of hydroxyl-modified polyolefins (A1), the weight average number of hydroxyl groups in all of the hydroxyl-modified polyolefins (A1) constituting the polyurethane resin (U) is preferably 1.5 to 2.0, more preferably 1.6 to 2.0, from the viewpoint of mechanical properties.

[0041] The polyurethane resin (U) in the present invention contains, as the active hydrogen-containing compound component (A), a hydroxyl group-containing polyolefin (A1) as an essential constituent monomer, but a polymer polyol (A2) other than the hydroxyl group-containing polyolefin (A1) may also be used. As the polymer polyol (A2), preferred is at least one selected from the group consisting of condensation type polyester polyols (A21), polylactone polyols (A22), polycarbonate polyols (A23), polyether polyols (A24) and polyacrylic polyols (A25). The high molecular weight polyol (A2) may be used alone or in combination of two or more kinds.

[0042] The condensation type polyester polyol (A21) may be, for example, one obtained by condensing a diol having an Mn of less than 500 with a dicarboxylic acid or an ester-forming derivative thereof [such as an acid anhydride, a lower (C1-4) alkyl ester, or an acid halide].

[0043] Examples of diols having an Mn of less than 500 include aliphatic dihydric alcohols having 2 to 8 carbon atoms [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.) and diols having branched alkyl chains (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.)]; Examples of the diol having an aromatic ring include 1,4-bis(hydroxymethyl)cyclohexane and 2,2-bis(4-hydroxycyclohexyl)propane, etc.; 8-20 carbon atom aromatic ring dihydric alcohols including m- or p-xylylene glycol, bis(hydroxyethyl)benzene and bis(hydroxyethoxy)benzene; AO adducts of bisphenols (such as bisphenol A, bisphenol S and bisphenol F), AO adducts of dihydroxynaphthalene and bis(2-hydroxyethyl)terephthalate, etc. Diols having an Mn of less than 500 may be used alone or in combination of two or more.

[0044] Examples of dicarboxylic acids or their ester-forming derivatives include aliphatic dicarboxylic acids having 2 to 15 carbon atoms [oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.], aromatic dicarboxylic acids having 8 to 12 carbon atoms [phthalic acid, terephthalic acid, isophthalic acid, etc.], and their ester-forming derivatives [acid anhydrides, lower alkyl esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides, etc.)], etc. One type of dicarboxylic acid may be used alone, or two or more types may be used in combination.

[0045] Specific examples of the condensation type polyester polyol (A21) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, poly(polyoxytetramethylene) adipate diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, and polybutylene sebacate diol. (A21) may be used alone or in combination of two or more. In addition, a commercially available product may be used as the condensation type polyester polyol (A21). Examples of such commercially available products include "Kuraray Polyol P-2010, Kuraray Polyol P-2011, Kuraray Polyol P-2012, Kuraray Polyol P-2020" manufactured by Kuraray Co., Ltd.

[0046] The polylactone polyol (A22) may be one obtained by ring-opening polymerization of lactone monomers (γ-butyrolactone, γ-valerolactone, ε-caprolactone, and mixtures of two or more of these, etc.) using the above-mentioned diol having an Mn of less than 500 as an initiator. Specific examples of the polylactone polyol (A22) include polybutyrolactone diol, polyvalerolactone diol, and polycaprolactone diol. (A22) may be used alone or in combination of two or more.

[0047] The polycarbonate polyol (A23) may be a polycarbonate diol produced by condensing the diol having an Mn of less than 500 with a low molecular weight carbonate compound (for example, a dialkyl carbonate having an alkyl group with 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group with 2 to 6 carbon atoms, and a diaryl carbonate having an aryl group with 6 to 9 carbon atoms) while causing a dealcoholization reaction. One type of (A23) may be used alone, or two or more types may be used in combination.

[0048] Specific examples of polycarbonate polyols (A23) include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly(tetramethylene / hexamethylene) carbonate diol (e.g., diols obtained by condensing 1,4-butanediol and 1,6-hexanediol with dialkyl carbonate while causing a dealcoholization reaction). In addition, commercially available products may be used as polycarbonate polyols (A23). Examples of such commercially available products include "Ethanacole UH-200" manufactured by Ube Industries, Ltd.

[0049] Examples of the polyether polyol (A24) include the above-mentioned AO adducts having 2 to 12 carbon atoms to the diols having an Mn of less than 500. The AO may be used alone or in combination of two or more types as block copolymers or random copolymers.

[0050] Among the polyether polyols (A24), those having branched alkyl chains are preferred from the viewpoint of sizing, that is, those using as raw materials diols having branched alkyl chains among diols having Mn less than 500, and those using 1,2-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide and 3-methyltetrahydrofuran as AO in the AO adduct, and more preferred are aliphatic polyether diols of dihydric alcohols having branched alkyl, and particularly preferred is polyoxypropylene glycol. (A24) may be used alone or in combination of two or more. In addition, commercially available products may be used as the polyether polyol (A24). Examples of such commercially available products include "PTMG2000, PTMG3000" manufactured by Mitsubishi Chemical Corporation.

[0051] The poly(meth)acrylic polyol (A25) is not particularly limited, and examples thereof include homopolymers and copolymers of (meth)acrylic acid esters having a hydroxy group. The (meth)acrylic polyol can also be obtained by copolymerizing a compound having a polymerizable unsaturated bond in addition to a (meth)acrylic acid ester having a hydroxy group. In the present invention, "(meth)acrylic" means "methacrylic and / or acrylic".

[0052] The (meth)acrylic acid ester having a hydroxy group includes those having one (meth)acryloyl group, and examples thereof include those having a hydroxyalkyl group having 2 to 20 carbon atoms {for example, hydroxyalkyl (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate}, and (meth)acrylic acid monoesters of trihydric alcohols {for example, (meth)acrylic acid monoesters of glycerin, and (meth)acrylic acid monoesters of trimethylolpropane}, and the like.

[0053] The compound having a polymerizable unsaturated bond includes a compound having one polymerizable unsaturated bond, and examples thereof include (meth)acrylic acid alkyl esters having 4 to 50 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, lauryl (meth)acrylate, glycidyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; unsaturated carboxylic acids having 3 to 50 carbon atoms, such as (meth)acrylic acid, maleic acid, and itaconic acid; unsaturated amides having 3 to 50 carbon atoms, such as (meth)acrylamide, N-methylol (meth)acrylamide, and diacetone (meth)acrylamide; and other polymerizable monomers, such as styrene, vinyl toluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0054] Examples of the polymerization method of the (meth)acrylic acid ester having a hydroxy group or the compound having a polymerizable unsaturated bond include emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization, etc. The emulsion polymerization can also be carried out in stages.

[0055] Specific examples of the commercially available poly(meth)acrylic polyol (A25) include, for example, "ARUFON UH-2000, UH-2041, UH-2190, UHE-2012, UH2032" manufactured by Toagosei Co., Ltd., and "Actflow UT-1001, UMM-1001" manufactured by Soken Chemical & Engineering Co., Ltd.

[0056] Among the poly(meth)acrylic polyols (A25), from the viewpoint of compatibility with the hydroxyl group-containing polyolefin (A1), it is preferable to use at least one compound having a polymerizable unsaturated bond selected from the group consisting of n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, lauryl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, and more preferably to use n-butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate as the compound having a polymerizable unsaturated bond. (A25) may be used alone or in combination of two or more kinds.

[0057] When the hydroxyl-containing polyolefin (A1) is used in combination with the polymer polyol (A2), the ratio of the total weight of the polymer polyol (A2) to the weight of the hydroxyl-containing polyolefin (A1) is preferably 100% by weight or less, more preferably 70% by weight or less, and even more preferably 55% by weight or less, from the viewpoint of mechanical strength. The Mn of the high molecular weight polyol (A2) other than the hydroxyl group-containing polyolefin (A1) is preferably 500 or more, more preferably 500 to 5,000, and particularly preferably 1,000 to 4,000, from the viewpoint of bundling ability.

