WO2024142590A1 - エポキシ樹脂硬化剤、エポキシ樹脂組成物及び塗料 - Google Patents

エポキシ樹脂硬化剤、エポキシ樹脂組成物及び塗料 Download PDF

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Publication number
WO2024142590A1
WO2024142590A1 PCT/JP2023/039172 JP2023039172W WO2024142590A1 WO 2024142590 A1 WO2024142590 A1 WO 2024142590A1 JP 2023039172 W JP2023039172 W JP 2023039172W WO 2024142590 A1 WO2024142590 A1 WO 2024142590A1
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Prior art keywords
epoxy resin
component
curing agent
mass
resin composition
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PCT/JP2023/039172
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English (en)
French (fr)
Japanese (ja)
Inventor
拓磨 花岡
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Publication date
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Priority to CN202380087870.4A priority Critical patent/CN120390763A/zh
Priority to JP2024567249A priority patent/JPWO2024142590A1/ja
Priority to EP23911374.9A priority patent/EP4644455A4/en
Priority to KR1020257020879A priority patent/KR20250127075A/ko
Priority to US19/139,409 priority patent/US20260085148A1/en
Publication of WO2024142590A1 publication Critical patent/WO2024142590A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • Patent Document 1 describes that an aqueous epoxy resin system comprising a water-dispersible epoxy resin A having on average at least one epoxy group per molecule and a water-soluble or water-dispersible curing agent B, the curing agent B comprising an amine B1 having at least one primary amino group and/or at least one secondary amino group, an adduct B2 of a polyalkylene ether polyol B21 and an epoxide component B22, and an aromatic compound B3 having at least one acidic group selected from the group consisting of a hydroxyl group and a carboxyl group, and a coating material containing the aqueous epoxy resin system have good corrosion resistance against salt water.
  • An object of the present invention is to provide an epoxy resin curing agent which can be applied to an aqueous epoxy resin composition and can form a coating film excellent in appearance, hardness and water resistance, and an epoxy resin composition and a coating material containing the curing agent.
  • a reaction composition (A) comprising a reaction product of the following component (a12) and component (a3): Component (a12): A reaction composition containing a reaction product of a polyalkylene glycol (a1) and a polyepoxy compound (a2) having a ring structure.
  • Component (a3) An epoxy resin curing agent containing a polyamine having a ring structure, an epoxy resin curing agent, wherein a mass ratio of the component (a1) to a total amount of the components (a1) and (a2), [(a1)/ ⁇ (a1)+(a2) ⁇ ], is 0.28 to 0.50, and a reaction molar ratio of the component (a12) to the component (a3), [(a12)/(a3)], is 1/4 to 1/2.
  • the present invention provides an epoxy resin curing agent that can be applied to water-based epoxy resin compositions and can form coating films that are excellent in appearance, hardness, and water resistance, as well as an epoxy resin composition and paint that contain the curing agent.
  • 4(a) to 4(c) are photographs showing the appearance of coating films formed using the epoxy resin compositions of Example 1, Example 2, and Comparative Example 1, respectively.
  • water-based epoxy resin composition refers to an epoxy resin composition containing at least a base epoxy resin, an epoxy resin curing agent, and a dispersion medium, the main component of which is water.
  • main component means that other components may be included within the scope of the present invention, and preferably means 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass of the total.
  • reaction composition containing a reactant of X and Y refers to a composition obtained by reacting X with Y, which contains not only the reactant (adduct) of X and Y, but also by-products other than the reactant, and unreacted raw materials X and Y.
  • the epoxy resin curing agent of the present invention (hereinafter, also simply referred to as “curing agent (of the present invention)”) comprises a reaction composition (A) containing a reaction product of the following component (a12) and component (a3): Component (a12): A reaction composition containing a reaction product of a polyalkylene glycol (a1) and a polyepoxy compound (a2) having a ring structure.
  • Component (a3) An epoxy resin curing agent containing a polyamine having a ring structure, wherein the mass ratio of the component (a1) to the total amount of the components (a1) and (a2), [(a1)/ ⁇ (a1)+(a2) ⁇ ], is 0.28 to 0.50, and the reaction molar ratio of the component (a12) to the component (a3), [(a12)/(a3)], is 1/4 to 1/2.
  • the curing agent of the present invention can be applied to an aqueous epoxy resin composition by containing the reactive composition (A).
  • the epoxy resin composition and the coating material containing the curing agent can form a coating film excellent in appearance, hardness, and water resistance.
  • the polyamine component (a3) is a compound that can act as an epoxy resin curing agent. Since component (a3) has a ring structure, it is believed that when used as an epoxy resin curing agent, it contributes to improving the hardness and water resistance of the coating film of the obtained epoxy resin composition. However, when a highly hydrophilic aqueous epoxy resin is used as the base epoxy resin, there is a limit to the improvement in water resistance of the resulting coating film even when a polyamine, component (a3), is used as a curing agent.
