WO2014034828A1 - 防錆用組成物およびこれを含む水分散体 - Google Patents
防錆用組成物およびこれを含む水分散体 Download PDFInfo
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Definitions
- the present invention relates to a rust-preventing composition and an aqueous dispersion containing the same, and more particularly to a rust-preventing composition capable of forming a rust-preventing coating film excellent in resistance to alkali treatment and an aqueous dispersion containing the same.
- the ionomer resin which is a partially neutralized product consisting of a polymer chain mainly composed of hydrocarbons and in which part of the carboxyl groups in the side chain is neutralized with a metal cation, It is well known that it has good adhesion. For example, Journal of the Adhesion Society of Japan, Vol. 19, no. 3, p95-101 (1983), it is reported that the coating properties and adhesion of ionomer resins differ depending on the type of cross-linking ions such as alkali metals and divalent metals. It is also known that an ionomer resin can be used as a rust preventive material for a metal substrate because the rust preventive layer made of this ionomer resin has excellent water resistance.
- Japanese Patent Laid-Open No. 11-012411 discloses an aqueous solution comprising an ionomer resin neutralized with a divalent metal to improve rust prevention performance, an epoxy group-containing compound, and a reaction product of an ionomer resin and an epoxy group-containing compound. Dispersion compositions are disclosed. However, as evaluated by the inventors, the steel sheet formed with the above disclosed composition is subjected to an alkaline degreasing treatment, and then the salt spray test results in rusting and sufficient rust prevention. (Hereinafter, the rust prevention after the alkali degreasing treatment is referred to as alkali resistance).
- Japanese Patent Laid-Open No. 2006-22127 discloses a composition for an anticorrosive coating containing an ionomer resin neutralized with a monovalent metal ion and / or an amine, a polyfunctional oxazoline resin, a catalyst and a silane coupling agent. It is disclosed that the coating film formed from this composition has high alkali resistance.
- the object of the present invention is to solve the above-mentioned problems of the prior art, that is, to provide a rust-preventing composition capable of forming a coating film excellent in alkali resistance, and in combination with appropriate components.
- Another object of the present invention is to provide a polymer capable of producing a rustproofing composition.
- the present inventors have obtained knowledge that the presence of acidic groups in the polymer forming the coating film may reduce the alkali resistance of the rust-preventing coating film. And by restricting the use of acid monomers as monomer components, and in combination with a polymer having at least a nitrile group, a hydroxyl group, and an alkoxysilyl group and a crosslinking agent, excellent substrate adhesion, water resistance, solvent resistance The present inventors have found that a rust-preventing composition capable of forming a coating film that is compatible with both properties and corrosion resistance and excellent alkali resistance can be obtained, and the present invention has been completed.
- a rust preventive composition containing a polymer (A) having at least a nitrile group, a hydroxyl group, and an alkoxysilyl group, and a crosslinking agent (B).
- the polymer (A) is a structural unit derived from a nitrile monomer (a-1) having an ⁇ , ⁇ -monoethylenically unsaturated group, a monomer having an ⁇ , ⁇ -monoethylenically unsaturated group ( a-2) (excluding the component (a-1)), a structural unit derived from a monomer (a-3) having a hydroxyl group, and an alkoxysilyl (meth) acrylate (a-4)
- the composition for rust prevention according to the above [1] which contains a derived structural unit.
- the composition for rust prevention according to the description.
- Structural unit derived from nitrile monomer (a-1) having ⁇ , ⁇ -monoethylenically unsaturated group, monomer (a-2) having ⁇ , ⁇ -monoethylenically unsaturated group (provided that A structural unit derived from the above (a-1) component), a structural unit derived from a monomer (a-3) having a hydroxyl group, and a structural unit derived from an alkoxysilyl (meth) acrylate (a-4) Rust polymer.
- the coating film obtained from the adhesive composition of the present invention is excellent in alkali resistance, and can secure sufficient alkali resistance even if it is thinned.
- composition for rust prevention of the present invention contains at least a polymer (A) having a nitrile group, a hydroxyl group, and an alkoxysilyl group, and a crosslinking agent (B).
- the polymer (A) is the main component of the present composition, and forms a rust-preventing coating film by crosslinking with the crosslinking agent (B).
- the polymer (A) includes a structural unit derived from a nitrile monomer (a-1) having an ⁇ , ⁇ -monoethylenically unsaturated group, an ⁇ , ⁇ -monoethylenically unsaturated group.
- a polymer (A1) comprising a structural unit derived from a monomer (a-2) having a structural unit derived from a hydroxyl group-containing monomer (a-3) and a structural unit derived from an alkoxysilyl (meth) acrylate (a-4) Can be mentioned.
- the polymer (A1) includes a nitrile monomer (a-1) having an ⁇ , ⁇ -monoethylenically unsaturated group, a monomer (a-2) having an ⁇ , ⁇ -monoethylenically unsaturated group, and a hydroxyl group-containing It can be obtained by copolymerizing the monomer (a-3) and the alkoxysilyl (meth) acrylate (a-4).