[0058] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer polyol (A2) other than the hydroxyl group-containing polyolefin (A1) in the present invention can be measured by GPC under the following conditions, for example. Apparatus: "Waters Alliance 2695" [Waters] Column: "Guardcolumn Super HL" (1 piece), "TSKgel A combination of one each of SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 (all manufactured by Tosoh Corporation) Sample solution: 0.25% by weight tetrahydrofuran solution Solution injection volume: 10μl Flow rate: 0.6ml / min Measurement temperature: 40℃ Detector: Refractive index detector Reference material: Standard polyethylene glycol

[0059] The hydroxyl value (mg KOH / g) of the polymer polyol (A2) other than the hydroxyl group-containing polyolefin (A1) is, from the viewpoint of reaction stability, preferably from 22 to 225, more preferably from 28 to 113. The hydroxyl value of the polymer polyol (A2) is a value measured in accordance with JIS K0070-1992.

[0060] In the present invention, an active hydrogen-containing compound having an Mn or a chemical formula weight of less than 500 may be used as the active hydrogen-containing compound component (A). For example, the following chain extender (C) and reaction terminator (D) may be used. Examples of the chain extender (C) include a compound (c1) containing an ionic polar group and two active hydrogen atoms, a polyhydric alcohol (c2) having an Mn or a chemical formula weight of less than 500, a polyalkylene polyamine (c3), hydrazine or a derivative thereof (c4), an amino alcohol having 2 to 10 carbon atoms (c5), a polyepoxy compound having 2 to 30 carbon atoms (c6), and water.

[0061] The compound (c1) containing an ionic polar group and two active hydrogen atoms is also used for introducing the ionic polar group into the polyurethane resin (U).

[0062] As the chain extender (C), one type may be used alone, or two or more types may be used in any combination.

[0063] <Compound (c1) containing an ionic polar group and two active hydrogen atoms> The compound (c1) containing an ionic polar group and two active hydrogen atoms includes a compound (c11) containing an anionic group and an active hydrogen atom and a compound (c12) containing a cationic group and an active hydrogen atom. One type of (c1) may be used alone, or two or more types may be used in combination.

[0064] The anionic group in the compound (c11) containing an anionic group and an active hydrogen atom means an acid group or a neutralized acid anion group. Examples of the compound (c11) containing an anionic group and an active hydrogen atom include compounds containing a carboxyl group as an anionic group and having 2 to 10 carbon atoms [dialkylolalkanoic acid (e.g., 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, and 2,2-dimethyloloctanoic acid), tartaric acid, and amino acids (e.g., glycine, alanine, and valine)], compounds containing a sulfonic acid group as an anionic group and having 2 to 16 carbon atoms [3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid, sulfoisophthalic acid di(ethylene glycol) ester, and the like], compounds containing a sulfamic acid group as an anionic group and having 2 to 10 carbon atoms [N,N-bis(2-hydroxyethyl)sulfamic acid, and the like], and salts of these compounds neutralized with a neutralizing agent.

[0065] Examples of the neutralizing agent used for the salt of the compound (c11) containing an anionic group and an active hydrogen atom include ammonia, an amine compound having 1 to 20 carbon atoms, and an alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide, and lithium hydroxide). Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine, and monoethanolamine; secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine, and methylpropanolamine; and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine, and triethanolamine.

[0066] As the neutralizing agent used for the salt of the compound (c11) containing an anionic group and an active hydrogen atom, a compound having a high vapor pressure at 25° C. is preferred from the viewpoint of the storage stability of the aqueous polyurethane dispersion (Q) described below. From this viewpoint, as the neutralizing agent used for the salt of the compound (c11) containing an anionic group and an active hydrogen atom, ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are preferred. From the viewpoint of dispersion stability of the polyurethane resin (U) in water, the amount of the neutralizer added is preferably such that the neutralization rate is 50 to 200%, more preferably 60 to 150%, based on the amount of acidic groups in the polyurethane resin (U). When the neutralization rate is 200% or less, the working environment and fluffing tend to be good, and when the neutralization rate is 50% or more, the dispersion stability of (U) in water tends to be good. In the present invention, the neutralization rate means the molar percentage of the neutralizing agent relative to the number of moles of the anionic group in the compound (c11) containing an anionic group and an active hydrogen atom used in the production of the polyurethane resin (U).

[0067] Among the compounds (c11) containing an anionic group and an active hydrogen atom, from the viewpoint of the dispersion stability of the polyurethane resin aqueous dispersion (Q) described below, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts thereof are preferred, and neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or an amine compound having 1 to 20 carbon atoms are more preferred.

[0068] The cationic group in the compound (c12) containing a cationic group and an active hydrogen atom means a group in which a proton is added to a tertiary amino group, an unneutralized tertiary amino group, or a quaternary ammonium group.

[0069] Examples of the compound (c12) containing a cationic group and an active hydrogen atom include a compound having a tertiary amino group as the cationic group and a hydroxyl group as the active hydrogen atom, and a salt obtained by neutralizing a compound such as a tertiary amino group-containing diol having 3 to 20 carbon atoms [N-alkyldialkanolamine (e.g., N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine), and N,N-dialkylmonoalkanolamine (e.g., N,N-dimethylethanolamine)] with a neutralizing agent.

[0070] Examples of the neutralizing agent used for the compound (c12) containing a cationic group and an active hydrogen atom include monocarboxylic acids having 1 to 10 carbon atoms (e.g., formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, and benzyl chloride.

[0071] The neutralizing agent used for the compound (c11) containing an anionic group and an active hydrogen atom and the compound (c12) containing a cationic group and an active hydrogen atom may be added at any time before, during, or after the urethanization reaction, or before, during, or after the water dispersion step, but is preferably added before or during the water dispersion step from the viewpoint of the stability of the urethane resin (U) and the stability of the polyurethane aqueous dispersion (Q) described below. In addition, the neutralizing agent that has volatilized during the desolvation may be added after the desolvation, and the type of neutralizing agent to be added may be freely selected from those described above.

[0072] Examples of the polyhydric alcohol (c2) having an Mn or a chemical formula weight of less than 500 include dihydric alcohols having 2 to 20 carbon atoms [aliphatic diols (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2- or 1,10-decanediol, 1,2- or 1,12-dodecanediol, etc.), alicyclic diols (1,2-, 1,3- or 1,4-cyclohexanediol, cyclohexanedimethanol, etc.), aromatic aliphatic diols {1-phenylethane-1,2-diol, 1,4-bis(hydroxyethyl)benzene, etc.}, ether group-containing diols {3-butoxy-1,2-propanediol, 3 -(2-ethylhexoxy)-1,2-propanediol, 3-phenoxy-1,2-propanediol, 3-(p-tert-butylphenoxy)-1,2-propanediol, etc.} and halogen group-containing diols (3-chloro-1,2-propanediol, etc.)], trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols (glycerin, trimethylolpropane, etc.)), and tetrahydric to octahydric alcohols having 5 to 20 carbon atoms (aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.) and sugars (sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof)].

[0073] Examples of the polyalkylene polyamine (c3) include aliphatic polyamines having 2 to 20 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.), alicyclic polyamines having 6 to 20 carbon atoms (diaminocyclohexane, dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines having 2 to 20 carbon atoms (phenylenediamine, tolylenediamine, diphenylmethanediamine, etc.), and heterocyclic polyamines having 2 to 20 carbon atoms (piperazine, N-aminoethylpiperazine, etc.).

[0074] Examples of the hydrazine or derivatives thereof (c4) include hydrazines (hydrazine and monoalkylhydrazines, etc.), dihydrazides (succinic acid dihydrazide, adipic acid dihydrazide, etc.), and the like.

[0075] Examples of the amino alcohol (c5) having 2 to 10 carbon atoms include ethanolamine, diethanolamine, 2-amino-2-methylpropanol, and triethanolamine.

[0076] Examples of the polyepoxy compound (c6) having 2 to 30 carbon atoms include AO having 2 to 4 carbon atoms (ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide), glycidol, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 1,2-epoxydecane, 1,2-epoxydodecane, cyclohexene oxide, styrene oxide, epichlorohydrin, 1,6-hexanediol diglycidyl ether, and trimethylolpropane polyglycidyl ether.

[0077] The polyepoxy compound (c6) having 2 to 30 carbon atoms is used as a chain extender when the compound (c1) containing an ionic polar group and two active hydrogen atoms has a carboxyl group, and the epoxy group reacts with the carboxyl group to cause an extension reaction.

[0078] Of the chain extenders (C), from the viewpoint of the storage stability of the polyurethane aqueous dispersion (Q) described below, preferred are a compound (c1) containing an ionic polar group and two active hydrogen atoms, a polyhydric alcohol (c2), a polyalkylene polyamine (c3), an amino alcohol (c5) and water, and more preferred are a compound (c1) containing an ionic polar group and two active hydrogen atoms, a dihydric alcohol, a trihydric alcohol, water, an aliphatic polyamine, an alicyclic polyamine and an amino alcohol (c5).

