Curable composition, coating agent, and laminate

Abstract

This curable composition comprises a component (A) and a component (B), wherein the component (B) content is 5.1-12.5 mass% with respect to the component (A). Component (A): a compound having at least one cationically polymerizable functional group. Component (B): a metal salt.

Description

Curable composition, coating agent, and laminate

[0001] The present invention relates to a curable composition, a coating agent, and a laminate.

[0002] Curable compositions, such as active energy ray curable compositions that harden by photoradical polymerization, are used as coating agents and complete the curing reaction in a short time. For this reason, they are attracting attention as they contribute to the high productivity of coated products.

[0003] Patent Document 1 discloses a composition that hardens by photocationic polymerization. Photocationic polymerization has the advantage of not being inhibited by oxygen and the shrinkage of the cured product is smaller compared to radical polymerization.

[0004] Japanese Patent Publication No. 2022-080366

[0005] However, photopolymerization initiators used in photocationic polymerization may consist of fluorine-containing counteranions, and the hydrogen fluoride generated by hydrolysis can corrode coated materials such as metals. The object of the present invention is to provide a curable composition with excellent rust prevention performance.

[0006] As a result of diligent research, the inventors of this invention discovered that a predetermined curable composition exhibits excellent rust prevention performance, and thus completed the present invention.

[0007] The present invention includes the following embodiments: [1] A curable composition comprising component (A) and component (B), wherein the content of component (B) is 5.1 to 12.5% ​​by mass relative to component (A). Component (A): A compound having at least one cationic polymerizable functional group Component (B): A metal salt [2] The curable composition according to [1], comprising component (C). Component (C): A cationic polymerization initiator that generates protonic acid by heat or active energy rays [3] The curable composition according to [1] or [2], wherein the cationic polymerizable functional group is at least one selected from the group consisting of epoxy groups, oxetanyl groups, and vinyl ether groups. [4] The curable composition according to any one of [1] to [3], wherein the metal salt is at least one selected from the group consisting of magnesium salts, calcium salts, barium salts, and zinc salts. [5] The curable composition according to any one of [2] to [4], wherein the counteranion of the cationic polymerization initiator is at least one selected from the group consisting of hexafluorophosphoric acid, tetrafluoroboric acid, hexafluoroantimonic acid, hexafluoroarsenic acid, fluorosulfonic acid, and trifluoromethanesulfonic acid. [6] The curable composition according to [2] to [5], wherein the content of component (C) is 0.1 to 10.0% by mass relative to component (A). [7] A coating agent comprising the curable composition according to any one of [1] to [6]. [8] A laminate made from the coating agent of [7].

[0008] According to the present invention, a curable composition with excellent rust prevention performance can be provided.

[0009] The embodiments of the present invention will be described in detail below, but the present invention is not limited thereto, and various modifications are possible without departing from its essence. In this specification, "(meth)acrylic" means acrylic and / or methacrylic, and "(meth)acrylate" means acrylate and / or methacrylate. Also, "(meth)acryloyl group" means acryloyl group and / or methacryloyl group. In the numerical ranges described stepwise in this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise, and the upper or lower limit of that numerical range may be replaced with the value shown in the example.

[0010] The present invention relates to a curable composition comprising component (A) and component (B). The content of component (B) in the curable composition of the present invention is 5.1 to 12.5% ​​by mass relative to component (A). Component (A): A compound having at least one cationic polymerizable functional group. Component (B): A metal salt.

[0011] The curable composition of the present invention refers to a composition that hardens when an active energy ray or heat is applied to it from an external source.

[0012] The curable composition of the present invention preferably further contains component (C). Component (C): A cationic polymerization initiator that generates protonic acid by heat or active energy rays.

[0013] <Component (A)> Component (A) is a compound having at least one cationic polymerizable functional group. Examples of cationic polymerizable functional groups include epoxy groups, oxetanyl groups, and vinyl ether groups.