- the polymer (A1) does not contain a structural unit derived from an acid monomer such as acrylic acid and methacrylic acid as an essential structural unit.
- (meth) acrylic acid means acrylic acid and methacrylic acid
- (meth) acrylate means acrylate and methacrylate
- the polymer (A1) can contain structural units other than the structural units derived from the above (a-1) to (a-4). However, the amount of the structural unit having an acidic group contained in the polymer (A) is limited.
- the acid value of the polymer (A) is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, and further preferably 15 mgKOH / g or less.
- the acid value of the polymer (A) is the number of mg of potassium hydroxide (KOH) necessary for neutralizing the acidic component contained in 1 g of the polymer (A).
- the acid value of the polymer (A) is determined by a method according to JIS K0070.
- the polymer (A) has a small content ratio of the structural unit having an acidic group as described above, and preferably does not include a structural unit having an acidic group. That is, the amount of acidic groups present in the polymer (A) is small, and preferably no acidic groups are present.
- the crosslinking agent (B) can improve the water resistance of the anticorrosive coating film by crosslinking with the polymer (A).
- the crosslinking agent (B) is a compound capable of crosslinking with the polymer (A), preferably an oxazoline compound, a silane coupling agent, an epoxy compound, an amino compound, a melamine compound, an isocyanate compound, An organic zirconium compound, an organic titanium compound, an epichlorohydrin compound, a carbodiimide compound, and an aziridine compound, particularly preferably an oxazoline compound (b1) and a silane coupling agent (b2).
- the polymer which is the main component of the conventional rust-preventing composition has acidic groups such as carboxyl groups at a certain ratio. This is because it is essential for the polymer as the main component to contain an acidic group at a certain ratio in order to crosslink with the silane coupling agent.
- the inventors' research has revealed that the presence of acidic groups in the polymer may reduce the alkali resistance of the anticorrosive coating film. Then, in the composition for rust prevention of this invention, the alkali resistance of the rust prevention coating film was improved by restrict
- the polymer (A1) includes a structural unit derived from the hydroxyl group-containing monomer (a-3) instead of the structural unit having an acidic group. That is, the polymer (A) has a hydroxyl group instead of an acidic group.
- the hydroxyl group of the polymer (A) reacts with the functional groups of the crosslinking agent (B), for example, the oxazoline compound (b1) and the silane coupling agent (b2).
- a crosslinked body is obtained.
- the functional group of the polymer (A) involved in crosslinking is a hydroxyl group
- the strength of crosslinking with the silane coupling agent (b2) or the like cannot be increased. Therefore, in the rust-preventing composition of the present invention, for example, the polymer (A1) contains a structural unit derived from the alkoxysilyl (meth) acrylate (a-4), thereby allowing the alkoxysilyl of the polymer (A).
- the composition for rust prevention of the present invention has a much higher alkali resistance than the conventional rust preventive composition while maintaining the same coating strength as that of the conventional rust preventive composition. It was possible to form a coating film.
- the hydroxyl value of the polymer (A) is preferably 1 to 90 mgKOH / g, more preferably 1 to 50 mgKOH / g, and further preferably 1 to 25 mgKOH / g.
- the hydroxyl value of the polymer (A) means the number of mg of potassium hydroxide (KOH) required to neutralize acetic acid bonded to the hydroxyl group when 1 g of the polymer (A) is acetylated. It is.
- the hydroxyl value of the polymer (A) is determined by a method according to JIS K0070.
- the structural unit derived from the nitrile monomer (a-1) having an ⁇ , ⁇ -monoethylenically unsaturated group is for improving the solvent resistance of the anticorrosive coating film formed from the antirust composition. It is contained in the polymer (A1).
- Examples of the nitrile monomer (a-1) having an ⁇ , ⁇ -monoethylenically unsaturated group include acrylonitrile and methacrylonitrile.
- the structural unit derived from the monomer (a-2) having an ⁇ , ⁇ -monoethylenically unsaturated group is a basic structural unit of the polymer (A1).
- the monomer (a-2) having an ⁇ , ⁇ -monoethylenically unsaturated group does not include the nitrile monomer (a-1) having the ⁇ , ⁇ -monoethylenically unsaturated group.
- Monomers (a-2) having an ⁇ , ⁇ -monoethylenically unsaturated group include esterified products of vinyls containing carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl isocyanate, isopropenyl isocyanate Isocyanate group-containing vinyls such as nates, aromatic vinyls such as styrene, ⁇ -methylstyrene, vinyltoluene and t-butylstyrene, other vinyl acetate, vinyl propionate, acrylamide, methacrylamide, methylolacrylamide and methylolmethacrylamide Etc.
- carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl isocyanate, isopropenyl isocyanate
- Isocyanate group-containing vinyls such as nates
- aromatic vinyls such as styrene, ⁇ -methylstyren
- esterified products of acrylic acid or methacrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylamino
- Examples include epoxy group-containing vinyls such as ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate and methyl glycid
- n-butyl acrylate is preferable from the viewpoints of copolymerization with other monomers and Tg adjustment.
- the structural unit derived from the hydroxyl group-containing monomer (a-3) is contained in the polymer (A1) in order to improve the alkali resistance of the anticorrosive coating film formed from the present antirust composition.
- a crosslinking reaction with the crosslinking agent (B) is performed in order to improve the alkali resistance of the anticorrosive coating film formed from the present antirust composition.
- Examples of the monomer (a-3) having a hydroxyl group include hydroxymethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3- Examples include hydroxyl group-containing (meth) acrylates such as phenoxypropyl (meth) acrylate. Among these, 2-hydroxyethyl methacrylate is preferable from the viewpoint of copolymerization with other monomers.
- the structural unit derived from the alkoxysilyl (meth) acrylate (a-4) is crosslinked with the silane coupling agent (b2) to form a polymer (A1) in order to increase the strength of the crosslinked structure.
- the alkoxysilyl (meth) acrylate (a-4) include trimethoxysilyl (meth) acrylate, triethoxysilyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane.
- 3-methacryloxypropyltrimethoxysilane 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, etc. it can.
- 3-methacryloxypropyltrimethoxysilane is preferable from the viewpoints of copolymerizability and cross-linking reactivity when forming a coating film.
- the content ratio of the structural units derived from the above (a-1) to (a-4) contained in the polymer (A1) is Each is as follows.
- the content ratio of the structural unit derived from the nitrile monomer (a-1) having an ⁇ , ⁇ -monoethylenically unsaturated group is preferably 30 to 90% by weight, more preferably 50 to 90% by weight, still more preferably 55 to 80% by weight.
- the content ratio of the structural unit derived from the monomer (a-2) having an ⁇ , ⁇ -monoethylenically unsaturated group is preferably 10 to 60% by weight, more preferably 10 to 50% by weight, and still more preferably 20 to 40% by weight.
- the content ratio of the structural unit derived from the hydroxyl group-containing monomer (a-3) is preferably 1 to 10% by weight, more preferably 2 to 7% by weight, and further preferably 3 to 6% by weight.
- the content ratio of the structural unit derived from the alkoxysilyl (meth) acrylate (a-4) is preferably 1 to 5% by weight, more preferably 1 to 4% by weight, and further preferably 1 to 3% by weight.
- Examples of structural units other than the structural units derived from (a-1) to (a-4) that can be contained in the polymer (A1) include methylene bis (meth) acrylamide, divinylbenzene, and polyethylene glycol chain-containing di (meta). ) Structural units derived from acrylate and the like can be mentioned.
- the content ratio of structural units other than the structural units derived from the above (a-1) to (a-4) that can be contained in the polymer (A1) can be within a range that does not impair the film formability.
- the amount of all structural units contained in the coalescence (A1) is 100% by weight, it is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, still more preferably 0.1 to 1% by weight. It is.
- the average particle size is preferably 10 to 500 nm, more preferably 10 to 200 nm, and more preferably 10 to 100 nm. Is more preferable.
- the average particle size of the polymer (A) is within the above range, the film formability is improved, and the water resistance, alkali resistance, and corrosion resistance of the coating film are improved.
- the composition for rust prevention of this invention does not have acidic groups, such as a carboxyl group, or its content is small. For this reason, we are anxious about the adhesiveness with respect to the steel plate etc. of the antirust coating film formed from this antirust composition.
- the average particle size of the polymer (A) is a small particle size within the above range, the contact area of the polymer (A) with the steel plate or the like increases, and the adhesion between the anticorrosive coating film and the steel plate or the like increases. It can also be expected to improve the performance.
- the average particle size of the polymer (A) can be determined by a light scattering method using a measuring instrument such as a particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
- Examples of the method for bringing the average particle diameter of the polymer (A) within the above range include a method for adjusting the amount of surfactant used when the polymer (A) is produced by emulsion polymerization. .
- the method for synthesizing the polymer (A), for example, the polymer (A1) is not particularly limited, but emulsion polymerization performed in a solvent containing water as a main component is preferable.
- the oxazoline compound (b1) is a substance that crosslinks the polymer (A) to form a crosslinked body.
- the composition for rust prevention contains the oxazoline compound (b1), the adhesion and water resistance of the rust prevention coating film are improved.
- oxazoline compound (b1) examples include addition-polymerizable oxazoline compounds such as 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and (meth) (Meth) acrylic esters such as methyl acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, (meth) acrylic acid amide vinyl acetate, styrene, ⁇ -methylstyrene
- a water-soluble or water-dispersed copolymer of a copolymer with a copolymerizable monomer that does not react with an oxazoline group such as sodium styrenesulfonate can be mentioned.
