Fiber bundling agent and fiber

Abstract

To provide a fiber bundling agent exhibiting superior resin impregnability, smoothness, and bundling performance.SOLUTION: A fiber bundling agent includes an ester compound (A) represented by a chemical formula (1) and a nonionic surfactant (B). In the chemical formula (1), an ester compound (A1) in which m is 1 and an ester compound (A2) in which m is 2 are included. R1 is a C1-C3 alkylene group. R2 is a C1-C4 alkylene group or alkenyl group. R3 is independently a C2 or C3 alkylene group. m is an integer of 1 or more and 2 or less. n1, n2, n3, and n4 are each independently an integer of 1 or more and 20 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fiber bundling agent and a fiber.

Background Art

[0002] A bundling agent is a chemical applied to fiber materials such as carbon fibers and is used for purposes such as suppressing damage to the fiber material and enhancing the bundling property of the fiber material.

[0003] Patent Document 1 describes a resin composition for bundling composite material reinforcing fibers, wherein the penetration rate (Pe) of wool felt impregnated with the resin composition for bundling into a methyl ethyl ketone solution (concentration 65% by weight) of a matrix resin is 1 to 40 seconds. A resin composition for bundling fibers is described.

[0004] The bundling agent described in Patent Document 1 is attached to various organic fibers or inorganic fibers used in composite materials, and comes into contact with various guides in the fiber processing step and can suppress the generation of fuzz and yarn breakage even when subjected to friction (abrasion resistance).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The bundling agent described in Patent Document 1 had room for improvement in terms of resin impregnability.

[0007] Therefore, an object of the present invention is to provide a fiber bundling agent excellent in resin impregnability, smoothness, and bundling property.

Means for Solving the Problems

[0008] The fiber sizing agent according to the present invention for achieving the above object is a fiber sizing agent containing an ester compound (A) represented by the following chemical formula (1) and a nonionic surfactant (B), and its characteristic configuration is that in the following chemical formula (1), it contains an ester compound (A1) where m is 1 and an ester compound (A2) where m is 2 and the mass ratio of the ester compound (A1) and the ester compound (A2) is 0.1 to 10, and the total content ratio of the ester compound (A1) and the ester compound (A2) in the non-volatile content of the fiber bundling agent is 0.5% by mass or more and 30% by mass or less which is characterized by the following point

[0009]

Chemical formula

[0010] R 1 : An alkylene group of C1 - C3 R 2 : An alkylene group or alkenyl group of C1 - C4 R 3 : Each independently an alkylene group of C2 or C3 (however, when n1, n2, n3, n4 are each 2 or more, the alkylene group can be one kind alone or two kinds) m: An integer of 1 or more and 2 or less The numerical values of n1 + n2 and n3 + n4 are 2 to 6

[0011] According to this configuration, by containing both the ester compound (A1) where m is 1 and the ester compound (A2) where m is 2 in the chemical formula (1), it can become a fiber sizing agent excellent in resin impregnation property, smoothness, and bundling property In addition, according to this configuration, the abundance ratios (total of mass ratio and content ratio) of the ester compound (A1) and the ester compound (A2) that can be a fiber bundling agent excellent in resin impregnation property, smoothness, and bundling property can be defined.

[0012] A further characteristic configuration of the fiber sizing agent according to the present invention is The mass ratio is 0.5 to 5 as follows

[0013] According to this configuration, the content ratios of the ester compound (A1) and the ester compound (A2) that can become a fiber sizing agent excellent in resin impregnation property, smoothness, and bundling property (mass ratio) in detail can be specified

[0014] A further characteristic configuration of the fiber bundling agent according to the present invention is that the total of the content ratios is 5 to 25% by mass.

[0015] According to this configuration, the abundance ratio (total of content ratios) of the ester compound (A1) and the ester compound (A2) that can be a fiber bundling agent excellent in resin impregnation property, smoothness, and bundling property can be defined in detail.

[0016] A further characteristic configuration of the fiber bundling agent according to the present invention is that the pH of a 1% by mass aqueous solution of the fiber bundling agent is 5.0 to 8.0.

[0017] According to this configuration, when the pH of the aqueous solution satisfies the above requirements, it can become a fiber bundling agent excellent in resin impregnation property, smoothness and bundling property, and particularly an excellent effect of smoothness can be obtained.

[0018] A further characteristic configuration of the fiber bundling agent according to the present invention is that when the total content ratio of the ester compound (A) and the nonionic surfactant (B) is 100% by mass, the ester compound (A) is 1 to 30% by mass, and the nonionic surfactant (B) is contained in a ratio of 10 to 99% by mass.

[0019] According to this configuration, the content ratios of the ester compound (A) and the nonionic surfactant (B) that can become a fiber bundling agent excellent in resin impregnation property, smoothness and bundling property can be defined.

[0020] A further characteristic configuration of the fiber bundling agent according to the present invention is that it further contains at least one resin (C) selected from polyester resins, epoxy resins, urethane resins, and vinyl ester resins other than the ester compound (A).

[0021] According to this configuration, by containing the resin (C), it becomes easier to impart bundling property to the fiber material.

