CN114058237B - Corrosion resistant coating composition - Google Patents

Corrosion resistant coating composition Download PDF

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Publication number
CN114058237B
CN114058237B CN202110894817.8A CN202110894817A CN114058237B CN 114058237 B CN114058237 B CN 114058237B CN 202110894817 A CN202110894817 A CN 202110894817A CN 114058237 B CN114058237 B CN 114058237B
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coating film
mass
resin
composition
coating
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CN114058237A (en
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田渕秀典
富田直树
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Chugoku Marine Paints Ltd
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Chugoku Marine Paints Ltd
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    • 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
    • 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
    • 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
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention aims to solve the technical problems that: provided is an anticorrosive coating composition which can form a coating film having excellent anticorrosive properties and water resistance, has a long shelf life, and has excellent drying and curing properties. The technical scheme for solving the technical problems is as follows: relates to an anticorrosive coating composition, a coating film, a substrate with a coating film and a manufacturing method thereof, wherein the anticorrosive coating composition comprises: a first agent containing an epoxy resin curing agent (A), (meth) acrylic resin (B) and water (D); and a second agent containing a non-aqueous epoxy resin (C) having an epoxy equivalent of 270 or less.

Description

Corrosion resistant coating composition
Technical Field
The present invention relates to an anticorrosive coating composition, a coating film, a substrate with a coating film, and a method for producing the same.
Background
Conventionally, for the purpose of preventing corrosion, for example, an anticorrosive coating film is provided on a substrate of a land, an offshore structure, or the like, such as a bridge, a storage tank, a plant, a container for (transportation), or the like.
In recent years, from the viewpoints of environmental protection, safety in working environment, and the like, the control of the content of volatile organic compounds (VOC: volatile Organic Compounds) has become strict, and there has been a demand for replacement of a solvent-based paint from a water-based paint for a paint which forms the above-described anticorrosive coating film.
As such water-based paint, patent documents 1 and 2 describe water-based anticorrosive paint of natural drying type (room temperature curability).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-222901
Patent document 2: japanese patent laid-open No. 11-166153
Disclosure of Invention
Technical problem to be solved by the invention
Although the conventional aqueous anticorrosive paint described in patent documents 1 and 2 and the like is dried and cured to some extent at a normal temperature of about 23 ℃, the drying and curing speeds thereof are not sufficiently high, and there is room for improvement particularly in the drying and curing speeds at low temperatures (for example: 5 ℃) such as winter.
Examples of the coating material having excellent corrosion resistance include epoxy-amine-based coating materials. In order to improve the drying and curing properties of such epoxy-amine-based coating materials, it is conceivable to increase the molecular weight of the epoxy resin or to use highly reactive amines.
However, the inventors of the present invention have tried these methods and found that although the drying and curing properties can be improved, in the former case, the corrosion resistance is lowered; in the latter case, the pot life of the coating material is shortened. In particular, there is a trade-off between the excellent (quick) drying and curing properties of the paint and the long shelf life of the paint, and the conventional paint cannot have both of these properties.
The present invention has been made in view of the above problems, and the technical problems to be solved by the present invention are as follows: provided is an anticorrosive coating composition which can form a coating film having excellent anticorrosive properties and water resistance, has a long shelf life, and has excellent drying and curing properties.
Technical scheme for solving technical problems
As a result of intensive studies on a method for solving the above-mentioned problems, it was found that the above-mentioned problems can be solved by using a specific composition, until the present invention has been completed.
The configuration of the present invention is described below.
< 1 > an anticorrosive coating composition comprising: a first agent containing an epoxy resin curing agent (A), (meth) acrylic resin (B) and water (D); and a second agent containing a non-aqueous epoxy resin (C) having an epoxy equivalent of 270 or less.
The anticorrosive coating composition according to claim 2 < 1, wherein the curing agent (A) contains 1 or more selected from the group consisting of an aqueous amine curing agent (A1) and an aqueous amine-modified epoxy resin (A2).
The anticorrosive coating composition of < 3 > as defined in < 1 > or < 2 >, wherein the nonvolatile content of the resin (B) is 20 to 95% by mass relative to 100% by mass of the total nonvolatile content of the curing agent (A), the resin (B) and the resin (C).