- EPOCROSS K-2010E, K-2020E, K-2030E, WS-500 and the like which are products of Nippon Shokubai Co., Ltd., but are not limited thereto. Of these, Epocross K-2020E and K-2030E are preferred.
- the oxazoline group equivalent of the oxazoline compound (b1) is usually 200 to 5000 g / equivalent, preferably 250 to 4000 g / equivalent, more preferably 300 to 3000 g / equivalent.
- the oxazoline group equivalent is in this range, it is preferable in terms of substrate adhesion, coating film strength, water resistance, and alkali resistance.
- the oxazoline compound (b1) is preferably water dispersible from the viewpoint of pot life.
- the content of the oxazoline-based compound (b1) in the rust-preventing composition of the present invention is preferably 1 to 40 parts by weight, more preferably 3 to 30 parts by weight, more preferably 100 parts by weight of the polymer (A).
- the amount is preferably 5 to 20 parts by weight.
- the silane coupling agent (b2) is a substance that crosslinks the polymer (A) to form a crosslinked body.
- the composition for rust prevention contains the silane coupling agent (b2), the water resistance of the rust prevention coating film is improved.
- the silane coupling agent (b2) include conventionally used normal silane coupling agents.
- the silane coupling agent (b2) preferably has a functional group capable of reacting with a functional group in the acrylic resin such as a hydroxyl group or a carboxyl group, and in particular, a glycidyl group, an epoxycyclohexyl group, a vinyl group, an amino group, an amide group, It preferably has a group selected from a ureido group, a thiol group, a sulfide group and an isocyanate group. Among these, it is preferable to have a glycidyl group, an amino group, an amide group, or an isocyanate group.
- silane coupling agent (b2) examples include Shin-Etsu Chemical's silane coupling agents KBM-303, KBM-403, KBM-603, KBM-903, and KBM-585. It is not limited.
- the content ratio of the silane coupling agent (b2) is preferably from 0.1 to 10 in terms of coating film strength and alkali resistance with respect to 100 parts by weight of the polymer (A). Parts by weight, more preferably 0.2 to 8 parts by weight, still more preferably 0.3 to 5 parts by weight.
- the rust-preventing composition of the present invention contains the polymer (A) and the crosslinking agent (B), it is substantially acid-free and has excellent crosslinking reactivity. Excellent alkalinity and coating stability. Furthermore, by making the polymer (A) small, water resistance, alkali resistance and coating film stability are excellent.
- the rust-preventing composition of the present invention comprises a hydroxyl group and an oxazoline group as necessary.
- a catalyst (C) for promoting the reaction and a water-soluble zirconium compound (D) having reactivity with a hydroxyl group can be contained.
- the catalyst (C) that promotes the reaction between the hydroxyl group and the oxazoline group is used to catalyze the reaction between the hydroxyl group of the polymer (A) and the oxazoline-based compound (b1) and promote the crosslinking reaction.
- the catalyst (C) include acids, acid esters, onium salts, lithium salts and the like. Specifically, quaternary phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, methyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, halides such as lithium, sodium, potassium, cesium and their hydroxides, etc.
- Phosphoric acid ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phenyl phosphoric acid, finyl ammonium phosphate, p-toluenesulfonic acid, ammonium p-toluenesulfonate, and ammonium salts thereof, tetramethylammonium chloride, tetraethyl Examples thereof include quaternary ammonium salts such as ammonium chloride, tetrabutylammonium chloride, and benzyldimethyl chloride, and hydroxides thereof.
- tetramethylphosphonium chloride lithium bromide, lithium chloride, lithium hydroxide, diammonium hydrogen phosphate, tetramethylammonium chloride, and tetramethyl hydroxide are preferable.
- ammonium dihydrogen phosphate, tetramethylammonium chloride, A compound selected from tetramethylammonium hydroxide, lithium halide and lithium hydroxide is preferred.
- the content ratio of the catalyst (C) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight with respect to 100 parts by weight of the polymer (A). More preferably, it is 0.3 to 5 parts by weight.
- the blending amount of the catalyst (C) is within this range, it is preferable in terms of coating film strength and alkali resistance.
- the water-soluble zirconium compound (D) capable of reacting with a hydroxyl group is used for improving substrate adhesion, water resistance, and alkali resistance.
- Examples of the water-soluble zirconium compound (D) include ammonium zirconium carbonate, zirconium carbonate potassium, zirconium nitrate, zirconium acetate, basic zirconium carbonate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, and zirconium bisacetylacetonate. Can do. Of these, ammonium zirconium carbonate and potassium zirconium carbonate are preferred in terms of reactivity with hydroxyl groups and adhesion to the substrate, and ammonium zirconium carbonate is particularly preferred.
- the content ratio of the water-soluble zirconium compound (D) capable of reacting with a carboxyl group is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymer (A) in terms of storage stability of the resin.
- the amount is preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight.
- the aqueous dispersion can be prepared by dispersing the antirust composition of the present invention in water. That is, the polymer (A), the crosslinking agent (B), the catalyst (C) added as necessary, the water-soluble zirconium compound (D) and the like can be dispersed in water to obtain an aqueous dispersion.