[0022] A further characteristic configuration of the fiber bundling agent according to the present invention is that when the total content ratio of the ester compound (A), the nonionic surfactant (B) and the resin (C) is 100% by mass, the ester compound (A) is 1 to 30% by mass, the nonionic surfactant (B) is 10 to 99% by mass, and the resin (C) is contained in a ratio of 0 to 89% by mass (excluding 0).

[0023] According to this configuration, the content ratios of an ester compound (A), a nonionic surfactant (B), and a resin (C), which can be a fiber bundling agent excellent in resin impregnation properties, smoothness, and particularly excellent in bundling properties, can be defined.

[0024] A characteristic configuration of the fiber according to the present invention lies in that the fiber bundling agent described in any one of the above is adhered thereto.

[0025] According to this configuration, the present invention is easily applicable to the reinforcement of composite materials having resins, ceramics, metals, etc. as base materials.

[0026] A further characteristic configuration of the fiber according to the present invention lies in that it is a reinforcing fiber.

[0027] According to this configuration, the present invention is even more easily applicable to the reinforcement of composite materials having resins, ceramics, metals, etc. as base materials.

[0028] A further characteristic configuration of the fiber according to the present invention lies in that the above-described fiber bundling agent is adhered to carbon fiber or glass fiber.

[0029] According to this configuration, the present invention is particularly easily applicable to the reinforcement of composite materials having resins, ceramics, metals, etc. as base materials.

Embodiments for Carrying Out the Invention

[0030] Hereinafter, embodiments of the present invention will be described. The fiber bundling agent of the present invention (hereinafter simply referred to as "bundling agent") is a fiber bundling agent containing an ester compound (A) represented by the following chemical formula (1) and a nonionic surfactant (B), and in the following chemical formula (1), it contains an ester compound (A1) in which m is 1 and an ester compound (A2) in which m is 2 and the mass ratio of the ester compound (A1) and the ester compound (A2) is 0.1 to 10, and the total content ratio of the ester compound (A1) and the ester compound (A2) in the non-volatile content of the fiber bundling agent is 0.5% by mass or more and 30% by mass or less and is characterized by that.

[0031]

Chemical formula

[0032] R 1 : An alkylene group of C1-C3 R 2 : An alkylene group or alkenyl group of C1-C4 R 3 : Each independently an alkylene group of C2 or C3 (however, when n1, n2, n3, and n4 are each 2 or more, the alkylene group can be one kind alone or two kinds) m: An integer of 1 or more and 2 or less The numerical values of n1 + n2 and n3 + n4 are 2 to 6

[0033] R 1 is an alkylene group of C1-C3 and can be, for example, a methylene group or an isopropylidene group.

[0034] R 2 is an alkylene group or alkenyl group of C1-C4, for example, a residue obtained by removing a carboxyl group from maleic acid, or a residue obtained by removing a carboxyl group from fumaric acid.

[0035] R 3 is an alkylene group of C2 or C3 and can be, for example, an ethylene group or a propylene group 。

[0036] The ester compound (A) represented by the above chemical formula (1) is a compound formed by the reaction of a raw material dihydric alcohol and a carboxylic acid. The dihydric alcohol can be produced, for example, as follows, but is not limited thereto.

[0037] That is, a mixture of a plurality of dihydric alcohols having different molecular weights is used as a raw material and dissolved in a solvent (tetrahydrofuran), and fractionated by molecular weight using a GPC fractionation device. The fractionated solution is charged into a reaction vessel equipped with a heating and cooling device and a stirring device, and the solvent (tetrahydrofuran) is gradually reduced in pressure to 20 mmHg at, for example, 80-100 °C to remove the solvent, and a dihydric alcohol can be obtained.

[0038] Examples of the mixture of dihydric alcohols include, but are not limited to, ethylene oxide adducts of bisphenol A (Newpol (registered trademark) BPE series manufactured by Sanyo Chemical Industries, Ltd. (Newpol (registered trademark) BPE-20, Newpol (registered trademark) BPE-40, Newpol (registered trademark) BPE-100, Newpol (registered trademark) BPE-60, etc.)), propylene oxide adducts of bisphenol A (Newpol (registered trademark) BP series manufactured by Sanyo Chemical Industries, Ltd. (Newpol (registered trademark) BP-2P, Newpol (registered trademark) BP-3P, Newpol (registered trademark) BP-5P, etc.)).

[0039] Examples of carboxylic acids that can be used include, but are not limited to, maleic acid, fumaric acid, adipic acid, etc.

[0040] The ester compound (A) can be produced as follows using the above dihydric alcohol and carboxylic acid.

[0041] That is, a dihydric alcohol and a carboxylic acid are added to a container such as a flask and heated and dissolved, for example, at 120°C, and then tetrabutoxytitanium is added under a nitrogen stream and heated to, for example, 180°C to carry out an esterification reaction to obtain an ester compound.

[0042] The obtained ester compound is fractionated by molecular weight using the above GPC fractionation apparatus, and then each fractionated solution is charged into the above reaction vessel equipped with a heating and cooling device and a stirring device, and the pressure is gradually reduced to 20 mmHg, for example, at 90°C to remove tetrahydrofuran, thereby obtaining the ester compound (A) represented by Chemical Formula (1).

[0043] The nonionic surfactant (B) can be any nonionic surfactant commonly used in the art. The nonionic surfactant (B) may be a single compound or a mixture of multiple compounds.

