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JP-7854765-B1 - Sizing agents for reinforcing fibers, reinforcing fibers, and fiber composite materials

JP7854765B1JP 7854765 B1JP7854765 B1JP 7854765B1JP-7854765-B1

Abstract

[Problem] To realize a sizing agent for reinforcing fibers that has emulsion stability while improving the penetration rate when impregnating reinforcing fibers with matrix resin. Furthermore, to realize reinforcing fibers in which the sizing agent for reinforcing fibers is attached to the fiber material, and fiber composite materials using such reinforcing fibers as a reinforcing material. [Solution] The sizing agent for reinforcing fibers contains a resin and a nonionic surfactant containing a benzylated phenol derivative (A), which is an alkylene oxide adduct of benzylated phenols having at least one benzyl group, wherein the benzylated phenol derivative (A) contains a dibenzylated phenol derivative (A2), which is an adduct in which a total of 1 to 100 moles of alkylene oxide are added to 1 mole of dibenzylated phenol. In the case of reinforcing fibers, the sizing agent for reinforcing fibers is attached to the fiber material. In the case of fiber composite materials, the matrix resin is impregnated into the reinforcing fibers. [Selection Diagram] None

Inventors

  • 加藤 岳人

Assignees

  • 竹本油脂株式会社

Dates

Publication Date
20260507
Application Date
20251210

Claims (9)

  1. resin and A nonionic surfactant containing a benzylated phenol derivative (A) which is an alkylene oxide adduct of benzylated phenols that are phenol-substituted products having at least one benzyl group, A sizing agent for reinforcing fibers, characterized in that the benzylated phenol derivative (A) contains a dibenzylated phenol derivative (A2) which is an adduct obtained by adding a total of 1 to 100 moles of alkylene oxide to 1 mole of dibenzylated phenol.
  2. The sizing agent for reinforcing fibers according to claim 1, wherein the alkylene oxide in the dibenzylated phenol derivative (A2) comprises at least ethylene oxide and propylene oxide.
  3. The sizing agent for reinforcing fibers according to claim 1, further comprising a tripenzylated phenol derivative (A3), which is an adduct in which a total of 1 to 100 moles of alkylene oxide are added to 1 mole of tripenzylated phenol.
  4. The sizing agent for reinforcing fibers according to claim 3, comprising the dibenzylated phenol derivative (A2) and the tripenzylated phenol derivative (A3) in a mass ratio of dibenzylated phenol derivative (A2) / tripenzylated phenol derivative (A3) = 10 / 90 to 80 / 20.
  5. The sizing agent for reinforcing fibers according to claim 1, wherein the benzylated phenol derivative (A) comprises at least one of the following: a monobenzylated phenol derivative (A1), which is an adduct obtained by adding a total of 1 to 100 moles of alkylene oxide to 1 mole of monobenzylated phenol; and a polybenzylated phenol derivative (A4), which is an adduct obtained by adding a total of 1 to 100 moles of alkylene oxide to 1 mole of polybenzylated phenol having four or more benzyl groups.
  6. The sizing agent for reinforcing fibers according to claim 1, comprising the benzylated phenol derivative (A) in a proportion of 5 to 50% by mass in the nonvolatile content.
  7. The sizing agent for reinforcing fibers according to claim 1, wherein the resin comprises at least one selected from the group consisting of epoxy resin, vinyl ester resin, polyolefin resin, polyurethane resin, acrylic resin, and polyester resin.
  8. A reinforced fiber characterized in that the sizing agent for reinforcing fibers described in any one of claims 1 to 7 is attached to the fiber material.
  9. A fiber composite material comprising reinforcing fibers impregnated with a matrix resin, as described in claim 8.