- This water dispersion may be prepared by preparing the rust preventive composition of the present invention and dispersing it in water. Each component of the rust preventive composition of the present invention is individually dispersed in water. It may be produced.
- the solid content concentration of the aqueous dispersion is not particularly limited, and is appropriately adjusted according to the coating method and the apparatus used for coating.
- the ratio is 100 to 3000 parts by weight of water, preferably 200 to 2000 parts by weight with respect to 100 parts by weight of the total amount of components (A), (B), (C) and (D). .
- the rust preventive composition of the present invention can further contain other components as long as the object of the present invention is not impaired.
- an inorganic filler can be used for the purpose of improving the corrosion resistance.
- the inorganic filler include colloidal silica and zirconium oxide, and the blending amount thereof is 100 parts by weight in total of the polymer (A), the crosslinking agent (B), the catalyst (C) and the zirconium compound (D). The amount is preferably 0 to 80 parts by weight, and more preferably 0 to 60 parts by weight.
- Other components include, for example, pH adjusters, chelating agents, pigments, wetting agents, antistatic agents, antioxidants, preservatives, ultraviolet absorbers, light stabilizers, fluorescent brighteners, colorants, leveling agents, A wetting agent, a foaming agent, a release agent, an antifoaming agent, a foam control agent, a fluidity improving agent, a thickening agent and the like can be mentioned, but are not limited thereto.
- the production method of the rust preventive composition of the present invention is not particularly limited, and can be produced by blending the above components.
- the rust-preventing composition of the present invention can be applied to a steel plate or the like as it is, or can be applied to a steel plate or the like after being pre-reacted.
- the pre-reaction conditions are usually 40 to 120 ° C. for 5 to 100 minutes, preferably 50 to 100 ° C. for 10 to 60 minutes, more preferably 50 to 80 ° C. for 10 to 60 minutes.
- the coating composition can be formed by applying the rust-preventing composition of the present invention as it is or pre-reacting to a steel sheet, drying and curing.
- the composition can be applied by any of spraying, curtaining, flow coating, roll coating, brushing, and dipping methods.
- the applied composition may be naturally dried, but is preferably baked.
- the baking temperature is 60 ° C. to 500 ° C., and the baking time is 1 to 120 seconds.
- a rust-proof steel sheet can be obtained by coating a steel sheet with a cured product of the rust-proofing composition of the present invention.
- Evaluation was performed as follows according to the number of squares peeled out of 25 squares by the grid. ⁇ : No peeling of the squares ⁇ : One or more squares are peeled [water resistance] The produced rust-proof steel plate sample was immersed in 80 degreeC warm water for 1 hour, and the subsequent surface state was evaluated visually. ⁇ : No change from before immersion ⁇ : Bleed occurred ⁇ : Whitening [alkali resistance] The produced rust-proof steel plate sample was immersed in a 2% aqueous sodium hydroxide solution at 50 ° C. for 5 minutes, and the subsequent surface condition was visually evaluated.
- Example 1 A separable flask equipped with a stirrer and reflux cooling was charged with 285 parts by weight of distilled water and 2.0 parts by weight of sodium lauryl sulfate, replaced with nitrogen gas, and then heated to 75 ° C. Next, 0.5 part by weight of potassium persulfate was added, and then a vinyl monomer emulsion having the following composition was continuously added over 4 hours and held for another 3 hours to complete the polymerization. An aqueous dispersion of a copolymer (polymer (A)) having a solid content of 24.0% by weight was obtained. The average particle size, acid value, and hydroxyl value of this copolymer were determined by the above methods. The results are shown in Table 1.
- Example 1 1 part by weight, 0.5 parts by weight of ammonium zirconium carbonate and 5 parts by weight of 3-glycidoxypropyltrimethoxysilane (silane coupling agent) were blended and stirred at room temperature to produce a rust-preventing composition.
- An aqueous dispersion was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1.
- Examples 2 to 5 A copolymer having a solid content of 24.0% by weight, except that the composition of the vinyl monomer emulsion is changed to the compositions shown in Examples 2 to 5 in Table 1, and the same operation as in Example 1 is performed.
- Example 1 An aqueous dispersion of (polymer (A)) was obtained. The average particle size, acid value, and hydroxyl value of this copolymer were determined by the above methods. The results are shown in Table 1.
- Example 1 An aqueous dispersion of the rusting composition was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1. [Comparative Examples 1, 3, 4] The same procedure as in Example 1 was performed except that the composition of the vinyl monomer emulsion was changed to the compositions shown in Comparative Examples 1, 3 and 4 in Table 1, and the solid content was 24.0% by weight. An aqueous dispersion of the polymer was obtained.
- Example 1 An aqueous dispersion of the rusting composition was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1.