[0044] The nonionic surfactant (B) can be, for example, an alkylene oxide adduct of a compound having a hydroxy group. Examples of the compound having a hydroxy group include aromatic alcohols such as tristyrenated phenol, distyrenated phenol, and bisphenol A, and aliphatic alcohols such as dodecyl alcohol, isododecyl alcohol, tetradecyl alcohol, tridecyl alcohol, secondary dodecyl alcohol, secondary tridecyl alcohol, 2-ethylhexyl alcohol, oleyl alcohol, and isononyl alcohol. Among them, aromatic alcohols are preferred. Examples of the alkylene oxide include, but are not limited to, ethylene oxide and propylene oxide. Therefore, the nonionic surfactant (B) can preferably be an alkylene oxide adduct of an aromatic alcohol.

[0045] In the nonionic surfactant (B), a plurality of types of alkylene oxides may be used in combination. The number of moles of the added alkylene oxide can be, but is not limited to, 6 moles or more and 40 moles or less per mole of the nonionic surfactant (B).

[0046] The nonionic surfactant (B) may be a single compound or a mixture of a plurality of compounds.

[0047] As in this configuration, by containing both the ester compound (A1) in which m is 1 and the ester compound (A2) in which m is 2 in Chemical Formula (1), a fiber bundling agent excellent in resin impregnation property, smoothness, and focusing property can be obtained. It is considered that the smoothness is excellent by containing the ester compound (A1), and the resin impregnation property is excellent by containing the ester compound (A2).

[0048] The mass ratio A2 / A1 of the ester compound (A1) and the ester compound (A2) is 0.1 to 10 is provided , preferably 0.5 to 5. is preferred

[0049] The sizing agent of the present invention has a total content ratio of the ester compound (A1) and the ester compound (A2) in the non-volatile matter of the sizing agent for fibers of 0.5% by mass or more and 30% by mass or less. is provided Furthermore, it is preferably 5 to 25% by mass. is preferred This is more preferable.

[0050] According to this configuration, the abundance ratios of the ester compound (A1) and the ester compound (A2) that can be sizing agents for fibers excellent in resin impregnability, smoothness, and bundling property can be defined.

[0051] The sizing agent of the present invention preferably has a pH of 5.0 to 8.0 for a 1% by mass aqueous solution of the sizing agent for fibers.

[0052] When the pH of the aqueous solution satisfies the above requirements, it can be a sizing agent for fibers excellent in resin impregnability, smoothness, and bundling property, and particularly an effect of excellent smoothness can be obtained.

[0053] When the total content ratio of the ester compound (A) and the nonionic surfactant (B) of the sizing agent of the present invention is 100% by mass, the ester compound (A) is preferably contained in a ratio of 1 to 30% by mass, and the nonionic surfactant (B) is preferably contained in a ratio of 10 to 99% by mass.

[0054] In this configuration, the content ratios of the ester compound (A) and the nonionic surfactant (B) that can be sizing agents for fibers excellent in resin impregnability, smoothness, and bundling property can be defined.

[0055] The sizing agent of the present invention preferably further contains at least one resin (C) selected from polyester resins, epoxy resins, urethane resins, and vinyl ester resins other than the ester compound (A).

[0056] The polyester resin is a copolymer of a diol monomer and a dicarboxylic acid monomer. Therefore, the polyester resin has, in its molecule, a diol residue which is a partial structure derived from the diol monomer (a diol compound or its derivative), and a dicarboxylic acid residue which is a partial structure derived from the dicarboxylic acid monomer (a dicarboxylic acid or its derivative). The composition of the polyester resin is specified by the ratio (molar ratio) of the monomers constituting the molecule.

[0057] As the diol monomer(s) constituting the polyester resin, one or more kinds of diol compounds may be included. Examples of the diol compounds include, but are not limited to, ethylene glycol, diethylene glycol, bisphenol A, ethylene oxide adducts of bisphenol A (Newpol (registered trademark) BPE series manufactured by Sanyo Chemical Industries, Ltd. (Newpol (registered trademark) BPE-20, Newpol (registered trademark) BPE-40, Newpol (registered trademark) BPE-100, Newpol (registered trademark) BPE-60, etc.)), propylene oxide adducts of bisphenol A (Newpol (registered trademark) BP series manufactured by Sanyo Chemical Industries, Ltd. (Newpol (registered trademark) BP-2P, Newpol (registered trademark) BP-3P, Newpol (registered trademark) BP-5P, etc.)).

[0058] As the dicarboxylic acid monomer(s) constituting the polyester resin, one or more kinds of dicarboxylic acid compounds may be included. Examples of the dicarboxylic acid compounds include, but are not limited to, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, alkali metal salts of 5-sulfoisophthalic acid (sodium salt, potassium salt, lithium salt, etc.).

[0059] Non-limiting examples of the polyester resin include a copolymer of diethylene glycol, isophthalic acid, and sodium 5-sulfoisophthalate; a copolymer of ethylene glycol, diethylene glycol, isophthalic acid, terephthalic acid, and sodium 5-sulfoisophthalate; a copolymer of an ethylene oxide adduct of bisphenol A and fumaric acid (in other words, a copolymer of bisphenol A, ethylene glycol, and fumaric acid); a copolymer of an ethylene oxide adduct of bisphenol A and maleic acid (in other words, a copolymer of bisphenol A, ethylene glycol, and maleic acid). Note that the polyester resin may be a single compound or a mixture of multiple compounds.