[0079] The amount of the compound (c1) containing an ionic polar group and two active hydrogen atoms used is adjusted so that the content of the ionic polar group in the polyurethane resin (U) is preferably 0.5 to 5.0% by weight, more preferably 0.5 to 4.8% by weight, and particularly preferably 0.5 to 4.5% by weight, based on the weight of the polyurethane resin (U). In the present invention, the content of ionic polar groups means the weight % of unneutralized cationic groups or anionic groups, and does not include the weight of counter ions. For example, the content of ionic polar groups in the compound (c11) containing an anionic group and an active hydrogen atom is the weight % of carboxyl groups (-COOH) in the case of the triethylamine salt of 2,2-dimethylolpropionic acid, and the weight % of sulfo groups (-SO) in the case of the triethylamine salt of 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid. 3 The content of the ionic polar group in the compound (c12) containing a cationic group and an active hydrogen atom means the weight % of only the nitrogen atoms in the tertiary amino group.

[0080] Examples of the reaction terminator (D) include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.) and monoamines having 1 to 10 carbon atoms (mono- or di-alkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine, monooctylamine, etc.; mono- or di-alkanolamines such as monoethanolamine, diethanolamine, diisopropanolamine, etc.). The reaction terminator may be used alone or in combination of two or more kinds.

[0081] <Isocyanate component (B)> Examples of the isocyanate component (B) in the present invention include aromatic polyisocyanates (B1) having 6 to 20 carbon atoms (excluding carbon atoms in isocyanate groups, the same applies below) having 2 to 3 or more isocyanate groups, aliphatic polyisocyanates (B2) having 2 to 18 carbon atoms, alicyclic polyisocyanates (B3) having 4 to 15 carbon atoms, araliphatic polyisocyanates (B4) having 8 to 15 carbon atoms, and modified products (B1) to (B4) (B5), etc. As the isocyanate component (B), one type may be used alone, or two or more types may be used in combination.

[0082] Examples of the aromatic polyisocyanate (B1) having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, and crude MDI.

[0083] Examples of the aliphatic polyisocyanate (B2) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0084] Examples of the alicyclic polyisocyanate (B3) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0085] Examples of the aralkyl polyisocyanate (B4) having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

[0086] The modified product (B5) of (B1) to (B4) may include modified products of (B1) to (B4) having a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group or an oxazolidone group.

[0087] As the isocyanate component (B), from the viewpoint of mechanical properties, the aliphatic polyisocyanates (B2) having 2 to 18 carbon atoms and the alicyclic polyisocyanates (B3) having 4 to 15 carbon atoms are preferred, (B3) is more preferred, and IPDI and hydrogenated MDI are particularly preferred.

[0088] The polyurethane resin (U) in the present invention may contain additives such as antioxidants, color inhibitors, weather stabilizers, plasticizers, and mold release agents, if necessary. The amount of these additives used is preferably as small as possible, based on the weight of the polyurethane resin (U), from the viewpoint of mechanical properties, within a range in which the additives can exert their effects, and is preferably 10% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less.

[0089] The urethane group content in the polyurethane resin (U) in the present invention is preferably from 0.5 to 3.0 mmol / g, more preferably from 0.7 to 2.5 mmol / g, and particularly preferably from 0.9 to 2.0 mmol / g, from the viewpoint of mechanical properties.

[0090] The urethane group content of the polyurethane resin (U) can be adjusted to a desired range by appropriately adjusting the molecular weight of the hydroxyl group-containing polyolefin (A1) and other active hydrogen-containing compound components used as necessary [polymer polyol (A2), chain extender (C), etc.], the ratio of the active hydrogen-containing compound component (A) to the isocyanate component (B), and the like. The urethane group content is determined by the N atom content quantified by a nitrogen analyzer. 1 It is calculated from the ratio of urethane groups and urea groups and the contents of allophanate groups and biuret groups quantified by H-NMR.

[0091] From the viewpoints of mechanical properties and sizing ability, the urea group content in the polyurethane resin (U) is preferably 1.5 mmol / g or less, more preferably 1.2 mmol / g or less, particularly preferably 1.0 mmol / g or less, and most preferably 0.8 mmol / g or less, based on the weight of the polyurethane resin (U).

[0092] In order to adjust the urea group content in the polyurethane resin (U) to fall within a desired range, the amino group content, water content and isocyanate group content in the raw materials for the polyurethane resin (U) may be appropriately adjusted. The urea group content is determined by the N atom content determined by a nitrogen analyzer. 1 It is calculated from the ratio of urethane groups and urea groups and the contents of allophanate groups and biuret groups quantified by H-NMR.

[0093] <Textile sizing agent> The fiber sizing agent of the present invention contains the polyurethane resin (U). From the viewpoint of ease of attachment to fibers, the polyurethane resin (U) is preferably contained in the fiber sizing agent as an aqueous polyurethane dispersion (Q) in which the polyurethane resin (U) is dispersed in a medium containing water.

[0094] <Polyurethane resin aqueous dispersion (Q)> The aqueous polyurethane dispersion (Q) can be produced, for example, by the following method. (1) A solution (for example, a solvent solution described later) of a polyurethane prepolymer (P) having an isocyanate group at its end, which contains a hydroxyl group-containing polyolefin (A1) and, if necessary, a high molecular weight polyol (A2) and an isocyanate component (B) as constituent monomers, is prepared. Next, water, and optionally a solvent, a chain extender (C) and a neutralizing agent are charged, followed by phase inversion emulsification, and optionally the solvent is distilled off to obtain an aqueous polyurethane dispersion (Q). (2) A solution (for example, an organic solvent solution described below) of a polyurethane prepolymer (P) having an isocyanate group at its end, which contains a hydroxyl group-containing polyolefin (A1) and, if necessary, a high molecular weight polyol (A2) and an isocyanate component (B) as constituent monomers, is prepared. Next, water and, if necessary, a mixture of a solvent, a neutralizing agent and a chain extender (C) are charged and dispersed using a disperser, and, if necessary, the solvent is distilled off to obtain an aqueous polyurethane dispersion (Q).

[0095] (3) A solution (for example, a solvent solution described later) of a polyurethane prepolymer (P) having an isocyanate group at its end, which contains a hydroxyl group-containing polyolefin (A1) and, if necessary, a high molecular weight polyol (A2) and an isocyanate component (B) as constituent monomers, is prepared. Next, a mixture containing the solution of the polyurethane prepolymer (P) and water is dispersed using a known dispersing machine, and then, if necessary, a neutralizing agent and a reaction terminator (D) are added, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane dispersion (Q). (4) A solvent solution of a polyurethane resin (U) containing a hydroxyl group-containing polyolefin (A1) and, if necessary, a high molecular weight polyol (A2) and an isocyanate component (B) as constituent monomers is prepared. Next, water is added, and the mixture is dispersed, for example, by a disperser, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane dispersion (Q).

[0096] In the process of obtaining the aqueous polyurethane dispersion, in addition to the polyurethane prepolymer (P), the solvent, the neutralizing agent, the chain extender (C), water, and the reaction terminator (D), an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant, such as the emulsifier (F) described in JP-A-2015-131889, may be used as necessary.

[0097] Examples of the solvent include organic solvents such as ketone-based solvents (e.g., acetone and methyl ethyl ketone), ester-based solvents [e.g., ethyl acetate and dibasic acid ester (DBE)], ether-based solvents (e.g., tetrahydrofuran), amide-based solvents (e.g., N,N-dimethylformamide and N-methylpyrrolidone), alcohol-based solvents (e.g., isopropyl alcohol), and aromatic hydrocarbon-based solvents (e.g., toluene).

[0098] The polyurethane aqueous dispersion (Q) is a dispersion of the polyurethane resin (U) in a medium containing water, and the medium may contain the above-mentioned solvent. From the viewpoint of the working environment, the content of the above-mentioned solvent in the medium is 30% by weight or less, more preferably 5% by weight or less.

[0099] The volume average particle size (Dv) of the polyurethane resin (U) particles in the aqueous polyurethane dispersion (Q) of the present invention is preferably 0.01 to 1 μm, more preferably 0.02 to 0.7 μm, and particularly preferably 0.03 to 0.4 μm, from the viewpoint of dispersion stability. When (Dv) is 0.01 μm or more, the viscosity is appropriate and the handling property is good, and when it is 1 μm or less, the dispersion stability is good.