Description

This invention relates to a sizing agent for reinforcing fibers, reinforcing fibers, and fiber composite materials. Fiber composite materials, in which reinforcing fibers such as carbon fibers and glass fibers are impregnated with matrix resins such as epoxy resins, are widely used in fields such as machinery, construction materials, and transportation equipment. Before impregnation with the matrix resin, the reinforcing fibers used in fiber composite materials undergo a treatment in which a sizing agent (also called a sizing agent) is applied to reduce damage to the reinforcing fibers and improve their ability to bundle. As an example of this type of sizing agent, Japanese Patent Publication No. 2019-99942 (Patent Document 1) discloses a carbon fiber sizing composition containing a sizing agent and a nonionic surfactant, wherein the nonionic surfactant includes an alkylene oxide adduct of distyrenated phenol and an alkylene oxide adduct of tristyrenated phenol. Japanese Patent Publication No. 2019-99942 Embodiments of the sizing agent for reinforcing fibers, reinforcing fibers, and fiber composite materials according to the present invention will be described. [1] Sizing agent for reinforcing fibers The sizing agent for reinforcing fibers according to this embodiment (hereinafter also simply referred to as the sizing agent) contains at least a resin and a nonionic surfactant. (1) Resin The type of resin is not limited as long as it is a resin that is dispersed or dissolved in the sizing agent. Preferably, the resin includes at least one selected from the group consisting of epoxy resins, vinyl ester resins, polyolefin resins, polyurethane resins, acrylic resins, and polyester resins. Any known epoxy resin can be used without particular limitation. The epoxy resin may be a commercially available product, and examples include, but are not limited to, the Epotote® series (manufactured by Nippon Steel Chemical & Material Co., Ltd.), Denacol (manufactured by Nagase ChemteX Corporation), and the KER series (manufactured by Kumho P&B Chemicals, Inc.). Vinyl ester resin is a thermosetting resin obtained, for example, by the reaction of an epoxy resin with an unsaturated monocarboxylic acid. Any known vinyl ester resin can be used without particular limitation. The vinyl ester resin may be a commercially available product; examples include commercially available epoxy resins reacted with unsaturated monocarboxylic acids. As the polyolefin resin, known polyolefin resins, modified polyolefin resins, etc., can be used without particular limitation. The polyolefin resin (especially the modified polyolefin resin) may be a commercially available product, and examples include, but are not limited to, the MGP series (manufactured by Maruyoshi Chemical Co., Ltd.), the Hi-Tec P series (manufactured by Toho Chemical Industry Co., Ltd.), and the Sumikaflex series (manufactured by Sumitomo Chemical Co., Ltd.). Any known urethane resin can be used without particular limitation. The urethane resin may be a commercially available product, and examples include, but are not limited to, the Superflex® series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Dispacol® series (manufactured by Sumika Covestro Urethane Co., Ltd.), Vibond® series (manufactured by Sumika Covestro Urethane Co., Ltd.), Vihydrol® series (manufactured by Sumika Covestro Urethane Co., Ltd.), ETERNACOLL® series (manufactured by UBE Co., Ltd.), Adekabon Titer® HUX series (manufactured by ADEKA Corporation), and MELUSI® series (manufactured by Toyo Polymer Co., Ltd.). Any known acrylic resin can be used without particular restriction. The acrylic resin may be a commercially available product; examples include the Acryset series (manufactured by Nippon Shokubai Co., Ltd.) and Nikazol (manufactured by Nippon Carbide Industries Co., Ltd.). Any known polyester resin can be used without particular limitation. The polyester resin may be a commercially available product; for example, the Hi-Tech PE series (manufactured by Toho Chemical Industry Co., Ltd.) is an example without limitation. The resin may be provided as a liquid resin and used by incorporating it into the sizing agent. Alternatively, the resin may be provided as a mixture, such as a solution or dispersion, when preparing the sizing agent; the commercially available products exemplified above may be such mixtures. In this case, components other than the resin in the mixture (such as solvents and dispersants) may be included in the sizing agent without being removed. Furthermore, the resin may consist of a single component or a mixture of multiple resins. In the sizing agent of this embodiment, the resin is preferably present in an amount of 45% by mass or more, and more preferably 50% by mass or more, within the non-volatile content of the sizing agent. Furthermore, it is preferably present in an amount of 90% by mass or less, and more preferably 85% by mass or less. If multiple types of resins are included