The anticorrosive coating composition according to any one of < 4 > to < 1 > to < 3 >, wherein the content of Volatile Organic Compounds (VOC) is 200g/L or less.
A coating film comprising the anticorrosive coating composition according to any one of < 1 > - < 4 >.
< 6 > a substrate with a coating film comprising a substrate and < 5 > said coating film.
< 7 > a method for producing a substrate with a coating film, comprising the following steps [1] and [2]:
[1] coating the anticorrosive coating composition according to any one of < 1 > - < 4 > on a substrate;
[2] and a step of drying the anticorrosive coating composition applied to the substrate to form a coating film.
Effects of the invention
The present invention can provide an anticorrosive coating composition which can form a coating film excellent in corrosion resistance and water resistance, has a long shelf life (5 hours or more), and is excellent in drying and curing properties (hereinafter also simply referred to as "drying properties").
In particular, the anticorrosive coating composition of the present invention has a low VOC content and a long shelf life, and can be dried and cured at a high rate even at a low temperature (for example, 5 ℃) in winter or the like, and therefore can significantly improve the coating workability in a coating site as compared with conventional coating materials.
Detailed Description
Corrosion-resistant coating compositions
The anticorrosive coating composition according to the present invention (hereinafter also referred to simply as "present composition") comprises: a first agent containing an epoxy resin curing agent (A), (meth) acrylic resin (B) and water (D); and a second agent containing a non-aqueous epoxy resin (C) having an epoxy equivalent of 270 or less.
Most of the conventional compositions contain a (meth) acrylic resin in a main agent containing an epoxy resin, but one of the characteristics of the present composition is that: the first agent is blended with an epoxy resin curing agent (A) and a (meth) acrylic resin (B). The composition having such a constitution is also considered to be one cause of the composition exerting the above effects which cannot be achieved by the conventional coating materials.
The composition is not particularly limited as long as it is a multi-component type composition containing the first agent and the second agent, and a three-component type composition or more containing a third agent other than the first agent and the second agent may be formed depending on the components used.
These first to third doses (hereinafter, these are also collectively referred to as "nth dose") are usually stored, transported, etc. in respective containers, and mixed at the time of coating (for example, immediately before coating) to form the present composition for use. That is, these nth agents can be said to be components of a kit for producing the present composition, in other words, the present composition can be said to be a kit for an anticorrosive coating composition containing the first agent and the second agent.
In the present invention, the nth agent is an agent which can be stored until the composition is prepared after the preparation of the agent, and for example, a polishing substrate described in the following examples is usually used in combination with other components immediately after the preparation of the polishing substrate, and thus is not an nth agent of the present invention.
The present composition is prepared by mixing the nth agent, but may be used after or during the preparation, after dilution according to a coating method or the like.
Except for the matters related to such dilution, the descriptions in this specification are all descriptions of the dilution.
The present composition is usually an aqueous coating composition because it contains water (D). The aqueous coating composition is a composition obtained by dispersing and/or dissolving components such as a curing agent (a), a resin (B), and a resin (C) in water or a medium (aqueous medium) containing water as a main component.
The water content in the aqueous coating composition is preferably 50 mass% or more, more preferably 60 to 100 mass%, and even more preferably 65 to 100 mass%, based on 100 mass% of the total amount of the dispersion medium and the solvent in the composition.
Regarding the environment in which the paint is applied to the base material of a container or the like, there are cases where the drying equipment is insufficient. In such an environment, when conventional aqueous paint is applied, the drying property is important, and a large amount of organic solvent is blended into the paint.
On the other hand, according to the present invention, a coating composition excellent in drying property can be obtained, and therefore, even if an organic solvent is not blended in a large amount as described above, a desired coating film can be easily formed at a place where drying equipment is insufficient and at a low temperature in winter or the like.
Therefore, the content of the Volatile Organic Compound (VOC) in the present composition is preferably 10 mass% or less, more preferably 8 mass% or less, from the viewpoints of environmental protection, safety of working environment, and the like; the VOC content in the present composition is preferably 200g/L or less, more preferably 180g/L or less.
The VOC content in the present composition can be calculated from the following formulas (1) and (2) using the values of the composition specific gravity, the heating residual component ratio (mass ratio of non-volatile components), and the moisture ratio. The specific gravity of the composition, the heating residual component ratio, and the water content ratio may be measured as follows or calculated from the raw materials used.