[0100] The volume average particle diameter (Dv) can be controlled by the ionic polar group in the polyurethane resin (U) and the type and operating conditions of the dispersing machine used in the dispersing step. Specifically, the volume average particle diameter can be reduced by increasing the amount of ionic polar group in the polyurethane resin (U), and the volume average particle diameter can be increased by decreasing the amount of ionic polar group in the polyurethane resin (U).

[0101] The fiber sizing agent of the present invention may contain, in addition to the polyurethane resin (U), at least one resin (Z) selected from the group consisting of polyurethane resins (Z1) other than the polyurethane resin (U), polyester resins (Z2) and epoxy resins (Z3).

[0102] The polyurethane resin (Z1) is a polyurethane resin obtained by reacting an active hydrogen-containing compound component (A) with an isocyanate component (B), and the active hydrogen-containing compound component (A) does not contain a hydroxyl group-containing polyolefin (A1). The polyurethane resin (Z1) is the same as the polyurethane resin (U) except that the hydroxyl group-containing polyolefin (A1) is not used (for example, the preferred ranges of the urethane group and urea group contents, Mn, and the ionic polar group contents). The polyurethane resin (Z1) is preferably contained in the fiber sizing agent as an aqueous polyurethane resin dispersion dispersed in a medium containing water, and the method for producing the aqueous polyurethane resin dispersion is the same as that for the aqueous polyurethane resin dispersion (Q) except that the hydroxyl group-containing polyolefin (A1) is not used as a raw material, and the preferred solid content concentration, volume average particle size, viscosity, pH, and the like are the same as those for the aqueous polyurethane resin dispersion (Q).

[0103] As the polyester resin (Z2), a polyester resin used in a known fiber sizing agent can be used, and preferably, the polyester resin (Z2) is contained in the fiber sizing agent in the form of an aqueous solution or aqueous emulsion containing the polyester resin (Z2) and an aqueous medium. For example, an aqueous liquid or aqueous emulsion polyester resin described in JP-A-2009-1954 can be mentioned. From the viewpoint of the storage stability of the aqueous polyurethane dispersion (Q), the polyester resin (Z2) is preferably one produced from a diol and a dicarboxylic acid or an anhydride thereof, and more preferably one produced from a diol, at least one of which has an oxyethylene group, and a dicarboxylic acid or an anhydride thereof.

[0104] As the epoxy resin (Z3), any epoxy resin used in a known fiber sizing agent can be used. Preferably, the epoxy resin (Z3) is contained in the fiber sizing agent in the form of an aqueous solution or aqueous emulsion containing the epoxy resin (Z3) and an aqueous medium. Examples of such epoxy resins include the aqueous liquid or aqueous emulsion epoxy resins described in JP-A-2009-121013 and the like. Examples of the epoxy resin (Z3) include diepoxides, phenol novolac type epoxy resins, and epoxidized unsaturated fatty acid triglycerides (epoxidized soybean oil, epoxidized rapeseed oil, etc.).

[0105] The diepoxides include diglycidyl ethers, diglycidyl esters, diglycidyl amines, and alicyclic diepoxides.

[0106] Examples of diglycidyl ethers include diglycidyl ethers of dihydric phenols and diglycidyl ethers of dihydric alcohols. Examples of diglycidyl ethers of dihydric phenols include condensates (including polycondensates) of dihydric phenols having 6 to 30 carbon atoms and epichlorohydrin, both ends of which are glycidyl ethers. Examples of dihydric phenols include bisphenols (such as bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, and halogenated bisphenol A), catechin, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4'-dihydroxybiphenyl, tetramethylbiphenyl, and 9,9'-bis(4-hydroxyphenyl)fluorene. Examples of diglycidyl ethers of dihydric alcohols include condensates (including polycondensates) of diols having 2 to 100 carbon atoms and epichlorohydrin, both ends of which are glycidyl ethers. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, neopentyl glycol, and an AO (1 to 20 moles) adduct of bisphenol A. Examples of the AO include the above AOs having 2 to 4 carbon atoms.

[0107] The molar ratio of the dihydric phenol unit or dihydric alcohol unit to the epichlorohydrin unit contained in the diglycidyl ether {(dihydric phenol unit or dihydric alcohol unit):(epichlorohydrin unit)} is expressed as n:n+1. n is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. The diglycidyl ether may be a mixture of n=1 to 10 (e.g., a mixture having different degrees of polycondensation).

[0108] Examples of diglycidyl esters include diglycidyl esters of aromatic dicarboxylic acids and diglycidyl esters of aliphatic dicarboxylic acids. Examples of diglycidyl esters of aromatic dicarboxylic acids include condensates (including polycondensates) of aromatic dicarboxylic acids and epichlorohydrin, which have two glycidyl groups. Examples of diglycidyl esters of aliphatic dicarboxylic acids include condensates (including polycondensates) of aromatic dicarboxylic acids with aromatic nuclei (hexahydrophthalic acid and 4-cyclohexene-1,2-dicarboxylic acid, etc.) or condensates (including polycondensates) of linear or branched aliphatic dicarboxylic acids (adipic acid and 2,2-dimethylpropanedicarboxylic acid, etc.) and epichlorohydrin, which have two glycidyl groups. In the diglycidyl ester, the molar ratio of aromatic dicarboxylic acid units or aliphatic dicarboxylic acid units to epichlorohydrin units {(aromatic dicarboxylic acid units or aliphatic dicarboxylic acid units):(epichlorohydrin units)} is expressed as n:n+1. n is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. The diglycidyl ester may be a mixture of n=1 to 10.

[0109] Examples of diglycidylamine include N-glycidyl compounds (N,N-diglycidylaniline and N,N-diglycidyltoluidine) obtained by reacting an aromatic amine (aniline, toluidine, etc.) having 6 to 20 carbon atoms and 2 to 4 active hydrogen atoms with epichlorohydrin. Diglycidylamine has a molar ratio of aromatic amine units to epichlorohydrin units [(aromatic amine units):(epichlorohydrin units)} expressed as n:(n+1). n is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. Diglycidylamine may be a mixture of n=1 to 10.

[0110] Examples of the alicyclic diepoxide include alicyclic epoxides having 6 to 50 carbon atoms and two epoxy groups [vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, ethylene glycol bisepoxydicyclopentyl ether, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)butylamine, etc.].

[0111] Of the epoxy resins (Z3), from the viewpoint of mechanical properties, diglycidyl ethers are preferred, more preferably diglycidyl ethers of dihydric phenols, particularly preferably diglycidyl ethers of bisphenols, and most preferably diglycidyl ethers of bisphenol A (bisphenol A-type epoxy resins).

[0112] The content of the polyurethane resin (U) in the fiber sizing agent of the present invention is preferably 10 to 100% by weight, more preferably 40 to 100% by weight, based on the weight of the solid content of the fiber sizing agent, from the viewpoint of mechanical properties. The content of the resin (Z) in the fiber sizing agent is preferably 90% by weight or less, and more preferably 60% by weight or less, based on the weight of the polyurethane resin (U) from the viewpoint of mechanical properties. In this specification, the solid content refers to the residue remaining after drying 1 g of a sample by heating at 130° C. for 45 minutes in a circulating air dryer.

[0113] From the viewpoint of ease of handling, the solids concentration of the fiber sizing agent (content of components other than volatile components) is preferably 5 to 50% by weight, more preferably 10 to 45% by weight, and even more preferably 15 to 40% by weight. The solids concentration can be obtained by precisely weighing 1 g of the fiber bundling agent, heating it at 130°C for 45 minutes, and then precisely weighing the weight, and calculating the ratio (percentage) of the remaining weight after heating to the weight before heating.

[0114] From the viewpoint of handleability, the viscosity of the fiber sizing agent at 25° C. is preferably 10 to 100,000 mPa·s, and more preferably 10 to 5,000 mPa·s. The viscosity can be measured at a constant temperature of 25° C. using a BL type viscometer.

[0115] From the viewpoint of blend stability, the pH of the fiber sizing agent is preferably 2 to 12, and more preferably 4 to 10. The pH can be measured at 25° C. using a pH Meter M-12 (manufactured by Horiba, Ltd.).