[0060] As the polyester resin other than the ester compound (A), any of the polyester resins exemplified above can be used.

[0061] Examples of the epoxy resin include, but are not limited to, the jER (registered trademark) series (such as jER (registered trademark) 828, jER (registered trademark) 834, jER (registered trademark) 1001, jER (registered trademark) 1002, jER (registered trademark) 1004, etc.) manufactured by Mitsubishi Chemical Corporation, the NPES series (such as NPES301, NPES302, etc.) manufactured by NAN YA PLASTIC CORPORATION, and the Sumiepoxy (registered trademark) series (such as Sumiepoxy (registered trademark) ELM-434, Sumiepoxy (registered trademark) ELM-100, etc.) manufactured by Sumitomo Chemical Co., Ltd.

[0062] Examples of the urethane resin include, but are not limited to, DISPERCOLL U 54 (manufactured by Covestro), Superflex 500M (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Superflex 650 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Superflex 860 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Superflex E-2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0063] The vinyl ester resin can be, for example, a reaction product of any of the epoxy resins exemplified above and methacrylic acid. Note that the quantitative ratio of the reaction substrates when producing the reaction product may be such that the epoxy value of the epoxy resin is equal to the acid value of methacrylic acid, or either one may be made larger.

[0064] By containing any of the above resins (C), the sizing agent of the present invention can easily impart sizing properties to the fiber material.

[0065] When the total content ratio of the ester compound (A), nonionic surfactant (B), and resin (C) of the sizing agent of the present invention is 100% by mass, it is preferably contained in a ratio of 1 to 30% by mass of the ester compound (A), 10 to 99% by mass of the nonionic surfactant (B), and 0 to 89% by mass (excluding 0) of the resin (C).

[0066] According to this configuration, the content ratios of the ester compound (A), nonionic surfactant (B), and resin (C) can be defined, which can result in a sizing agent for fibers that is excellent in resin impregnation properties and smoothness and even more excellent in sizing properties.

[0067] (Other components) The sizing agent according to this embodiment may contain other components in addition to the ester compound (A), nonionic surfactant (B), and resin (C). Examples of such other components include, but are not limited to, preservatives, antistatic agents, antioxidants, ultraviolet absorbers, defoaming agents (such as modified silicone), and resins other than the resin (C).

[0068] In addition, as a typical embodiment when the sizing agent is used for sizing treatment of a fiber material, an embodiment in which a non-volatile component such as the ester compound (A) is diluted with a diluent (generally also referred to as a sizing solution) is exemplified. Such a diluent is also an example of other components. Examples of the diluent include, but are not limited to, water (such as tap water, industrial water, ion-exchanged water, distilled water), acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, and the like. The concentration of the non-volatile component in the sizing agent in the form of diluting the non-volatile component with a diluent is not particularly limited, but can be, for example, 10% by mass or more and 60% by mass or less. The non-volatile component of the sizing agent refers to the component that remains without volatilization after heating the sizing agent in a hot air dryer at 105°C for 2 hours, and the concentration thereof refers to the ratio of the mass of the non-volatile component in the sizing agent to the mass of the sizing agent.

[0069] 〔Method for producing sizing agent〕 The sizing agent according to the present embodiment can be obtained by mixing the ester compound (A), the nonionic surfactant (B), and optionally added components by a known method. For example, it can be produced by adding water while stirring the ester compound (A), the nonionic surfactant (B), and optionally added components at a temperature between 20°C and 90°C over 5 hours.

[0070] 〔Method for using sizing agent〕 The sizing agent according to the present embodiment is used for sizing treatment of a fiber material. The sizing treatment is a treatment for attaching a sizing agent to the fiber material, and as a method thereof, a method usually used for attaching this type of sizing agent to a fiber material in the art can be applied. That is, an immersion oiling method, a spray oiling method, a roller oiling method, a guide oiling method, and the like can be adopted. In addition, when applying each method, the sizing agent can be appropriately diluted with a diluent such as water.

[0071] The amount of the sizing agent attached to the fiber material is not particularly limited. For example, it is preferable that the sizing agent is attached in an amount of 0.1% by mass or more and 3% by mass or less based on the entire fiber material to which the sizing agent is attached.

[0072] When the sizing agent according to the present embodiment is applied during the production of the reinforcing fibers, reinforcing fibers with the sizing agent adhering to the fiber material can be obtained. These reinforcing fibers are an example of the fibers according to the present invention. The fiber material is preferably an inorganic fiber, and in this case, the reinforcing fibers are inorganic fibers with the sizing agent adhering thereto. Further, it is more preferable that the inorganic fiber is a carbon fiber or a glass fiber.

[0073] These reinforcing fibers can be used in composite materials having a base material such as resin, ceramic, or metal. A composite material characterized by including the above-mentioned reinforcing fibers and a matrix resin that is a thermosetting resin is one embodiment of the present invention.