VOC content (% by mass) = (100-heating residual component rate-moisture rate)/100 … (1)
VOC content (g/L) =composition specific gravity×1000× (100-heating residual component rate-moisture rate)/100 … (2)
Specific gravity of composition (g/ml): the present composition (composition immediately after the nth dose was mixed) was filled into a specific gravity cup having an internal volume of 100ml at a temperature of 23℃and the mass of the composition was measured to calculate a value.
Heating residual component ratio (mass%): the composition (composition immediately after mixing the nth agent) and 1.+ -. 0.1g of each component were measured and placed in a pan, and the composition was uniformly spread with a wire having a known mass, and heated at a heating temperature of 125℃for 1 hour (at normal pressure), and the values of the heated residual components (nonvolatile components) and the mass of the wire at this time were measured to calculate mass percentages.
Hereinafter, the heated residual component of the present composition is also referred to as the nonvolatile component of the present composition. The nonvolatile components of the components (for example, nonvolatile components of the curing agent (A)) refer to components other than the solvent and the dispersion medium in the components.
Moisture content (mass%): a value of the mass percentage of water contained in 100 mass% of the present composition, as measured by karl fischer titration.
When the present composition is coated and dried at 23℃according to ASTM D5895, the time until the dried state of the coating film surface reaches the semi-cured state (Tack-free) is preferably 10 to 60 minutes, more preferably 10 to 50 minutes; the time until the fully cured state (Dry-Hard) is reached is preferably 10 to 90 minutes, more preferably 10 to 60 minutes.
The present composition having these respective times (drying and curing rates) in the above-described ranges is excellent in drying properties, can greatly improve the coating workability as compared with conventional coating materials, and can be applied to a substrate which is not easily heated at the time of forming a coating film.
Further, when the present composition is coated and dried at 5℃based on ASTM D5895, the time until the dried state of the coating film surface reaches the semi-cured state (Tack-free) is preferably 20 to 60 minutes, more preferably 20 to 50 minutes; the time until the fully cured state (Dry-Hard) is reached is preferably 20 to 60 minutes, more preferably 20 to 50 minutes.
The present composition having these respective times (drying and curing rates) in the above-described ranges is excellent in drying properties at low temperatures, can greatly improve the coating workability as compared with conventional coating materials, and can be applied to a substrate which is not easily heated at the time of forming a coating film.
The pot life of the present composition is preferably 3 hours or more, more preferably 5 hours or more, as measured by the method described in the following examples.
The composition can be a composition having a shelf life in the above range and a drying and curing rate in the above range, and thus can significantly improve the coating workability as compared with conventional coating materials.
The composition is suitable for substrates such as steel (iron, steel, alloy iron, carbon steel, mild steel (mill steel), alloy steel, etc.), nonferrous metals (zinc, aluminum, copper, brass, zinc plating, zinc spraying, etc.), stainless steel (SUS 304, SUS410, etc.), and is particularly suitable for substrates made of steel or stainless steel. Such a substrate is particularly suitable for use in (large) steel or stainless steel structures such as ships, offshore structures, plants, bridges, tanks, containers (particularly refrigerated containers) and the like.
The present composition can be applied to the above-mentioned substrate as an anticorrosive coating composition.
The composition can be used as a primer coating (primer) for the above substrate, as an intermediate coating formed between a primer coating and a top coating, and as a top coating. More specifically, the present composition can be suitably used as a primer coating for the above-mentioned substrate, a primer coating for an intermediate paint, a top coating for the inner surface of a storage tank, a container or the like, a zinc primer containing zinc powder.
< first agent >)
The first agent of the present composition is not particularly limited as long as it contains the epoxy resin curing agent (a), (meth) acrylic resin (B) and water (D).
Other components such as pigment (E) (for example, extender pigment, coloring pigment, rust preventive pigment), anti-flash rust agent, dispersant, defoaming agent, thixotropic agent (anti-sagging, anti-settling agent), leveling agent, wetting agent, tackifier, film forming aid, plasticizer, drying agent, fibrous substance, surfactant, organic solvent, mildew preventive, preservative, ultraviolet absorber, light stabilizer, pH regulator and the like may be blended as needed in the first agent within the range not impairing the effect of the present invention.