[0116] From the viewpoint of cost, etc., it is preferable that the fiber sizing agent of the present invention has a high concentration as described above when distributed and a low concentration (e.g., 0.05 to 5% by weight, etc.) when producing fiber bundles. That is, by distributing it at a high concentration, transportation costs and storage costs can be reduced, and by treating the fibers at a low concentration, a fiber bundle that gives an excellent molded product strength can be produced.

[0117] <Fiber bundle> The fiber bundle of the present invention is obtained by treating fibers with a fiber bundling agent. Examples of the fibers include carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slag fibers (such as those described in International Publication No. 2003 / 47830), and from the viewpoint of the strength of the molded product, carbon fibers are preferred. Two or more of these fibers may be used in combination.

[0118] The fiber bundle of the present invention is obtained by treating the above-mentioned fibers with the fiber sizing agent of the present invention, and is preferably a fiber bundle having about 3,000 to 50,000 fibers bundled together. For example, a carbon fiber bundle is obtained by treating carbon fibers with the fiber sizing agent of the present invention, and is preferably a carbon fiber bundle having about 3,000 to 50,000 carbon fibers bundled together.

[0119] Methods for treating the fibers include spraying and dipping. Specifically, a fiber sizing agent is diluted in an aqueous medium to prepare an aqueous diluted solution (S) of the fiber sizing agent having a weight percentage of solids of 0.05 to 5% by weight, and (S) is sprayed onto fibers or fibers are immersed in (S) and then dried to adhere the solids. The amount of the fiber sizing agent adhered to the fiber, which is the weight of the solid content of the fiber sizing agent, is preferably 0.05 to 5% by weight, more preferably 0.2 to 3.0% by weight, based on the weight of the fiber before treatment. This range is preferable because it improves the strength of the molded product.

[0120] <Complex intermediate> The composite intermediate of the present invention contains the fiber bundle of the present invention and a matrix resin. The matrix resin may be a thermoplastic resin (e.g., polyolefin resin such as polypropylene resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene sulfide resin, etc.) or a thermosetting resin (epoxy resin, unsaturated polyester resin (e.g., those described in Japanese Patent No. 3723462, etc.), vinyl ester resin, phenol resin (e.g., those described in Japanese Patent No. 3723462, etc.)), etc.), preferably a polyolefin resin, and more preferably a polypropylene resin.

[0121] The composite intermediate of the present invention may contain a modifier as necessary. When the modifier is contained, the strength of the molded article is further improved. Examples of the modifier include acid-modified polyolefin (for example, product name "UMEX 1001" manufactured by Sanyo Chemical Industries, Ltd.).

[0122] The weight ratio of the matrix resin to the fiber bundles (matrix resin / fiber bundles) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 50 / 50, and particularly preferably 20 / 80 to 40 / 60, from the viewpoint of molded body strength, etc. When a modifier is contained, the content (wt%) of the modifier relative to the matrix resin is preferably 0.1 to 50, more preferably 1 to 20, and particularly preferably 3 to 10, from the viewpoint of molded body strength, etc.

[0123] The composite intermediate can be produced by impregnating a fiber bundle with a matrix resin that has been thermally melted (preferably at a melting temperature of 60 to 350°C) or a matrix resin that has been diluted with a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, etc.). When a solvent is used, it is preferable to remove the solvent by drying the composite intermediate.

[0124] <Fiber-reinforced composite materials> The fiber-reinforced composite material of the present invention is obtained by molding the composite intermediate. When the matrix resin is a thermoplastic resin, the composite intermediate can be heated and molded, and solidified at room temperature to form a molded product. The method of heat molding is not particularly limited, and examples thereof include a filament winding molding method (a method of winding a composite intermediate sheet around a rotating mandrel under tension and heat molding it), a press molding method (a method of stacking composite intermediate sheets and heat molding it), an autoclave method (a method of pressing a composite intermediate sheet against a mold with pressure and heat molding it), and a method of mixing chopped fibers or milled fibers with a matrix resin and injection molding it. EXAMPLES

[0125] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0126] <Production Example 1> A reaction vessel was charged with 1,000 parts by weight of a high molecular weight polyolefin (A00-1) whose constituent monomers were 91% by weight of propylene and 9% by weight of ethylene [Mn: 113,000, isotacticity: 50%, product name "Vistamaxx3980", manufactured by Exxonmobil], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. Thermal degradation was then carried out with stirring at 370°C for 85 minutes, yielding polyolefin (A01-1). In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-1) and 6.5 parts by weight of maleic anhydride (E-1) (weight parts after subtracting the distilled amount described below. The same applies to the following production examples) were charged, and after nitrogen replacement, the mixture was heated to 180°C under nitrogen aeration to dissolve uniformly, and a solution of 0.5 parts by weight of a radical initiator [dicumyl peroxide, trade name "Percumyl D", NOF Corp.] (F-1) dissolved in 5 parts by weight of xylene was dropped over 5 minutes, and stirring was continued for 1 hour under xylene reflux. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (X-1). Next, 100 parts by weight of (X-1) and 6.4 parts by weight of 2-aminoethanol (G-1) (weight parts are shown after subtracting the amount distilled off, which will be described later. The same applies to the following Production Examples) were charged into a reaction vessel, and reacted at 180°C for 1 hour under a nitrogen gas atmosphere. Next, unreacted 2-aminoethanol was distilled off at 180° C. under a reduced pressure of 2.7 kPa to obtain a hydroxyl-containing polyolefin (A1-1). The weight ratio of ethylene to propylene, which are the constituent monomers of the hydroxyl-containing polyolefin (A1-1), [ethylene / propylene] was 1 Confirmation by H-NMR revealed that the ratio was 9 / 91. The hydroxyl value of (A1-1) was 29, the acid value was 0.2, the Mn was 3,500, the isotacticity was 43%, and the number of hydroxyl groups per molecule was 1.8. The number of double bonds per 1,000 carbons of the polyolefin (A01-1) used for modification was 7.5.

[0127] <Production Example 2> A reaction vessel was charged with 1,000 parts by weight of a high molecular weight polyolefin (A00-1) whose constituent monomers were 91% by weight of propylene and 9% by weight of ethylene [Mn: 113,000, isotacticity: 50%, product name "Vistamaxx3980", manufactured by Exxonmobil], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. Thermal degradation was then carried out with stirring at 380°C for 65 minutes, yielding polyolefin (A01-2). In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-2) and 8 parts by weight of maleic anhydride (E-1) were charged, and after replacing with nitrogen, the mixture was heated to 180°C under nitrogen aeration to dissolve uniformly, and stirring was continued for 1 hour. After that, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (X-2). Next, 100 parts by weight of (X-2) and 6.4 parts by weight of 2-aminoethanol (G-1) were charged into a reaction vessel, and the mixture was reacted at 180° C. for 1 hour under a nitrogen gas atmosphere. Next, unreacted 2-aminoethanol was distilled off at 180° C. under a reduced pressure of 2.7 kPa to obtain a hydroxyl-containing polyolefin (A1-2). The weight ratio of ethylene to propylene, which are the constituent monomers of the hydroxyl-containing polyolefin (A1-2), [ethylene / propylene] was 1 Confirmation by H-NMR revealed that the ratio was 9 / 91. The hydroxyl value of (A1-2) was 29, the acid value was 0.1, the Mn was 3,300, the isotacticity was 43%, and the number of hydroxyl groups per molecule was 1.7. The number of double bonds per 1,000 carbons of the polyolefin (A01-2) used for modification was 8.8.

[0128] <Production Example 3> A reaction vessel was charged with 1,000 parts by weight of a high molecular weight polyolefin (A00-2) whose constituent monomers were 85% by weight of propylene and 15% by weight of ethylene [Mn: 76,000, isotacticity: 20%, product name "Vistamaxx6202", manufactured by Exxonmobil], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. Thermal degradation was then carried out with stirring at 400°C for 50 minutes, yielding polyolefin (A01-3). In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-3) and 11 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen replacement, the mixture was heated to 180°C under nitrogen aeration to dissolve uniformly, and a solution in which 3 parts by weight of a radical initiator [dicumyl peroxide, trade name "Percumyl D", NOF Corp.] (F-1) was dissolved in 10 parts by weight of xylene was dropped over 5 minutes, and stirring was continued for 1 hour under xylene reflux. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (X-3). Next, 100 parts by weight of (X-3) and 10 parts by weight of 2-aminoethanol (G-1) were charged into a reaction vessel, and the mixture was reacted at 180° C. for 1 hour under a nitrogen gas atmosphere. Next, unreacted 2-aminoethanol was distilled off at 180° C. under a reduced pressure of 2.7 kPa to obtain a hydroxyl-containing polyolefin (A1-3). The weight ratio of ethylene to propylene, which are the constituent monomers of the hydroxyl-containing polyolefin (A1-3), [ethylene / propylene] was 1 Confirmation by 1 H-NMR revealed a value of 15 / 85. The hydroxyl value of (A1-3) was 46, the acid value was 0.1, the Mn was 2,300, the isotacticity was 18%, and the number of hydroxyl groups per molecule was 1.9. The number of double bonds per 1,000 carbons of the polyolefin (A01-3) used for modification was 9.5.