- Example 2 The same procedure as in Example 1 was performed except that the composition of the vinyl monomer emulsion was changed to the composition shown in Comparative Example 2 of Table 1. An aqueous dispersion of coalescence (A)) was obtained. The average particle size, acid value, and hydroxyl value of this copolymer were determined by the above methods. The results are shown in Table 1.
- Example 1 An aqueous dispersion of the rusting composition was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1.
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Abstract
Description
[1]少なくともニトリル基、水酸基、およびアルコキシシリル基を有する重合体(A)ならびに架橋剤(B)を含有する防錆用組成物。
[2]重合体(A)が、α,β-モノエチレン性不飽和基を有するニトリル系モノマー(a-1)から導かれる構造単位、α,β-モノエチレン性不飽和基を有するモノマー(a-2)(ただし、前記(a-1)成分を除く)から導かれる構造単位、水酸基を有するモノマー(a-3)から導かれる構造単位およびアルコキシシリル(メタ)アクリレート(a-4)から導かれる構造単位を含むものである上記[1]に記載の防錆用組成物。
[3]重合体(A)が、重合体(A)に含まれる全構造単位の量を100重量%としたとき、α,β-モノエチレン性不飽和基を有するニトリル系モノマー(a-1)から導かれる構造単位を30~90重量%、α,β-モノエチレン性不飽和基を有するモノマー(a-2)(ただし、前記(a-1)成分を除く)から導かれる構造単位を10~60重量%、水酸基を有するモノマー(a-3)から導かれる構造単位を1~10重量%、およびアルコキシシリル(メタ)アクリレート(a-4)から導かれる構造単位を1~5重量%含むものである上記[1]または[2]に記載の防錆用組成物。
[4]重合体(A)は粒子として存在し、その平均粒径が10~500nmである上記[1]~[3]のいずれかに記載の防錆用組成物。
[5]重合体(A)は、酸価が30mgKOH/g以下である上記[1]~[4]のいずれかに記載の防錆用組成物。
[6]重合体(A)は、水酸基価が1~90mgKOH/gである上記[1]~[5]のいずれかに記載の防錆用組成物。
[7]さらに、水酸基との反応性を有する水溶性ジルコニウム化合物(D)を含有する上記[1]~[6]のいずれかに記載の防錆用組成物。
[8]水溶性ジルコニウム化合物(D)が炭酸ジルコニウムアンモニウムである上記[7]に記載の防錆用組成物。
[9]架橋剤(B)が、オキサゾリン化合物(b1)およびシランカップリング剤(b2)から選ばれた少なくとも1種である上記[1]~[8]のいずれかに記載の防錆用組成物。
[10]オキサゾリン系化合物(b1)は、水分散性で、かつ、オキサゾリン基当量が200~5000g/当量である上記[9]に記載の防錆用組成物。
[11]シランカップリング剤(b2)が、グリシジル基、アミノ基、アミド基、またはイソシアネート基を有する化合物である上記[9]または[10]に記載の防錆用組成物。
[12]架橋剤(B)が、オキサゾリン化合物(b1)およびシランカップリング剤(b2)である上記[9]~[11]のいずれかに記載の防錆用組成物。
[13]重合体(A)100重量部に対して、オキサゾリン系化合物(b1)を1~40重量部、シランカップリング剤(b2)を0.1~10重量部の割合で含有する上記[12]に記載の防錆用組成物。
[14]さらに、水酸基とオキサゾリン基との反応を促進する触媒(C)を含有する上記[12]または[13]に記載の防錆用組成物。
[15]水酸基との反応性を有する水溶性ジルコニウム化合物(D)を含有し、重合体(A)100重量部に対して、オキサゾリン系化合物(b1)を1~40重量部、シランカップリング剤(b2)を0.1~5重量部、触媒(C)を0.1~10重量部、水溶性ジルコニウム化合物(D)を0.1~5重量部の割合で含有する上記[14]に記載の防錆用組成物。
[16]触媒(C)がリン酸二水素アンモニウム、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムヒドロキサイド、ハロゲン化リチウムおよび水酸化リチウムから選ばれた化合物である上記[14]または[15]に記載の防錆用組成物。
[17]上記[1]~[16]のいずれかに記載の防錆用組成物を含む水分散体。
[18]上記[1]~[16]のいずれかに記載の防錆用組成物の硬化物で鋼板を被覆してなる防錆鋼板。
[19]α,β-モノエチレン性不飽和基を有するニトリル系モノマー(a-1)から導かれる構造単位、α,β-モノエチレン性不飽和基を有するモノマー(a-2)(ただし、前記(a-1)成分を除く)から導かれる構造単位、水酸基を有するモノマー(a-3)から導かれる構造単位およびアルコキシシリル(メタ)アクリレート(a-4)から導かれる構造単位を含む防錆用重合体。