These may be used alone or in combination of 1 kind or 2 or more kinds.
In addition, from the viewpoint of coating workability, the present composition preferably contains no sand.
[ epoxy resin curing agent (A) ]
The curing agent (a) is not particularly limited as long as it contains active hydrogen and can react with the epoxy resin (C), and examples thereof include an amine curing agent and an acid anhydride curing agent. Among these, the amine curing agent is preferable in that a coating film having more excellent corrosion resistance can be easily formed.
The curing agent (A) contained in the composition may be 1 kind or 2 kinds or more.
Since the first agent of the present composition contains water (D), an aqueous compound that can be dispersed in water or dissolved in water is preferable.
Preferable examples of such an aqueous compound include an aqueous amine curing agent (A1) and an aqueous amine-modified epoxy resin (A2), and more preferably 1 or more selected from the group consisting of an aqueous amine curing agent (A1) and an aqueous amine-modified epoxy resin (A2).
The content of the nonvolatile component of the curing agent (a) in the present composition is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, relative to 100% by mass of the nonvolatile component of the present composition, from the viewpoint that a composition excellent in drying property can be easily obtained, a coating film excellent in water resistance and corrosion resistance can be easily formed, and the like.
Aqueous amine curing agent (A1)
Examples of the curing agent (A1) include a water-soluble amine compound and an amine emulsion.
Examples of the water-soluble amine compound include the following amine compound and a compound obtained by hydrophilizing the following amine compound by a known method. Examples of the method of hydrophilization include: introduction of a water-soluble group such as a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, or a hydroxyl group; and the introduction of hydrophilic groups such as addition modification of a glycidyl ether of a polyalkylene glycol.
The water-soluble amine compound is a compound having a transparent appearance in a state of being sufficiently stirred by mixing 30 mass% of water and 70 mass% of the amine compound at 25 ℃.
Examples of the amine emulsion include an emulsion in which the following amine compound is dispersed in an aqueous medium such as water.
As the curing agent (A1), 1 kind may be used, or 2 or more kinds may be used.
The amine compound is not particularly limited as long as it is an amine compound other than a tertiary amine (amine compound having only a tertiary amino group), and examples thereof include amine compounds having 2 or more amino groups in 1 molecule, and preferably amine compounds of aliphatic, alicyclic, aromatic, heterocyclic and the like.
Examples of the aliphatic amine compound include alkylene polyamine, polyalkylene polyamine, and alkylaminoalkylamine.
Examples of the alkylene polyamine include the formula: "H 2 N-R 1 -NH 2 ”(R 1 Is a divalent hydrocarbon group having 1 to 12 carbon atoms. ) Specific examples of the compounds include methylenediamine, ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, and trimethylhexamethylenediamine.
Examples of the polyalkylene polyamine include the formula: "H 2 N-(C m H 2m NH) n Specific examples of the compounds represented by H "(m is an integer of 1 to 10. N is an integer of 2 to 10, preferably an integer of 2 to 6) include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis (hexamethylene) triamine, triethylenebis (trimethylene) hexamine.
Examples of the alkylaminoalkylamine include the formula: "R 2 2 N-(CH 2 ) p -NH 2 ”(R 2 Independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (wherein at least 1R 2 Is an alkyl group having 1 to 8 carbon atoms. ) P is an integer of 1 to 6. ) Specific examples of the compounds include dimethylAminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminobutylamine.
Examples of aliphatic amines other than these include tetrakis (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1, 3-bis (2 ' -aminoethylamino) propane, tris (2-aminoethyl) amine, bis (cyanoethyl) diethylenetriamine, polyoxyalkylene polyamines (especially diethylene glycol bis (3-aminopropyl) ether), bis (aminomethyl) cyclohexane, isophorone diamine (IPDA), menthane Diamine (MDA), o-xylylene diamine, m-xylylene diamine (MXDA), p-xylylene diamine, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene, 1, 4-bis (3-aminopropyl) piperazine, 1- (2 ' -aminoethylpiperazine), 1- [2' - (2 "-aminoethylamino) ethyl ] piperazine.
Specific examples of the alicyclic amine include cyclohexane diamine, diaminodicyclohexylmethane (particularly 4,4 '-methylenedicyclohexylamine), 4' -isopropylidenedicyclohexylamine, norbornanediamine, and 2, 4-bis (4-aminocyclohexylmethyl) aniline.