[0074] 〔Other Embodiments〕 The fiber bundling agent of the present invention is a fiber bundling agent containing an ester compound (A) represented by the following chemical formula (1) and a nonionic surfactant (B), and in the following chemical formula (1), it may contain an ester compound (A1) in which m is 1 and an ester compound (A2) in which m is 2.

[0075]

Chemical

[0076] R 1 : An alkylene group having 1 to 3 carbon atoms R 2 : An alkylene group or alkenyl group having 1 to 4 carbon atoms R 3 : Each independently an alkylene group having 2 or 3 carbon atoms (however, when n 1 、n 2 、n 3 、n 4 is 2 or more, the alkylene group can be a single species or two species) m: An integer of 1 or more and 2 or less n 1 ,n 2 ,n 3 ,n 4 : Each independently an integer of 1 or more and 20 or less

[0077] R 1 is an alkylene group having 1 to 3 carbon atoms, and can be, for example, a methylene group or an isopropylidene group.

[0078] R 2 is an alkylene group or alkenyl group having 1 to 4 carbon atoms, and can be, for example, a residue obtained by removing a carboxyl group from maleic acid, or a residue obtained by removing a carboxyl group from fumaric acid.

[0079] R 3 is an alkylene group having 2 or 3 carbon atoms, and can be, for example, an ethylene group or a propylene group. n 1 ,n 2 ,n 3 ,n 4 Although it is an integer of 1 or more and 20 or less, it is preferably 1 to 10.

[0080] According to this configuration, in the chemical formula (1), by containing both the ester compound (A1) in which m is 1 and the ester compound (A2) in which m is 2, it can become a fiber bundling agent excellent in resin impregnation property, smoothness, and bundling property.

[0081] In the fiber bundling agent of this embodiment, the total content ratio of the ester compound (A1) and the ester compound (A2) in the nonvolatile content of the fiber bundling agent is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 5 to 25% by mass.

[0082] According to this configuration, the abundance ratios of the ester compound (A1) and the ester compound (A2) that can become a fiber bundling agent excellent in resin impregnation property, smoothness, and bundling property can be defined.

[0083] Regarding other configurations as well, it should be understood that all the embodiments disclosed in this specification are illustrative in all respects and the scope of the present invention is not limited thereby. Those skilled in the art will easily understand that appropriate modifications can be made without departing from the spirit of the present invention. Therefore, other embodiments modified without departing from the spirit of the present invention are naturally included in the scope of the present invention.

Example

[0084] 〔Example 1〕 The ester compound (A) represented by the chemical formula (1) of the present invention was produced by the following method.

[0085] First, a dihydric alcohol as a raw material was produced. A total of 400 g of Newpol (registered trademark) BPE-20 (manufactured by Sanyo Chemical Industries, Ltd.) 200 g and Newpol (registered trademark) BPE-60 (manufactured by Sanyo Chemical Industries, Ltd.) 200 g was dissolved in tetrahydrofuran as a solvent so that the solid content concentration became 2%, and fractionated by molecular weight using a GPC fractionation apparatus (Recycling fractionation HPLC: LC-9130NEXT (manufactured by Japan Analytical Industry Co., Ltd.)).

[0086] Thereafter, each fractionated solution was charged into a reaction vessel (glass four-necked flask reaction vessel) equipped with a heating and cooling device and a stirring device, and the pressure was gradually reduced to 20 mmHg at 90 °C to remove tetrahydrofuran, and the following compounds (N-1) to (N-5) (dihydric alcohol) were obtained.

[0087] · R in Chemical Formula (2) 4 is an isopropylidene group, R 5 is an ethylene group, and a compound (N-1) (molecular weight 316) obtained by adding 2 moles of ethylene oxide to bisphenol A where n5 + n6 is 2 · R in Chemical Formula (2) 4 is an isopropylidene group, R 5 is an ethylene group, and a compound (N-2) (molecular weight 360) obtained by adding 3 moles of ethylene oxide to bisphenol A where n5 + n6 is 3 · R in Chemical Formula (2) 4 is an isopropylidene group, R 5 is an ethylene group, and a compound (N-3) (molecular weight 404) obtained by adding 4 moles of ethylene oxide to bisphenol A where n5 + n6 is 4 · R in Chemical Formula (2) 4 is an isopropylidene group, R 5 is an ethylene group, and a compound (N-4) (molecular weight 448) obtained by adding 5 moles of ethylene oxide to bisphenol A where n5 + n6 is 5 · R in Chemical Formula (2) 4 is an isopropylidene group, R 5 is an ethylene group, and a compound (N-5) (molecular weight 492) obtained by adding 6 moles of ethylene oxide to bisphenol A where n5 + n6 is 6

[0088]

Chemical Structure

[0089] Also, 400 g of Newpol (registered trademark) BP-2P (manufactured by Sanyo Chemical Industries, Ltd.) was dissolved in tetrahydrofuran so that the solid content concentration became 2%, and fractionated by molecular weight using the above GPC fractionation apparatus. Then, each fractionated solution was charged into the above reaction vessel equipped with a heating and cooling device and a stirring device, and the pressure was gradually reduced to 20 mmHg at 90 °C to remove tetrahydrofuran, and the following compound (N-6) (dihydric alcohol) was obtained.