  • component (a2) is preferably a polyepoxy compound having an aromatic ring or an alicyclic structure, more preferably a polyepoxy compound having an aromatic ring, even more preferably at least one selected from the group consisting of polyfunctional epoxy resins having glycidyloxy groups derived from bisphenol A and polyfunctional epoxy resins having glycidyloxy groups derived from bisphenol F, and even more preferably a polyfunctional epoxy resin having glycidyloxy groups derived from bisphenol A.
  • the heating temperature during the reaction of component (a1) with component (a2) is preferably 60 to 180°C, more preferably 80 to 160°C, and even more preferably 100 to 150°C, from the viewpoint of improving production efficiency and suppressing thermal degradation of component (a1) and component (a2).
  • the reaction time between component (a1) and component (a2) depends on the production scale, etc., but is usually in the range of 0.5 to 12 hours, and preferably 0.5 to 6 hours.
  • the mass X (g/mol) per mole of component (a12) is the value obtained by multiplying the epoxy equivalent (g/equivalent) of component (a12) by the number of epoxy groups in one molecule of the "reaction product of polyalkylene glycol (a1) and polyepoxy compound (a2) having a ring structure.”
  • the epoxy equivalent of component (a12) can be measured by the titration method described in the Examples, as described above.
  • the non-aqueous epoxy resin may be any epoxy resin having a glycidyl group that reacts with the active hydrogen of the epoxy resin curing agent. From the viewpoint of improving the appearance, hardness and water resistance of the coating film of the obtained epoxy resin composition, it is preferable that the non-aqueous epoxy resin contains an aromatic ring or an alicyclic structure in the molecule.
  • the epoxy resin composition may further contain an aqueous solvent other than water.
  • aqueous solvent include protic polar solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol (propylene glycol monomethyl ether), 1-ethoxy-2-propanol, and 1-propoxy-2-propanol, and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.
  • reaction composition A1 The component (a12) in the separable flask was cooled to 80°C, and 43.2 g (0.318 mol) of metaxylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is the component (a3), was added dropwise thereto over 1 hour. After the dropwise addition was completed, the mixture was stirred at 80°C for 1 hour to react, thereby obtaining a reaction composition A1 containing a reaction product of the component (a12) and MXDA.
  • the reaction molar ratio [(a12)/(a3)] of the component (a12) and the component (a3) used in the production of the reaction composition A1 was 1/3.
  • a comparative reaction composition A' containing a reaction product of the component (a12) and MXDA was obtained by carrying out the same operation as in Production Example 1, except that the amount of metaxylylenediamine used in Production Example 1 was changed to 72.0 g (0.530 mol). Furthermore, the comparative reaction composition A' was diluted with pure water to a non-volatile content of 50 mass %, to obtain a comparative reaction composition solution A'.
  • the reaction molar ratio [(a12)/(a3)] of the component (a12) and the component (a3) used in the production of the comparative reaction composition A' was 1/5.
  • the AHEW of the comparative reaction composition solution A' (total amount including water and PGM) was 167.
  • Example 1 (Preparation and Evaluation of Epoxy Resin Composition)
  • the reaction composition solution A1 obtained in Production Example 1 was used as the curing agent solution, and the pigment-containing base solution 1 obtained in Production Example 4 was used as the base solution. These were mixed in the ratio shown in Table 2, and water was further added and mixed so that the non-volatile content was 40 mass %, to prepare an epoxy resin composition having the composition shown in Table 2.
  • the obtained epoxy resin composition was used to carry out the above-mentioned evaluations. The results are shown in Table 2.
  • Example 2 An epoxy resin composition was prepared and evaluated in the same manner as in Example 1, except that the reaction composition solution A2 obtained in Production Example 2 was used instead of the reaction composition solution A1 in Example 1. The results are shown in Table 2.
  • Example 3 The reaction composition solution A1 obtained in Production Example 1 was used as the curing agent solution, and a polyfunctional epoxy resin having a glycidyloxy group derived from bisphenol A (bisphenol A diglycidyl ether (DGEBA), "jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g/equivalent) was used as the base resin. These were mixed in the ratio shown in Table 3, and water was further added and mixed so that the non-volatile content was 40 mass %, to prepare an epoxy resin composition having the composition shown in Table 3. The above-mentioned evaluations were performed using the obtained epoxy resin composition. The results are shown in Table 3.
  • an epoxy resin curing agent which can be applied to an aqueous epoxy resin composition and can form a coating film excellent in appearance, hardness and water resistance, as well as an epoxy resin composition and a coating material containing the curing agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
PCT/JP2023/039172 2022-12-27 2023-10-31 エポキシ樹脂硬化剤、エポキシ樹脂組成物及び塗料 Ceased WO2024142590A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202380087870.4A CN120390763A (zh) 2022-12-27 2023-10-31 环氧树脂固化剂、环氧树脂组合物及涂料
JP2024567249A JPWO2024142590A1 (https=) 2022-12-27 2023-10-31
EP23911374.9A EP4644455A4 (en) 2022-12-27 2023-10-31 EPOXY RESIN HARDENING AGENT, EPOXY RESIN COMPOSITION AND COATING AGENT
KR1020257020879A KR20250127075A (ko) 2022-12-27 2023-10-31 에폭시 수지 경화제, 에폭시 수지 조성물 및 도료
US19/139,409 US20260085148A1 (en) 2022-12-27 2023-10-31 Epoxy resin curing agent, epoxy resin composition, and coating agent