[0129] <Production Example 4> A reaction vessel was charged with 1,000 parts by weight of a high molecular weight polyolefin (A00-2) whose constituent monomers were 85% by weight of propylene and 15% by weight of ethylene [Mn: 76,000, isotacticity: 20%, product name "Vistamaxx6202", manufactured by Exxonmobil], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. Then, while stirring, the mixture was thermally degraded at 400°C for 100 minutes to obtain polyolefin (A01-4). In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-4) and 23.5 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen replacement, the mixture was heated to 180°C under nitrogen aeration to dissolve uniformly, and a solution in which 3 parts by weight of a radical initiator [dicumyl peroxide, trade name "Percumyl D", NOF Corp.] (F-1) was dissolved in 10 parts by weight of xylene was dropped over 5 minutes, and stirring was continued for 1 hour under xylene reflux. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (X-4). Next, 100 parts by weight of (X-4) and 27 parts by weight of 2-aminoethanol (G-1) were charged into a reaction vessel, and the mixture was reacted at 180° C. for 1 hour under a nitrogen gas atmosphere. Next, unreacted 2-aminoethanol was distilled off at 180° C. under a reduced pressure of 2.7 kPa to obtain a hydroxyl-containing polyolefin (A1-4). The weight ratio of ethylene to propylene, which are the constituent monomers of the hydroxyl-containing polyolefin (A1-4), [ethylene / propylene] was 1 Confirmation by 1 H-NMR revealed a value of 15 / 85. The hydroxyl value of (A1-4) was 108, the acid value was 0.2, the Mn was 1,050, the isotacticity was 17%, and the number of hydroxyl groups per molecule was 2.0. The number of double bonds per 1,000 carbons of the polyolefin (A01-4) used for modification was 22.4.

[0130] <Production Example 5> A reaction vessel was charged with 1,000 parts by weight of a high molecular weight polyolefin (A00-3) whose constituent monomers were 73% by weight propylene and 27% by weight ethylene [Mn: 200,000, isotacticity: 33%, product name "Tafmer S4030", manufactured by Mitsui Chemicals], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. Thermal degradation was then carried out with stirring at 380°C for 80 minutes, to obtain polyolefin (A01-5). In a reaction vessel, 100 parts by weight of the obtained polyolefin (A01-5) and 4.5 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen replacement, the mixture was heated to 180°C under nitrogen aeration to dissolve uniformly, and a solution in which 0.5 parts by weight of a radical initiator [dicumyl peroxide, trade name "Percumyl D", NOF Corp.] (F-1) was dissolved in 5 parts by weight of xylene was dropped over 5 minutes, and stirring was continued for 1 hour under xylene reflux. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (X-5). Next, 100 parts by weight of (X-5) and 4.6 parts by weight of 2-aminoethanol (G-1) were charged into a reaction vessel, and the mixture was reacted at 180° C. for 1 hour under a nitrogen gas atmosphere. Next, unreacted 2-aminoethanol was distilled off at 180° C. under a reduced pressure of 2.7 kPa to obtain a hydroxyl-containing polyolefin (A1-5). The weight ratio of ethylene to propylene, which are the constituent monomers of the hydroxyl-containing polyolefin (A1-5), [ethylene / propylene] was 1 Confirmation by 1 H-NMR revealed a value of 27 / 73. The hydroxyl value of (A1-5) was 21, the acid value was 0.2, the Mn was 4,500, the isotacticity was 31%, and the number of hydroxyl groups per molecule was 1.7. The number of double bonds per 1,000 carbons of the polyolefin (A01-5) used for modification was 5.4.

[0131] <Production Example 6> [Production of aqueous emulsion polyester resin (Z2-1)] 366.1 parts of EO adduct of bisphenol A in which 2.3 molar parts of EO are added to 1 molar part of bisphenol A, 50.3 parts of PO adduct of bisphenol A in which 3 molar parts of PO are added to 1 molar part of bisphenol A (manufactured by Sanyo Chemical Industries Co., Ltd.: Newpol BP-3P), 170.5 parts of terephthalic acid, and 0.3 parts of tetraisopropoxy titanate were reacted for 10 hours in a glass reaction vessel under nitrogen flow at 225 ° C. and reduced pressure to -0.1 MPa while distilling off water. 28.1 parts of fumaric acid and 0.5 parts of tetraisopropoxy titanate were further added thereto and reacted for 3 hours while distilling off water at 170 ° C. 433.4 parts of EO adduct of bisphenol A in which 34 molar parts of EO are added to 1 molar part of bisphenol A were further added thereto and reacted for 16 hours while distilling off water at 180 ° C. and reduced pressure to -0.1 MPa to obtain polyester resin (Z2). 900 parts of the obtained polyester resin (Z2) and 100 parts of a nonionic surfactant {PO and EO adduct of styrenated phenol, "Soprophor796 / P" manufactured by Rhodia Nikka} were uniformly mixed in a universal mixer (Universal mixer manufactured by San-ei Seisakusho Co., Ltd.) at 70°C for 30 minutes. A total of 2,030 parts of water was dropped into the mixture over 6 hours to obtain an aqueous emulsion polyester resin (Z2-1) having a polyester resin (Z2) concentration of 29.7% by weight.

[0132] <Production Example 7> [Production of aqueous emulsion polyepoxy resin (Z3-1)] 800 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation: Epicoat 1001) (Z3) and 200 parts of a nonionic surfactant {PO and EO adduct of styrenated phenol, Rhodia Nikka's "Soprophor796 / P"} were mixed uniformly in a universal mixer (Sanei Seisakusho Co., Ltd. universal mixer) at 70°C for 30 minutes. A total of 2,030 parts of water was added dropwise to the mixture over 6 hours to obtain an aqueous emulsion polyepoxy resin (Z3-1) with an epoxy resin (Z3) concentration of 26.4% by weight.

[0133] <Comparative Manufacturing Example 1> A reaction vessel was charged with 1000 parts by weight of polyolefin (comparison A00-1) whose constituent monomers were 98% by weight of propylene and 2% by weight of ethylene [Mn: 100,000, isotacticity: 90%, product name "SunAllomer PZA20A", manufactured by SunAllomer Co., Ltd.], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. Thermal degradation was then carried out with stirring at 400°C for 1200 minutes, yielding polyolefin (comparison A01-1). In a reaction vessel, 100 parts by weight of the obtained polyolefin (comparison A01-1) and 28 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen replacement, the mixture was heated to 180°C under nitrogen aeration to dissolve uniformly, and a solution in which 3 parts by weight of a radical initiator [dicumyl peroxide, trade name "Percumyl D", NOF Corp.] (F-1) was dissolved in 10 parts by weight of xylene was dropped over 5 minutes, and stirring was continued for 1 hour under xylene reflux. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (comparison X-1). Next, 100 parts by weight of (composition X-1) and 22 parts by weight of 2-aminoethanol (G-1) were charged into a reaction vessel, and the mixture was reacted at 180° C. for 1 hour under a nitrogen gas atmosphere. Next, unreacted 2-aminoethanol was distilled off at 180° C. under a reduced pressure of 2.7 kPa to obtain a hydroxyl-containing polyolefin (comparison A1-1). The weight ratio of ethylene to propylene, which are the constituent monomers of the hydroxyl-containing polyolefin (comparison A1-1), [ethylene / propylene] was 1 Confirmation by H-NMR revealed a value of 2 / 98. The hydroxyl value of (Comparative A1-1) was 122, the acid value was 0.2, the Mn was 940, the isotacticity was 84%, and the number of hydroxyl groups per molecule was 2.0. The number of double bonds per 1,000 carbons of the polyolefin (Comparative A01-1) used for modification was 22.5.