[0090] · R in Chemical Formula (2) 4 is an isopropylidene group, R 5 is a propylene group, and a compound (N-6) (molecular weight 344) obtained by adding 2 moles of propylene oxide to bisphenol A where n5 + n6 is 2

[0091] Using the dihydric alcohol and carboxylic acid produced as described above, an ester compound (A) was produced as follows.

[0092] 116 parts by mass of maleic acid and 632 parts by mass of compound (N-1) were added to a four-necked flask made of glass and heated and dissolved at 120 °C. Then, 1 part by mass of tetrabutoxytitanium was added under a nitrogen stream and heated to 180 °C to carry out an esterification reaction for 10 hours to obtain an ester compound.

[0093] The obtained ester compound was fractionated by molecular weight using the above GPC fractionation apparatus. Then, each fractionated solution was charged into the above reaction vessel equipped with a heating and cooling device and a stirring device, and the pressure was gradually reduced to 20 mmHg at 90 °C to remove tetrahydrofuran. R in Chemical Formula (1) 1 is an isopropylidene group, R 2 is a residue obtained by removing two carboxyl groups from maleic acid, R 3 is an ethylene group, m is 1, n1 + n2 is 2, n3 + n4 is 2, and an ester compound (A1-1) (molecular weight 712) was obtained.

[0094] For other ester compounds (A1-2) to (A1-7) where m is 1 and ester compounds (A2-1) to (A2-7) where m is 2, they were produced in the same manner except that the carboxylic acid and dihydric alcohol used were changed. Table 1 shows the outlines of ester compounds (A1-1) to (A1-7), and Table 2 shows the outlines of ester compounds (A2-1) to (A2-7).

[0095]

Table 1

[0096]

Table 2

[0097] 〔Example 2〕 The flocculant of the present invention was produced by the above method for producing a flocculant (Examples 1 to 11 of the present invention). That is, it was produced by adding water over 5 hours while stirring an ester compound (A), a nonionic surfactant (B), and optionally added components at a temperature between 20°C and 90°C. In Examples 1 to 11 of the present invention, the ester compound (A) contains an ester compound (A1) and an ester compound (A2), and the nonionic surfactant (B) contains at least one of (B-1) to (B-3) shown below.

[0098] (B-1): A compound obtained by adding 20 moles of ethylene oxide and 8 moles of propylene oxide to 1 mole of tristyrenated phenol (B-2): A compound obtained by adding 35 moles of ethylene oxide to 1 mole of tristyrenated phenol (B-3): A compound obtained by adding 20 moles of ethylene oxide to 1 mole of bisphenol A

[0099] Also, in Examples 1 to 9 of the present invention, the resin (C) contains at least one of (EP-1), (EP-2), (EP-3), (PE-1), (PE-2), (PE-3), (PE-4), (PE-5), (PU-1), (VE-1) shown below.

[0100] (EP-1): Epotope YD-128 (manufactured by Nippon Steel Chemical & Material Co., Ltd.) (epoxy resin) (EP-2): Epotope YD-011 (manufactured by Nippon Steel Chemical & Material Co., Ltd.) (epoxy resin) (EP-3): Epotope YD-012 (manufactured by Nippon Steel Chemical & Material Co., Ltd.) (epoxy resin) (PE-1): In chemical formula (1), R 1 is an isopropylidene group, R 2 is a residue obtained by removing a carboxyl group from maleic acid, R 3A resin compound in which the alkylene group has 2 carbon atoms, n1 + n2 = 4, n3 + n4 = 4, and m = 4 (PE-2): In chemical formula (1), R 1 is an isopropylidene group, R 2 is the residue obtained by removing the carboxyl group from fumaric acid, R 3 is an alkylene group having 2 carbon atoms, n1 + n2 = 4, n3 + n4 = 4, and m = 3 (PE-3): In chemical formula (1), R 1 is an isopropylidene group, R 2 is the residue obtained by removing the carboxyl group from fumaric acid, R 3 is an alkylene group having 2 carbon atoms, n1 + n2 = 8, n3 + n4 = 8, and m = 5 (PE-4): In chemical formula (1), R 1 is an isopropylidene group, R 2 is the residue obtained by removing the carboxyl group from maleic acid, R 3 is an alkylene group having 2 carbon atoms, n1 + n2 = 12, n3 + n4 = 12, and m = 6 (PE-5): A polyester resin with a molar ratio of 5-sodium sulfoisophthalic acid: isophthalic acid: diethylene glycol of 4:46:50 and a number average molecular weight of 15,000 (PU-1): A urethane resin that is the non-volatile resin portion of DISPERCOLL U 54 (manufactured by Covestro) (VE-1): A vinyl ester resin produced by reacting jER828 (manufactured by Mitsubishi Chemical Corporation) and methacrylic acid in a molar ratio of 1:2

[0101] Table 3 shows the mass percentages of the ester compound (A), nonionic surfactant (B), and resin (C) in Invention Examples 1 to 11 of the present invention (total 100 mass%). For example, the proportion of each component in Invention Example 1 of the present invention is: ester compound (A1-1): 5 mass%, ester compound (A2-1): 10 mass%, nonionic surfactant (B-1): 30 mass%, resin (EP-1): 15 mass%, resin (EP-2): 10 mass%, resin (PE-1): 30 mass%.