Examples of the aromatic amine include aromatic polyamine compounds having 2 or more primary amino groups bonded to an aromatic ring such as a benzene ring or naphthalene ring.
Specific examples of the aromatic amine include phenylenediamine, naphthalenediamine, diaminodiphenylmethane, 2-bis (4-aminophenyl) propane, 4 '-diaminodiphenyl ether, 4' -diaminobenzophenone, 4 '-diaminodiphenyl sulfone, 3' -dimethyl-4, 4 '-diaminodiphenylmethane, diaminodiethylphenylmethane, 2,4' -diaminobiphenyl, 2,3 '-dimethyl-4, 4' -diaminobiphenyl, and 3,3 '-dimethoxy-4, 4' -diaminobiphenyl.
Specific examples of the heterocyclic amine include 1, 4-diazacycloheptane, 1, 11-diazaeicosane, and 1, 15-diazaoctacosane.
Examples of the amine compound include the modified amine, a fatty acid modified product such as polyamide amine, an amine adduct with an epoxy compound, a Mannich modified product (e.g., phenol amine (phenolic amide)), a Michael adduct, ketimine, and aldimine. Among these, polyamidoamines, amine adducts with epoxy compounds, and mannich modifications are preferable.
As the water-soluble amine compound, commercially available ones can be used, and examples thereof include "Daitocurar I-6020" (manufactured by Daitocurar Co., ltd.), "Cardolite NX-8102" (manufactured by Cardolite Corporation), "Anquamine 401" (manufactured by Evonik Industries Co., ltd.), "Beckopoox EH 613w/80WA" (manufactured by ALLNEX Co., ltd.), "Sunmide WH-900" (manufactured by Evonik Industries Co., ltd.).
As the amine emulsion, commercially available products may be used, and examples thereof include "Fujicure FXS-918-FA" (manufactured by T & K TOKA Co., ltd.), "EPILINK701" (manufactured by Evonik Industries Co., ltd.), and "YUKARESIN HD-03" (manufactured by Jicun oil chemical Co., ltd.).
The curing agent (A1) is preferably a water-soluble amine compound, particularly a water-soluble polyamine, from the viewpoints of the miscibility with the (meth) acrylic resin (B) described later, the storage stability after mixing with other components used in the first agent, and the like.
The active hydrogen equivalent of the nonvolatile component of the curing agent (A1) is preferably 30 to 500, more preferably 40 to 300, from the viewpoints that a composition excellent in drying property can be easily obtained, a coating film excellent in corrosion resistance and the like can be easily formed, and the like.
Aqueous amine modified epoxy resin (A2)
The resin (A2) is not particularly limited, and specific examples thereof include reaction products of 1 or 2 or more epoxy resins (a 1) and 1 or 2 or more amines (A2), preferably aqueous resins having 1 or more carboxyl groups in 1 molecule and an acid value of 1 to 20mgKOH/g of nonvolatile components.
By using such a resin (A2), a composition having more excellent drying properties can be easily obtained, and a coating film having more excellent corrosion resistance and adhesion to a substrate can be easily formed.
The resin (A2) of the present invention is a resin in which the monomer component constituting the epoxy resin exceeds 50% by mass based on 100% by mass of the entire monomer components constituting the resin.
As the resin (A2), 1 kind may be used, or 2 or more kinds may be used.
In the present invention, the "aqueous resin" is a resin in which water is a solvent or a dispersion medium or water is a main solvent or a dispersion medium, or a resin which can be mixed with water (can be diluted with water), and more specifically, a water-dispersible resin, a water-soluble resin, a self-emulsifiable resin, and the like are exemplified. Such an aqueous resin can be synthesized by a conventionally known method, for example, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a miniemulsion polymerization method, a microemulsion polymerization method, an emulsifier-free (soap-free) emulsion polymerization method, or the like. In addition, the aqueous resin may be obtained by a known method such as inversion emulsification, D-phase emulsification, forced emulsification, gel emulsification, inversion emulsification, high-pressure emulsification, or the like.
In addition, if the resin having no epoxy group is a resin using a compound having an epoxy group as a raw material, a generic term containing "epoxy" may be used, and thus the resin having no epoxy group is contained similarly to the "epoxy resin" in the present invention.