[0134] <Comparative Manufacturing Example 2> A reaction vessel was charged with 1,000 parts by weight of a polyolefin (comparison A00-2) whose constituent monomers were 27% by weight of propylene and 73% by weight of ethylene [Mn: 40,000, isoactivity: 3%, product name "TAFMER P0280", manufactured by Mitsui Chemicals, Inc.], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater. While stirring, the mixture was thermally degraded at 385°C for 210 minutes to obtain a polyolefin (comparison A01-2). In a reaction vessel, 100 parts by weight of the obtained polyolefin (comparison A01-2) and 9 parts by weight of maleic anhydride (E-1) were charged, and after nitrogen replacement, the mixture was heated to 180°C under nitrogen aeration to dissolve uniformly, and a solution in which 0.5 parts by weight of a radical initiator [dicumyl peroxide, trade name "Percumyl D", NOF Corp.] (F-1) was dissolved in 5 parts by weight of xylene was dropped over 5 minutes, and stirring was continued for 1 hour under xylene reflux. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (comparison X-2). Next, 100 parts by weight of (composition X-2) and 10 parts by weight of 2-aminoethanol (G-1) were charged into a reaction vessel, and reacted at 180° C. for 1 hour under a nitrogen gas atmosphere. Next, unreacted 2-aminoethanol was distilled off at 180°C under a reduced pressure of 2.7 kPa to obtain a hydroxyl-containing polyolefin (comparison A1-2). The weight ratio of ethylene to propylene, which are the constituent monomers of the hydroxyl-containing polyolefin (comparison A1-2), [ethylene / propylene] was 1 Confirmation by 1 H-NMR revealed a value of 73 / 27. The hydroxyl value of (Comparative A1-2) was 35, the acid value was 0.1, the Mn was 3,000, the isotacticity was 1%, and the number of hydroxyl groups per molecule was 1.9. The number of double bonds per 1,000 carbons of the polyolefin (Comparative A01-2) used for modification was 10.5.

[0135] <Example 1> A simple pressurized reaction apparatus equipped with a stirrer and a heater was charged with 179.26 parts by weight of a hydroxyl group-containing polyolefin (A1-1), 92.19 parts by weight of a polyol (A2-1), 82.65 parts by weight of an isocyanate component (B-1) [IPDI, isophorone diisocyanate], 4.18 parts by weight of [1,4-butanediol] as a chain extender (C), 17.03 parts by weight of [2,2-dimethylolpropionic acid], and 124.69 parts by weight of an organic solvent [THF, tetrahydrofuran], and the mixture was stirred at 85°C for 10 hours to carry out a urethanization reaction, producing a THF solution of a urethane prepolymer (P-1). A simple pressurized reaction apparatus equipped with a stirrer and a heating reaction apparatus was charged with 500.00 parts by weight of the obtained urethane prepolymer THF solution (P-1), and while stirring at 50°C, 359.28 parts by weight of THF and 12.81 parts by weight of triethylamine (neutralizing agent) were added, and the mixture was homogenized at 60 rpm for 30 minutes. After that, the temperature was kept at 50°C, and while stirring at 500 rpm, 676.04 parts by weight of ion-exchanged water was gradually added to emulsify the mixture. Then, 86.82 parts by weight of a chain extender (C-3) [aqueous solution of 5% by weight of diethylenetriamine] was added, and the THF was distilled off under reduced pressure at 65°C for 12 hours to obtain an aqueous polyurethane resin dispersion (Q-1), which was used as it is as a fiber bundling agent (1).

[0136] <Examples 2 to 25 and Comparative Examples 1 to 3> Fiber sizing agents (2) to (25) and (1') to (3') of each example were obtained in the same manner as in Example 1, except that the raw materials shown in Table 1 or Table 2 were used as the raw materials in Example 1.

[0137] <Example 26> A simple pressurized reaction apparatus equipped with a stirrer and a heater was charged with 179.26 parts by weight of a hydroxyl group-containing polyolefin (A1-1), 92.19 parts by weight of a polyol (A21-1), 82.65 parts by weight of an isocyanate component (B-1) [IPDI, isophorone diisocyanate], 4.18 parts by weight of [1,4-butanediol] as a chain extender (C), 17.03 parts by weight of [2,2-dimethylolpropionic acid], and 124.69 parts by weight of an organic solvent [THF, tetrahydrofuran], and the mixture was stirred at 85°C for 10 hours to carry out a urethanization reaction, producing a THF solution of a urethane prepolymer (P-1). A simple pressurized reaction apparatus equipped with a stirrer and a heating reaction apparatus was charged with 500.00 parts by weight of the obtained urethane prepolymer THF solution (P-1), and while stirring at 50°C, 359.28 parts by weight of THF and 12.81 parts by weight of triethylamine (neutralizing agent) were added, and the mixture was homogenized at 60 rpm for 30 minutes. After that, the temperature was kept at 50°C, and while stirring at 500 rpm, 676.04 parts by weight of ion-exchanged water was gradually added to emulsify the mixture. Then, 86.82 parts by weight of chain extender (C-3) [5 wt% aqueous diethylenetriamine solution] was added, and the THF was distilled off under reduced pressure at 65°C for 12 hours. The mixture was then cooled to 40°C to obtain an aqueous polyurethane resin dispersion (Q-26). Furthermore, 121.10 parts by weight of the polyurethane resin aqueous dispersion (comparison Q-3) prepared in Comparative Example 3 (Z1-1) as a polyurethane resin (Z1) other than (U) (12.8% by weight of (comparison U-3), which is the polyurethane resin (Z1), based on the weight of the polyurethane resin (U)) was added to 1000 parts by weight of the obtained polyurethane resin aqueous dispersion (Q-26), and the mixture was stirred at 40°C for 2 hours to obtain a fiber sizing agent (26).

[0138] <Examples 27 and 28> Fiber sizing agents (27) to (28) of each example were obtained in the same manner as in Example 26, except that the raw materials shown in Table 1 were used as the raw materials in Example 26. Based on the weight of the polyurethane resin (U), the fiber sizing agent (27) contains 21.8% by weight of the polyester resin (Z2), and the fiber sizing agent (28) contains 14.6% by weight of the epoxy resin (Z3).

[0139] The fiber sizing agents (1) to (28) and (1') to (3') thus obtained were evaluated according to the procedures described below. The results are shown in Tables 1 and 2.

[0140] The volume average particle diameter (Dv) was measured using a laser diffraction particle size distribution analyzer "LA-750" (manufactured by Horiba, Ltd.).

[0141] [Table 1]

[0142] [Table 2]

[0143] The raw materials used in the examples and comparative examples are as follows. Hydroxyl-containing polyolefin (A1) Products manufactured in Manufacturing Examples 1 to 5 and Comparative Manufacturing Examples 1 to 2 ○High molecular weight polyol (A2) (A21-1): Kuraray Polyol P-2010: Poly(3-methyl-1,5-pentanediol, adipic acid polycondensate) with Mn=2,000, manufactured by Kuraray Co., Ltd. (A21-2): Kuraray Polyol P-2011: Poly(3-methyl-1,5-pentanediol, adipic acid, and terephthalic acid polycondensate) with Mn=2,000, manufactured by Kuraray Co., Ltd. (A21-3): Kuraray Polyol P-2012: Poly(3-methyl-1,5-pentanediol, adipic acid, isophthalic acid polycondensate) with Mn=2,000, manufactured by Kuraray Co., Ltd. (A21-4): Kuraray Polyol P-2020: Poly(3-methyl-1,5-pentanediol, terephthalic acid polycondensate) with Mn=2,000, manufactured by Kuraray Co., Ltd. (A23-1): Ethanacole UH-200: Polyhexamethylene carbonate diol with Mn=2,000 [manufactured by Ube Industries, Ltd.] (A24-1): PTMG2000: Poly(oxytetramethylene) glycol with Mn=2,000 [Mitsubishi Chemical Co., Ltd.] (A24-2): PTMG3000: Poly(oxytetramethylene) glycol with Mn=3,000 [Mitsubishi Chemical Co., Ltd.] (A25-1): Actflow UT-1001: Polyacrylic diol with Mn=2000 [manufactured by Soken Chemical Industries, Ltd.] (A25-2): ARUFON UH-2032: Polyacrylic diol with Mn=2000 [manufactured by Toagosei Co., Ltd.] Catalyst Neostan U-600: Bismuth tris(2-ethylhexanoate) [manufactured by Nitto Kasei Co., Ltd.] Surfactants (emulsifiers) Emulmin 50: Ethylene oxide (EO) adduct of higher alcohol [manufactured by Sanyo Chemical Industries, Ltd.] ○Resin (Z) emulsion Z1-1: Polyurethane resin aqueous dispersion prepared in Comparative Example 3 (Comparative Example Q-3) Z2-1: Water-based emulsion polyester resin (Z2-1) produced in Production Example 6 Z3-1: Aqueous emulsion polyepoxy resin (Z3-1) produced in Production Example 7