[0014] (A) For example, aliphatic glycidyl ethers such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether can be used, as well as polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin.

[0015] (A) Examples of components include aromatic glycidyl ethers. Examples of aromatic glycidyl ethers that can be used include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, resorcinol diglycidyl ether, and monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by adding alkylene oxides to these.

[0016] (A) Ingredients that can be used include, for example, glycidyl esters of higher fatty acids such as epoxidized soybean oil and epoxidized linseed oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized polybutadiene, diglycidyl esters of aliphatic long-chain dibasic acids, and monoglycidyl ethers of aliphatic higher alcohols.

[0017] (A) Examples of components include alicyclic epoxys. Examples of alicyclic epoxys include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meth-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, limonene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxytetrahydrophthalate, and di-2-ethylhexyl epoxytetrahydrophthalate.

[0018] Component (A) is preferably bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, resorcinol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, or neopentyl glycol diglycidyl ether, with 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate being more preferred.

[0019] (A) Examples of components include oxetane compounds. Examples of oxetane compounds include various oxetane compounds described in Japanese Patent Publication No. 8-85775 and Japanese Patent Publication No. 8-134405, etc. Examples of oxetane compounds include monofunctional oxetanes and difunctional oxetanes.

[0020] Examples of monofunctional oxetanes include 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, and 3-ethyl-3-(chloromethyl)oxetane. Examples of difunctional oxetanes include 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene and bis(3-ethyl-3-oxetanylmethyl) ether. Oxetane compounds are commercially available from Toagosei Co., Ltd. as Aronoxetane OXT-101, OXT-121, OXT-211, OXT-221, and OXT-212 (all trade names).

[0021] (A) As component, silsesquioxane compounds having an oxetanyl group, as described in Japanese Patent Publication No. 11-116682, etc., can also be used. Among these, 3-ethyl-3-(hydroxymethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis(3-ethyl-3-oxetanylmethyl) ether, and silsesquioxane compounds having an oxetanyl group are preferred.

[0022] (A) Examples of components include oxolanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; cyclic acetals such as trioxane, 1,3-dioxolane, and 1,3,6-trioxanecyclooctane; cyclic lactones such as β-propiolactone and ε-caprolactone; vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether; spiroorthoesters obtained by the reaction of epoxy compounds with lactones; and derivatives of the above compounds.

[0023] (A) Component can be used by combining one or more compounds as appropriate.

[0024] <Component (B)> Component (B) is a metal salt. Component (B) can capture fluoride ions derived from hydrogen fluoride.

[0025] (B) Component is preferably (meth)acrylic acid, stearic acid, alginic acid, maleic acid, itaconic acid, crotonic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, acrylamide 2-methylpropanesulfonic acid, styrenesulfonic acid, and (meth)allylsulfonic acid, as well as organic acid salts such as esters of phosphoric acid and (meth)acrylic acid, metal chlorides, and sulfates.

[0026] Examples of metals that make up the metal salt include alkaline earth metals such as calcium, barium, and magnesium, and zinc. Calcium salts are preferred from the viewpoint of effectively capturing fluoride ions.

[0027] (B) Component can be used by combining one or more metal salts as appropriate.

[0028] The content of component (B) is 5.1 to 12.5% ​​by mass relative to component (A). A content of 5.1% by mass or more of component (A) provides rust prevention. A content of 12.5% ​​by mass or less prevents hardening inhibition caused by component (B) shielding active energy rays. The content of component (B) is preferably 6.0 to 12.0% by mass, more preferably 7.5 to 11.0% by mass.

[0029] <Component (C)> Component (C) is a cationic polymerization initiator that generates protonic acid by heat or active energy rays. The photo-cationic polymerization initiator is preferably a compound that cleaves and releases a strong acid by the action of active energy rays. The thermal cationic polymerization initiator is preferably a compound that cleaves and releases a strong acid by the action of heat.