[0102] In addition, the values of the weight ratio A2 / A1 of the ester compound (A1) and the ester compound (A2) are shown in Table 3.

[0103] [Table 3]

[0104] In addition, Example 11 of the present invention contains acetic acid (E-1) as other components.

[0105] The sizing agents of the comparative examples were produced by the above-described method for producing a sizing agent (Comparative Examples 1 to 3). In Comparative Example 1, the ester compound (A) was not contained, the nonionic surfactant (B) contained (B-1) and (B-2), and the resin (C) contained (EP-1) and (PE-3). In Comparative Example 2, the ester compound (A) contained (A1-1), the nonionic surfactant (B) contained (B-1), and the resin (C) contained (EP-1), (EP-2), and (PE-1). In Comparative Example 3, the ester compound (A) contained (A2-1), the nonionic surfactant (B) contained (B-1), and the resin (C) contained (EP-1), (EP-2), and (PE-1). The mass percentages of the ester compound (A), the nonionic surfactant (B), and the resin (C) in Comparative Examples 1 to 3 are shown in Table 3 (total 100 mass%).

[0106] [Evaluation Method] Regarding the above-described Examples 1 to 11 and Comparative Examples 1 to 3 of the present invention, the resin impregnability, smoothness, and sizing property of the sizing agent were evaluated. A sizing solution (nonvolatile content concentration 4%) containing the sizing agent of each Example of the present invention and each Comparative Example was filled in a sizing bath, and the sizing agent was applied by passing carbon fibers through the sizing bath.

[0107] (Resin Impregnability) After applying the sizing agent, the carbon fiber bundle was opened to a width of 1 cm using a chromium-plated satin pin with a diameter of 1 cm as an opening fiber bar. 0.06 g of epoxy resin (trade name: jER828, manufactured by Mitsubishi Chemical Corporation) as a matrix resin was dropped onto the carbon fiber bundle at 25°C, and the maximum diameter of the epoxy resin 60 seconds after dropping was measured. Based on this measurement result, the impregnability with the matrix resin was evaluated according to the following criteria.

[0108] A: The maximum diameter is 4 mm or more. B: The maximum diameter is less than 4 mm.

[0109] (Smoothness) 1.5 m of the carbon fiber bundle after applying the sizing agent was taken out, one end was clamped by the clip of the autograph, a 50 g weight was hung at the opposite end, and a chromium satin rubbing body with a diameter of 1 cm rotating at 500 rpm was brought into contact at an angle of 135°, and the average load when pulling at 0.25 m / min was measured, and the smoothness was evaluated according to the following criteria.

[0110] A: Less than 2.5 N. B: 2.5 N or more and less than 3 N. C: 3 N or more.

[0111] (Bundle property) The roll of the carbon fiber bundle after applying the sizing agent was set on the creel and unwound at a speed of 5 m per minute, and the state of the fiber material passing through the roller immediately after unwinding was observed. According to the observation results, the bundling properties of the carbon fiber bundles brought about by the sizing agents of each inventive example and each comparative example were evaluated in the following three levels.

[0112] A: Almost no carbon fiber wound around the roller, and the aggregation of the carbon fibers that passed through was good. B: A small amount of carbon fiber wound around the roller was seen, but the aggregation of the carbon fibers that passed through was good. C: A large amount of carbon fiber wound around the roller was seen, and the passed carbon fibers were scattered.

[0113] <Evaluation results> The evaluation results of the resin impregnability, smoothness, and bundling properties of each inventive example and each comparative example are shown in Table 3.

[0114] Regarding the resin impregnability, for Invention Examples 1 to 11 of the present invention, an A evaluation was obtained, while for Comparative Examples 1 and 2, a B evaluation was obtained. For Comparative Example 3, an A evaluation was obtained.

[0115] Regarding the smoothness, for Invention Examples 1 to 10 of the present invention, an A evaluation was obtained, and for Invention Example 11, a B evaluation was obtained. For Comparative Examples 1 and 2, an A evaluation was obtained, and for Comparative Example 3, a C evaluation was obtained.

[0116] Regarding the focusing property, for Invention Examples 1 to 9 of the present invention, an A evaluation was obtained, and for Invention Examples 10 and 11, a B evaluation was obtained. For Comparative Examples 1 to 3, an A evaluation was obtained.

[0117] The focusing agent of the present invention (Invention Examples 1 to 11) contains both ester compound (A1) and ester compound (A2). In contrast, Comparative Examples 1 to 3 are configured not to contain both ester compound (A1) and ester compound (A2) (either only one of them or neither).

[0118] From the above, it was recognized that the focusing agent of the present invention (Invention Examples 1 to 11) can be a fiber focusing agent excellent in resin impregnability, smoothness, and focusing property by containing both ester compound (A1) and ester compound (A2).

[0119] In Invention Examples 1 to 11 of the present invention, the mass ratio A2 / A1 of ester compound (A1) and ester compound (A2) was 1.43 to 4.00.

[0120] In Invention Examples 1 to 11 of the present invention, the total content ratio of ester compound (A1) and ester compound (A2) was 5 to 25% by mass.

[0121] It was recognized that when the abundance ratios of ester compound (A1) and ester compound (A2) satisfy the above requirements, it can be a fiber focusing agent excellent in resin impregnability, smoothness, and focusing property.