[0144] <1> Storage stability of fiber sizing agents (40℃) 30 g of the fiber sizing agent was placed in a screw bottle [50 mL (body diameter 35 mm × height 78 mm)] and stored for 14 days at 40° C. From the results of measuring the volume average particle size (μm) before and after storage, the storage stability at 40° C. was calculated using the following formula and evaluated according to the following criteria. (Storage stability at 40°C) (%) = (Volume average particle size after storage) x 100 / (Volume average particle size before storage)

[0145] <Evaluation criteria> ◎: Less than 110% ○: 110% or more, less than 115% △: 115% or more, less than 120% ×: 120% or more

[0146] <2> Storage stability of fiber sizing agents (5℃) 30 g of the fiber sizing agent was placed in a screw bottle [50 mL (body diameter 35 mm × height 78 mm)] and stored at 5° C. for 14 days. From the results of measuring the volume average particle size (μm) before and after storage, the storage stability at 5° C. was calculated using the following formula and evaluated according to the following criteria. (Storage stability at 5°C) (%) = (Volume average particle size after storage) x 100 / (Volume average particle size before storage)

[0147] <Evaluation criteria> ◎: Less than 110% ○: 110% or more, less than 115% △: 115% or more, less than 120% ×: 120% or more

[0148] <3> Bundling of inorganic fibers The fiber sizing agent was diluted with water to a solid content of 3%, to obtain a diluted solution. Carbon fibers (number of filaments = 12,000) were immersed in this diluted solution to be impregnated, and then dried at 170 ° C for 20 seconds to obtain a carbon fiber bundle (adhesion amount of solid content of fiber sizing agent based on the weight of untreated carbon fiber: 1 wt%). The carbon fiber bundle was measured for bundling ability in accordance with JIS L1096-1999 (8.19.1A method, 45 degree cantilever method). The larger the measured value of bundling ability, the better the bundling ability. The bundling ability is preferably 15 cm or more.

[0149] <4> Inorganic fiber bundle fluff A chrome-plated stainless steel rod with a diameter of 2 mm was placed on the surface of the <3> Obtained in Five carbon fiber bundles were arranged in a zigzag pattern at 15 mm intervals so that they would pass while in contact with each other at a contact angle of 120°. The carbon fiber bundle was hung between these stainless steel rods in a zigzag pattern and a tension of 1 kg was applied. Just before the take-up roll, the carbon fiber bundle was sandwiched between two 10 cm x 10 cm sheets of urethane foam with a load of 1 kg applied, and rubbed at a speed of 1 m / min for 5 minutes. During this time, the weight (mg / m) of the fluff attached to the sponge was measured. The smaller the weight of the fluff, the less fluff was generated. The weight of the fluff is preferably less than 0.20 mg / m.

[0150] <5> Flexural strength of fiber-reinforced composite materials As the matrix resin, 95 parts by weight of "Sunallomer PL500A" [polypropylene, manufactured by Sunallomer Co., Ltd.] and 5 parts by weight of "UMEX 1001" [maleic anhydride modified polypropylene, acid value 26, manufactured by Sanyo Chemical Industries, Ltd.] were melt-kneaded and melt-impregnated so that the carbon fiber bundle obtained above was 30% by weight and the matrix resin was 70% by weight. The carbon fiber bundle was cut into 5 mm pieces using a pelletizer, and then uniformly mixed at 200°C to obtain a composite intermediate. The fiber-reinforced composite material was press-molded and its bending strength was measured in accordance with JIS K7074 (Bending test method for carbon fiber reinforced plastics). The higher the bending strength, the better the mechanical strength. The bending strength is preferably 220 MPa or more.

[0151] From the results in Table 1, it can be seen that the fiber sizing agent of the present invention has excellent fiber bundling properties, the fiber bundle obtained using the fiber sizing agent of the present invention has little fuzz, and the fiber reinforced composite material obtained using this fiber bundle has excellent mechanical strength. Furthermore, it can be seen that the fiber sizing agent of the present invention also has excellent storage stability. On the other hand, the fiber sizing agent (3') of Comparative Example 3, which contains only polyurethane resin produced without using hydroxyl group-containing polyolefin (A1), has good fiber bundling properties and the fiber bundles obtained have little fluff, but the mechanical strength of the fiber reinforced composite material obtained is very low. In addition, the fiber sizing agent (1') of Comparative Example 1, which is produced using hydroxyl group-containing polyolefin (ratio A1-1) with [ethylene / α-olefin] of 2 / 98, which is outside the lower limit of the present invention, has very poor fiber bundling properties, the fiber bundles obtained have a lot of fluff, and the mechanical strength of the fiber reinforced composite material obtained is also low. In addition, the fiber sizing agent (2') of Comparative Example 2, which is produced using hydroxyl group-containing polyolefin (ratio A1-2) with [ethylene / α-olefin] of 73 / 27, which is outside the upper limit of the present invention, has good fiber bundling properties and the fiber bundles obtained have little fluff, but the mechanical strength of the fiber reinforced composite material obtained is very low. Furthermore, it is clear that the fiber sizing agents of Comparative Examples 1 and 2 have low storage stability, and in particular, the storage stability at 40°C is extremely low. [Industrial Applicability]

[0152] The fiber sizing agent of the present invention has excellent fiber bundling properties, the fiber bundle obtained has little fuzz, and the fiber-reinforced composite material obtained using this fiber bundle has excellent mechanical strength, so that the fiber sizing agent of the present invention can be used as a bundling agent for various fibers (carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, or slug fibers). In addition, resin compositions and fiber-reinforced composite materials can be provided by using the fiber bundle obtained by treatment with the fiber sizing agent of the present invention as reinforcing fibers and various resins as matrix resins, and are extremely useful for various applications (for example, engines, automobile parts, electronics, machinery industry, etc.).

Claims

1. A fiber sizing agent comprising a polyurethane resin (U), the polyurethane resin (U) is a polyurethane resin obtained by reacting an active hydrogen-containing compound component (A) with an isocyanate component (B), the active hydrogen-containing compound component (A) contains a hydroxyl group-containing polyolefin (A1); The hydroxyl group-containing polyolefin (A1) contains, as constituent monomers, ethylene and an α-olefin having 3 to 8 carbon atoms, The sizing agent for fibers is one in which the weight ratio [ethylene / α-olefin] of ethylene, which are constituent monomers of the hydroxyl group-containing polyolefin (A1), to an α-olefin having 3 to 8 carbon atoms is 3 / 97 to 65 / 35, and the hydroxyl group-containing polyolefin (A1) is obtained by reacting an acid-modified polyolefin (X) in which a polyolefin (A01) having a carbon-carbon double bond containing ethylene and an α-olefin having 3 to 8 carbon atoms is modified with an unsaturated (poly)carboxylic acid (anhydride) (E), with an amino alcohol (G).

2. 2. The fiber sizing agent according to claim 1, wherein the hydroxyl group-containing polyolefin (A1) has a hydroxyl value (mg KOH / g) of 12 to 120.

3. 3. The fiber sizing agent according to claim 1, wherein the α-olefin portion of the hydroxyl group-containing polyolefin (A1) has an isotacticity of 1 to 50%.

4. The fiber sizing agent according to any one of claims 1 to 3, further comprising at least one resin (Z) selected from the group consisting of a urethane resin (Z1) other than the polyurethane resin (U), a polyester resin (Z2), and an epoxy resin (Z3).

5. A fiber bundle obtained by treating at least one type of fiber selected from the group consisting of carbon fibers, glass fibers, aramid fibers, ceramic fibers, metal fibers, mineral fibers, rock fibers, and slag fibers with the fiber sizing agent according to any one of claims 1 to 4.

6. A composite intermediate comprising the fiber bundle according to claim 5 and a matrix resin.

7. A fiber-reinforced composite material obtained by molding the composite intermediate product according to claim 6.

Images