The epoxy equivalent of the nonvolatile component of the resin (A2) is preferably 1500 or more, more preferably 2000 or more, and particularly preferably the resin (A2) has no epoxy group, from the viewpoint that a composition having more excellent drying property can be easily obtained.
The above epoxy equivalent may be based on JIS K7236: 2001.
The acid value of the nonvolatile component of the resin (A2) is preferably 20mgKOH/g or less, more preferably 15mgKOH/g or less, preferably 1mgKOH/g or more, more preferably 2mgKOH/g or more.
By using the resin (A2) having an acid value in the above range, a composition having more excellent drying properties can be easily obtained, and a coating film having excellent corrosion resistance can be easily formed.
The acid value may be based on JIS K0070: 1992.
The amine value of the nonvolatile component of the resin (A2) is preferably 150mgKOH/g or less, more preferably 100mgKOH/g or less, preferably 1mgKOH/g or more, more preferably 25mgKOH/g or more.
By using the resin (A2) having an amine value in the above range, a composition having more excellent drying properties can be easily obtained, and a coating film having excellent corrosion resistance can be easily formed.
The amine value may be based on JIS K7273: 1995.
The amine (a 2) is not particularly limited, and monoamines and polyamines such as aliphatic amines, alicyclic amines, aromatic aliphatic amines and heterocyclic amines may be mentioned. The amine may be used alone or in combination of 1 kind or 2 or more kinds.
The amines are not particularly limited, and examples thereof include: primary alkylamines such as butylamine, octylamine, oleylamine, and 2-ethylhexyl amine; primary alkanolamines such as monoethanolamine, 2-ethoxyethanolamine and 2-hydroxypropanolamine; aliphatic polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine; alicyclic polyamines such as 1, 3-diaminocyclohexane and isophorone diamine; aromatic polyamines such as diaminodiphenylmethane; aromatic aliphatic amines such as o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine; mannich bases formed from polycondensates of polyamines, aldehyde compounds and 1-valent or multivalent phenols; polyamide polyamines obtained by reaction of polyamines with polycarboxylic and/or dimer acids; polyoxyalkylene amines such as polyoxyethylene amine and polyoxypropylene amine. From the viewpoint of excellent dispersibility into an aqueous medium and storage stability of a dispersion dispersed in an aqueous medium, primary alkylamines, primary alkanolamines, polyoxyalkylene amines are preferable, and primary alkanolamines and polyoxyalkylene polyamines are more preferable.
Examples of the polyoxyalkylene amine include compounds represented by the following structural formula (a 2-1).
[ formula, R 1 Is hydrogen, methyl, ethyl, propyl or tert-butyl, R 2 Independently ethylene, 1, 2-propylene, 2, 3-propylene, 1, 3-propylene, R 3 The average value of the repeating units represented by methylene, ethylene, 1, 2-propylene, 2, 3-propylene and 1, 3-propylene is 2 to 100.]
The molecular weight of the polyoxyalkylene amine is preferably 300 to 5,000, more preferably 400 to 1,500, from the viewpoint that a composition excellent in storage stability and corrosion resistance can be easily obtained.
As the polyoxyalkylene amine, commercially available ones can be used, and examples thereof include "JEFFAMINE M-600" (weight average molecular weight: 600), "JEFFAMINE M-1000" (weight average molecular weight: 1,000), "JEFFAMINE M-2005" (weight average molecular weight: 2,000), "JEFFAMINE M-2070" (weight average molecular weight: 2,000) (both of which are manufactured by Huntsman corporation). Of these, "JEFFAMINE M-600", "JEFFAMINE M-1000" are preferred.
The epoxy resin (a 1) is preferably a bisphenol type epoxy resin, more preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol AD type epoxy resin, and even more preferably a bisphenol a type epoxy resin, from the viewpoints of toughness of the obtained coating film, adhesion to a substrate, and the like.
The epoxy resin (a 1) may be used alone or in an amount of 2 or more.
In order to make the reaction product a resin having 1 or more carboxyl groups in the molecule, a compound having carboxyl groups may be used as the epoxy resin (a 1), a compound having carboxyl groups may be used as the compound (a 2), carboxyl groups may be generated when they are reacted, and the resultant resin may be modified after the reaction so as to have carboxyl groups, but it is preferable to use an unsaturated carboxylic acid (a 3) other than the epoxy resin (a 1) and the compound (a 2) when the reaction is performed.