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Application Number Priority Date Filing Date Title
JP2022-209325 2022-12-27
JP2022209325 2022-12-27

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US (1) US20260085148A1 (https=)
EP (1) EP4644455A4 (https=)
JP (1) JPWO2024142590A1 (https=)
KR (1) KR20250127075A (https=)
CN (1) CN120390763A (https=)
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04351628A (ja) * 1991-05-28 1992-12-07 Asahi Denka Kogyo Kk 水性エポキシ樹脂硬化性組成物
JPH09176292A (ja) * 1995-12-26 1997-07-08 Asahi Denka Kogyo Kk 水性エポキシ樹脂硬化性組成物
CN111849143A (zh) * 2020-07-22 2020-10-30 增城市惠顺化工有限公司 一种高防腐环保型的水性环氧固化剂及其制备方法
CN115028803A (zh) * 2022-06-29 2022-09-09 湖北三棵树新材料科技有限公司 一种高光泽水性环氧固化剂及其制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197389A (en) * 1977-07-18 1980-04-08 Hoechst Aktiengesellschaft Hardening agent for aqueous epoxy resin compositions
EP2028244A1 (en) 2007-08-02 2009-02-25 Cytec Surface Specialties Austria GmbH Water-borne paints based on epoxy resins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04351628A (ja) * 1991-05-28 1992-12-07 Asahi Denka Kogyo Kk 水性エポキシ樹脂硬化性組成物
JPH09176292A (ja) * 1995-12-26 1997-07-08 Asahi Denka Kogyo Kk 水性エポキシ樹脂硬化性組成物
CN111849143A (zh) * 2020-07-22 2020-10-30 增城市惠顺化工有限公司 一种高防腐环保型的水性环氧固化剂及其制备方法
CN115028803A (zh) * 2022-06-29 2022-09-09 湖北三棵树新材料科技有限公司 一种高光泽水性环氧固化剂及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4644455A1 *

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Publication number Publication date
TW202428681A (zh) 2024-07-16
EP4644455A4 (en) 2026-04-29
CN120390763A (zh) 2025-07-29
EP4644455A1 (en) 2025-11-05
KR20250127075A (ko) 2025-08-26
JPWO2024142590A1 (https=) 2024-07-04
US20260085148A1 (en) 2026-03-26

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