[0030] Examples of photocationic polymerization initiators include compounds described in Section 3.1.5, pages 63 to 65 of UV / EB Curing Materials [CMC Co., Ltd., published in 1992], and sulfonium salts or onium salts are preferred among these.

[0031] As the counter anion for sulfonium salts or onium salts, for example, onium salts having hexafluorophosphoric acid, tetrafluoroboric acid, hexafluoroantimonic acid, hexafluoroarsenic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, or the like are preferred, and onium salts having hexafluorophosphoric acid, tetrafluoroboric acid, or hexafluoroantimonic acid are more preferred. The component (C) may be used by appropriately combining one or two or more metal salts.

[0032] Examples of thermal cationic polymerization initiators include sulfonium salts, phosphonium salts, and quaternary ammonium salts, with sulfonium salts being preferred. Examples of counter anions in the thermal cationic polymerization initiator include AsF ６ － , SbF ６ － , PF ６ － , and B(C ６ F ５ ) ４ － are mentioned.

[0033] The content of the component (C) is preferably 0.1 to 10.0% by mass relative to the component (A). When the content of the component (C) is 0.1 to 10.0% by mass, curing tends to proceed sufficiently. The content of the component (C) is preferably 0.5 to 8% by mass, more preferably 0.8 to 7.5% by mass.

[0034] <Other Components> The curable composition of the present invention may optionally contain additives such as photoradical polymerization initiators, organic solvents, antioxidants, ultraviolet absorbers, pigments, dyes, leveling agents, and silane coupling agents. As disclosed in Japanese Patent Application Laid-Open No. 2019-108426, Japanese Patent Application Laid-Open No. 2019-196461, Japanese Patent Application Laid-Open No. 2022-172885, and the like, the additives are well known to those skilled in the art, and those skilled in the art can appropriately select the type thereof and appropriately set the content thereof for use. The curable composition of the present invention can be used as a solvent-free composition, and can also be used as a solvent-based composition by blending an organic solvent therein. By containing an organic solvent, the coatability can be improved by adjusting the viscosity of the composition, and the film thickness can be adjusted according to the purpose.

[0035] <Usage Aspects of the Curable Composition of the Present Invention> The curable composition of the present invention can be used, for example, as a coating agent. A coating obtained by supplying and curing the curable composition of the present invention can exhibit excellent rust prevention performance.

[0036] Therefore, the curable composition of the present invention can be used as a coating agent composition for forming a coating intended for rust prevention, and can also be used as a coating agent composition for forming a coating intended for acid scavenging. When the coating is intended for rust prevention, the object to be coated has a surface made of a metal material such as stainless steel or aluminum as the coating target.

[0037] The thickness of the coating is appropriately set according to the application destination of the coating, and can be, for example, a film thickness of about several μm to several tens of μm.

[0038] The method for obtaining a coating using the curable composition of the present invention may follow a conventional method. For example, after supplying the curable composition of the present invention to a coating target by various methods, irradiation with active energy rays or heating may be performed.

[0039] When the curable composition of the present invention is irradiated with active energy rays to form a coating, examples of the active energy rays include ultraviolet rays, visible light, and electron beams, with ultraviolet rays being preferred. Examples of ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, UV electrodeless lamps, and LEDs. The irradiation energy should be appropriately set according to the type of active energy ray and the blending composition; by way of example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm 2 , and 200 to 1,000 mJ / cm 2 is more preferred.

[0040] When the curable composition of the present invention is heated to form a coating, it is preferred that the temperature is 60 to 200°C and the heating time is 30 minutes to 10 hours.

[0041] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the technical scope of the present invention is not limited thereto. In the following Examples, unless otherwise specified, "parts" and "%" each mean parts by mass and mass%, respectively.

[0042] [Examples 1 to 8, Comparative Examples 1 to 6] <Preparation of Curable Composition> The compounds shown in Table 1 were stirred, mixed and dissolved in the proportions shown in Table 1 in a stainless steel container to prepare a curable composition. In addition, the compositions shown in Table 2 were similarly prepared as Comparative Examples.