[鋼板]
鋼板としては亜鉛溶融メッキ鋼板(JIS G3302)を用いた。以下の実施例および比較例において得られた防錆用組成物をこの鋼板の片面の全面に塗布後、表面温度120℃で60秒間乾燥することにより厚み2μmの塗膜を形成し、防錆鋼板試料を作製した。得られた塗膜の特性を以下の評価方法により評価した。
[基材密着性]
塗膜の基材密着性をJIS K5600-5-6に準じた碁盤目試験によって評価した。碁盤目による25の升目のうち剥がれた升目の数により以下のように評価した。
○:剥がれている升目がない
×:1以上の升目が剥がれている
[耐水性]
作製した防錆鋼板試料を、80℃温水に1時間浸漬し、その後の表面状態を目視にて評価した。
○:浸漬前と変化なし
△:ブリードが生じた
×:白化した
[耐アルカリ性]
作製した防錆鋼板試料を、50℃の2%水酸化ナトリウム水溶液に5分間浸漬し、その後の表面状態を目視にて評価した。
○:浸漬前と変化なし
△:黄変したが、剥がれは生じなかった
×:黄変と剥がれが生じた
[耐溶剤性]
得られた塗膜について、メチルエチルケトンによるラビング試験を実施した。メチルエチルケトンを染み込ませたガーゼを用いて、2kgfの荷重で10往復ラビングを行い、その後の状態を目視にて評価した。
○:ラビング前と変化なし
△:表面が荒れたが、溶解はしなかった
×:表面が溶解した
[耐食性]
得られた塗膜の表面を基材の金属に届くようにクロスカット後、5%食塩水を噴霧した。25℃で5日間経過した後の錆の発生状態を目視にて評価した。
○:塗膜面への錆の浸入が5mm以下である
×:塗膜面への錆の浸入が5mmより大きい
[重合体(A)の酸価の測定方法]
重合体(A)の酸価は、JIS K0070に準じて測定した。
[重合体(A)の水酸基価の測定方法]
重合体(A)の水酸基価は、JIS K0070に準じて測定した。
[重合体(A)の平均粒径の測定方法]
重合体(A)の平均粒径は、大塚電子(株)製の粒径アナライザーFPAR-1000により光散乱法によって測定した。
[実施例1]
攪拌機、還流冷却付きのセパラブルフラスコに蒸留水285重量部及びラウリル硫酸ナトリウムを2.0重量部仕込み、窒素ガスで置換した後、75℃に昇温した。次いで過硫酸カリウム0.5重量部を添加してから下記組成のビニル単量体乳化物を4時間かけて連続的に添加し、更に3時間保持し、重合を完結させた。固形分が24.0重量%である共重合体(重合体(A))の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表1に示した。
(ビニル単量体乳化物)
アクリロニトリル 65.0重量部
n-ブチルアクリレート 28.0重量部
2-ヒドロキシエチルメタクリレート 5.0重量部
3-メタクリロキシプロピルトリメトキシシラン 2.0重量部
ラウリル硫酸アンモニウム 0.2重量部
蒸留水 40.0重量部
この水分散体を固形分として100重量部とり、そこへエポクロスK-2030E(日本触媒社製オキサゾリン系化合物、オキサゾリン基当量:550)を10重量部、触媒であるリン酸二水素アンモニウムを1重量部、炭酸ジルコニウムアンモニウムを0.5重量部、3-グリシドキシプロピルトリメトキシシラン(シランカップリング剤)を5重量部、を配合し、室温にて攪拌して防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表1に示した。
[実施例2~5]
ビニル単量体乳化物の組成を表1の実施例2~5に示した組成に変更する以外は、実施例1と同様の操作を行い、固形分が24.0重量%である共重合体(重合体(A))の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表1に示した。エポクロスK-2030E、リン酸二水素アンモニウム、炭酸ジルコニウムアンモニウムおよび3-グリシドキシプロピルトリメトキシシランの配合量を表1に示したように変更する以外は実施例1と同様の操作を行い、防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表1に示した。
[比較例1、3、4]
ビニル単量体乳化物の組成を表1の比較例1、3および4に示した組成に変更する以外は、実施例1と同様の操作を行い、固形分が24.0重量%である共重合体の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表1に示した。エポクロスK-2030E、リン酸二水素アンモニウム、炭酸ジルコニウムアンモニウムおよび3-グリシドキシプロピルトリメトキシシランの配合量を表1に示したように変更する以外は実施例1と同様の操作を行い、防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表1に示した。
[比較例2]
ビニル単量体乳化物の組成を表1の比較例2に示した組成に変更する以外は、実施例1と同様の操作を行い、固形分が24.0重量%である共重合体(重合体(A))の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表1に示した。エポクロスK-2030E、リン酸二水素アンモニウム、炭酸ジルコニウムアンモニウムおよび3-グリシドキシプロピルトリメトキシシランの配合量を表1に示したように変更する以外は実施例1と同様の操作を行い、防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表1に示した。