[0122] Total content ratio of ester compound (A1) and ester compound (A2) If it is contained in a ratio of 0.5% by mass or more and 30% by mass or less, it is considered that the same effects as above can be obtained.

[0123] In Invention Examples 1 to 11 of the present invention, the pH of the aqueous liquid was 4.5 to 7.5.

[0124] It was recognized that when the pH of the aqueous liquid satisfies the above requirements, it can become a fiber sizing agent excellent in resin impregnation property, smoothness, and bundling property.

[0125] In Invention Examples 1 to 10 of the present invention, an A evaluation was obtained for smoothness, and the pH of the aqueous liquid at this time was 5.5 to 7.5. Therefore, for example, if the pH of the aqueous liquid is 5.0 to 8.0, it is considered that an effect of particularly excellent smoothness can be obtained.

[0126] In Invention Examples 10 and 11, the total content ratio of ester compound (A) and nonionic surfactant (B) was 100% by mass. That is, in Invention Examples 10 and 11, the content ratio of ester compound (A) (ester compound (A1) and ester compound (A2)) was 20% by mass, and the content ratio of nonionic surfactant (B) was 78 to 80% by mass.

[0127] It was recognized that when the abundance ratio of each constituent component satisfies the above requirements, it can become a fiber sizing agent excellent in resin impregnation property, smoothness, and bundling property.

[0128] When the total content ratio of ester compound (A) and nonionic surfactant (B) is 100% by mass (Invention Examples 10 and 11), if ester compound (A) is contained in a ratio of 1 to 30% by mass and nonionic surfactant (B) is contained in a ratio of 10 to 99% by mass, it is considered that the same effects as above can be obtained.

[0129] In Invention Examples 1 to 9, the total content ratio of the ester compound (A), nonionic surfactant (B), and resin (C) was 100% by mass. That is, in Invention Examples 1 to 11, the content ratio of the ester compound (A) was 5 to 25% by mass, the content ratio of the nonionic surfactant (B) was 25 to 32% by mass, and the content ratio of the resin (C) was 45 to 65% by mass.

[0130] In Invention Examples 1 to 9, since an A evaluation was obtained for the focusing property, it was recognized that by containing the resin (C) as in Invention Examples 1 to 9, it becomes easier to impart focusing property to the fiber material.

[0131] When the total content ratio of the ester compound (A), nonionic surfactant (B), and resin (C) is 100% by mass, if the ester compound (A) is contained in a ratio of 1 to 30% by mass, the nonionic surfactant (B) is contained in a ratio of 10 to 99% by mass, and the resin (C) is contained in a ratio of 0 to 89% by mass (excluding 0), it is considered that the same effects as above can be obtained.

[0132] Since Comparative Examples 1 to 3 do not contain both the ester compound (A1) and the ester compound (A2), it was recognized that they cannot achieve excellent results in terms of all of crystal suppression property, smoothness, and focusing property like the focusing agent of the present invention.

Industrial Applicability

[0133] The present invention can be used, for example, in the sizing treatment of fiber materials.

Claims

1. A fiber sizing agent containing an ester compound (A) represented by the following chemical formula (1) and a nonionic surfactant (B), The fiber sizing agent is characterized by containing an ester compound (A1) in which m is 1 and an ester compound (A2) in which m is 2 in the following chemical formula (1). 【Chemical 1】 R １ : An alkylene group of C1 to C3 R ２ : An alkylene or alkenyl group having 1 to 4 carbon atoms R ３ : Each independently a C2 or C3 alkylene group (provided that when n １ , n ２ , n ３ , n ４ are each 2 or more, the alkylene group can be one kind alone or two kinds) m: An integer of 1 or more and 2 or less n １ ,n ２ ,n ３ ,n ４ : each independently an integer of 1 or more and 20 or less

2. The fiber sizing agent according to Claim 1, wherein the total content ratio of the ester compound (A1) and the ester compound (A2) in the nonvolatile content of the fiber sizing agent is 0.5% by mass or more and 30% by mass or less.

3. The fiber sizing agent according to Claim 1, wherein the pH of a 1% by mass aqueous solution of the fiber sizing agent is 5.0 to 8.

0.

4. When the total content ratio of the ester compound (A) and the nonionic surfactant (B) is 100% by mass, the ester compound (A) is contained in a ratio of 1 to 30% by mass, and the nonionic surfactant (B) is contained in a ratio of 10 to 99% by mass. The fiber sizing agent according to Claim 1.

5. The fiber sizing agent according to Claim 1, further containing at least one resin (C) selected from polyester resins, epoxy resins, urethane resins, and vinyl ester resins other than the ester compound (A).

6. When the total content ratio of the ester compound (A), the nonionic surfactant (B), and the resin (C) is 100% by mass, the ester compound (A) is 1 to 30% by mass, the nonionic surfactant (B) is 10 to 99% by mass, and the resin (C) is 0 to 89% by mass (excluding 0). The fiber sizing agent according to Claim 5.

7. A fiber characterized in that the fiber sizing agent according to any one of Claims 1 to 6 is attached.

8. The fiber according to Claim 7, which is a reinforcing fiber.

9. The fiber according to Claim 7, wherein the fiber sizing agent is attached to carbon fiber or glass fiber.

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