[0043] <Evaluation of Rust Prevention Performance> A cured product was produced by the following procedure. 1 cm of an electrolytic solution ("Lithium hexafluorophosphate solution", manufactured by Sigma Aldrich) was placed on an SS400 steel plate test piece ２ was applied in an amount of 0.01 g per application, and then the prepared composition was applied onto the electrolytic solution using a bar coater. In the case of photocuring, ultraviolet light of 365 nm was irradiated using an LED light source to produce a cured product. The ultraviolet intensity was 250 mW / cm ２ , and the integrated light intensity was 1000 mJ / cm ２In the case of thermosetting, the applied composition was heated in a 120°C constant temperature oven for 24 hours. The film thickness of the cured material was set to 10 μm. Next, the prepared cured material was left for 72 hours under conditions of 60°C and 90% RH, and the area where rust occurred in the area where the electrolyte was applied was calculated and evaluated according to the following criteria: ○: Rust occurred in less than 5% of the total applied area ×: Rust occurred in 5% or more of the total applied area

[0044]

[0045]

[0046] The numbers in Tables 1 and 2 represent the number of copies, and the meanings of the abbreviations are as follows: • EHPE3150: Polyfunctional alicyclic epoxy resin (epoxy equivalent: 177 g / eq), manufactured by Daicel Corporation • CEL2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation as "Celoxide 2021P" • TRPAG-30201: Bis(4-tert-butylphenyl)iodonium hexafluorophosphate, manufactured by Changzhou Strong Electronic New Materials Co., Ltd. as "TR-PAG-30201" • SI-110: 4-hydroxyphenylbenzylmethylsulfonium hexafluorophosphate, manufactured by Sanshin Chemical Industry Co., Ltd. as "San-Aid SI-110" • Ca(Me) ２ : Calcium methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd. "Calcium Methacrylate" ・Ca(St) ２ Calcium stearate, manufactured by Tokyo Chemical Industry Co., Ltd., "Calcium Stearate" ・Ca(Alg) ２ Calcium alginate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; Omnirad 184D: 1-hydroxycyclohexyl phenyl ketone, manufactured by IGM Resins.

[0047] <Results> As is clear from the results of Examples 1 to 8, the photocurable compositions of the present invention showed high rust prevention performance. Compared with Comparative Examples 1 to 6, compositions that did not contain or contained little calcium salt showed insufficient rust prevention performance. This suggests that the calcium salt combined with the fluoride ions of the acid that cause rust, forming water-insoluble and inert calcium fluoride, which prevented rust.

Claims

1. A curable composition comprising component (A) and component (B), wherein the content of component (B) is 5.1 to 12.5% ​​by mass relative to component (A). (A) Component: A compound having at least one cationic polymerizable functional group. (B) Component: A metal salt.

2. The curable composition according to claim 1, comprising component (C). Component (C): A cationic polymerization initiator that generates protonic acid by heat or active energy rays.

3. The curable composition according to claim 1, wherein the cationic polymerizable functional group is at least one selected from the group consisting of epoxy groups, oxetanyl groups, and vinyl ether groups.

4. The curable composition according to claim 1, wherein the metal salt is at least one selected from the group consisting of magnesium salts, calcium salts, barium salts, and zinc salts.

5. The curable composition according to claim 2, wherein the counteranion of the cationic polymerization initiator is at least one selected from the group consisting of hexafluorophosphate, tetrafluoroboric acid, hexafluoroantimonic acid, hexafluoroarsenic acid, fluorosulfonic acid, and trifluoromethanesulfonic acid.

6. The curable composition according to claim 2, wherein the content of component (C) is 0.1 to 10.0% by mass relative to component (A).

7. A coating agent comprising the curable composition according to any one of claims 1 to 6.

8. A laminate made from the coating agent described in claim 7.

Images