Claims (19)
- 少なくともニトリル基、水酸基、およびアルコキシシリル基を有する重合体(A)ならびに架橋剤(B)を含有する防錆用組成物。
- 重合体(A)が、α,β-モノエチレン性不飽和基を有するニトリル系モノマー(a-1)から導かれる構造単位、α,β-モノエチレン性不飽和基を有するモノマー(a-2)(ただし、前記(a-1)成分を除く)から導かれる構造単位、水酸基を有するモノマー(a-3)から導かれる構造単位およびアルコキシシリル(メタ)アクリレート(a-4)から導かれる構造単位を含むものである請求項1記載の防錆用組成物。
- 重合体(A)が、重合体(A)に含まれる全構造単位の量を100重量%としたとき、α,β-モノエチレン性不飽和基を有するニトリル系モノマー(a-1)から導かれる構造単位を30~90重量%、α,β-モノエチレン性不飽和基を有するモノマー(a-2)(ただし、前記(a-1)成分を除く)から導かれる構造単位を10~60重量%、水酸基を有するモノマー(a-3)から導かれる構造単位を1~10重量%、およびアルコキシシリル(メタ)アクリレート(a-4)から導かれる構造単位を1~5重量%含むものである請求項1または2記載の防錆用組成物。
- 重合体(A)は粒子として存在し、その平均粒径が10~500nmである請求項1~3のいずれかに記載の防錆用組成物。
- 重合体(A)は、酸価が30mgKOH/g以下である請求項1~4のいずれかに記載の防錆用組成物。
- 重合体(A)は、水酸基価が1~90mgKOH/gである請求項1~5のいずれかに記載の防錆用組成物。
- さらに、水酸基との反応性を有する水溶性ジルコニウム化合物(D)を含有する請求項1~6のいずれかに記載の防錆用組成物。
- 水溶性ジルコニウム化合物(D)が炭酸ジルコニウムアンモニウムである請求項7に記載の防錆用組成物。
- 架橋剤(B)が、オキサゾリン化合物(b1)およびシランカップリング剤(b2)から選ばれた少なくとも1種である請求項1~8のいずれかに記載の防錆用組成物。
- オキサゾリン系化合物(b1)は、水分散性で、かつ、オキサゾリン基当量が200~5000g/当量である請求項9に記載の防錆用組成物。
- シランカップリング剤(b2)が、グリシジル基、アミノ基、アミド基、またはイソシアネート基を有する化合物である請求項9または10に記載の防錆用組成物。
- 架橋剤(B)が、オキサゾリン化合物(b1)およびシランカップリング剤(b2)である請求項9~11のいずれかに記載の防錆用組成物。
- 重合体(A)100重量部に対して、オキサゾリン系化合物(b1)を1~40重量部、シランカップリング剤(b2)を0.1~10重量部の割合で含有する請求項12に記載の防錆用組成物。
- さらに、水酸基とオキサゾリン基との反応を促進する触媒(C)を含有する請求項12または13に記載の防錆用組成物。
- 水酸基との反応性を有する水溶性ジルコニウム化合物(D)を含有し、重合体(A)100重量部に対して、オキサゾリン系化合物(b1)を1~40重量部、シランカップリング剤(b2)を0.1~5重量部、触媒(C)を0.1~10重量部、水溶性ジルコニウム化合物(D)を0.1~5重量部の割合で含有する請求項14に記載の防錆用組成物。
- 触媒(C)がリン酸二水素アンモニウム、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムヒドロキサイド、ハロゲン化リチウムおよび水酸化リチウムから選ばれた化合物である請求項14または15に記載の防錆用組成物。
- 請求項1~16のいずれかに記載の防錆用組成物を含む水分散体。
- 請求項1~16のいずれかに記載の防錆用組成物の硬化物で鋼板を被覆してなる防錆鋼板。
- α,β-モノエチレン性不飽和基を有するニトリル系モノマー(a-1)から導かれる構造単位、α,β-モノエチレン性不飽和基を有するモノマー(a-2)(ただし、前記(a-1)成分を除く)から導かれる構造単位、水酸基を有するモノマー(a-3)から導かれる構造単位およびアルコキシシリル(メタ)アクリレート(a-4)から導かれる構造単位を含む防錆用重合体。
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CN104611108A (zh) * | 2015-01-28 | 2015-05-13 | 安徽祈艾特电子科技有限公司 | 一种长效快干型金属防锈油 |
CN104611099A (zh) * | 2015-01-28 | 2015-05-13 | 安徽祈艾特电子科技有限公司 | 一种金属除锈防锈混合油 |
CN104629880A (zh) * | 2015-01-28 | 2015-05-20 | 安徽祈艾特电子科技有限公司 | 一种高抗湿热抗盐雾防锈油 |
CN113004517A (zh) * | 2021-03-08 | 2021-06-22 | 广州市白云化工实业有限公司 | 改性环氧树脂、胶粘剂及其制备方法与应用 |
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CN112142903B (zh) * | 2019-06-28 | 2022-07-15 | 长兴化学工业(中国)有限公司 | 有机硅改性丙烯酸树脂及其制备方法 |
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