Examples of the unsaturated carboxylic acid (a 3) include (meth) acrylic acid. These may be used singly or in combination of 2 or more.
The order of reacting the epoxy resin (a 1), the compound (a 2) and the unsaturated carboxylic acid (a 3) is not particularly limited, and it is preferable to react the epoxy resin (a 1) with the compound (a 2) (hereinafter also referred to as "reaction 1") and then react the compound obtained in the reaction 1 with the unsaturated carboxylic acid (a 3) (hereinafter also referred to as "reaction 2") in view of easily obtaining a resin satisfying the acid value and the amine value as described above.
These reactions 1 and 2 can be carried out by methods known per se.
Regarding the mixing ratio of the epoxy resin (a 1) and the compound (A2) in the reaction 1, when epoxy groups remain in the obtained resin (A2), the storage stability of the present composition may be lowered, and therefore, the ratio in which epoxy groups remain as little as possible in the obtained resin (A2) is preferably such that the amino groups are preferably in an amount of about 1.1 to 1.5 mol, more preferably in an amount of about 1.1 to 1.3 mol, relative to 1 mol of epoxy groups.
Regarding the mixing ratio of the compound obtained in the reaction 1 and the unsaturated carboxylic acid (a 3) in the reaction 2, when a primary amino group or a secondary amino group remains in the obtained resin (A2), the corrosion resistance of the obtained coating film may be lowered, and therefore, the amount of the carboxyl group is preferably about 1.1 to 1.5 mol, and more preferably about 1.1 to 1.3 mol, relative to 1 mol of the amino group.
As the resin (A2), commercially available ones can be used, and examples thereof include EPICLON C-250EP (manufactured by DIC Co., ltd., without an epoxy group, an acid value of a nonvolatile component: 5.7mgKOH/g, and an amine value of a nonvolatile component: 60 mgKOH/g) which is an aqueous amine-modified epoxy resin having a bisphenol A structure and 1 or more carboxyl groups in the molecule.
The content of the nonvolatile component (resin) in 100 mass% of the resin (A2) is preferably 30 to 75 mass%, more preferably 35 to 60 mass%, from the viewpoint of obtaining a composition excellent in the ease of production, storage stability, and the like.
The remaining portion of the resin (A2) preferably contains water, and may contain a conventionally known component such as a surfactant, if necessary.
[ (meth) acrylic resin (B) ]
The resin (B) is not particularly limited as long as it is a resin obtained by using a (meth) acrylic compound as a monomer, and is preferably an aqueous resin, more preferably an emulsion (including latex) in view of the ease of obtaining the present composition having excellent storage stability.
In the present composition, since the resin (B) is blended in the first agent in the composition containing the curing agent (a) and the water (D) as the first agent and the resin (C) as the second agent, in particular, a composition having a long shelf life and excellent drying property can be easily obtained, and a coating film having excellent water resistance can be easily formed.
The resin (B) contained in the composition may be 1 or 2 or more.
Wherein, in the present invention, (meth) acrylic acid means acrylic acid and/or methacrylic acid. The same kind of expression means the same meaning. That is, the (meth) acrylic resin (B) may be an acrylic resin or a methacrylic resin.
The resin (B) may be a homopolymer or copolymer of a (meth) acrylic monomer, or a copolymer of a (meth) acrylic monomer and another monomer.
Examples of the (meth) acrylic monomer include:
(meth) acrylic acid;
alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like;
cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate;
aryl (meth) acrylates such as phenyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate;
alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like;
(meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, hydroxymethyl (meth) acrylamide, alkoxymethyl (meth) acrylamide, and the like, or derivatives thereof;
epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate.
These (meth) acrylic monomers may be used in an amount of 1 or 2 or more.
The (meth) acrylic acid monomer preferably contains at least 1 monomer selected from the group consisting of (meth) acrylic acid and alkyl (meth) acrylate, more preferably contains at least 1 monomer selected from the group consisting of (meth) acrylic acid, methyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and octyl (meth) acrylate, and particularly preferably contains at least 2-ethylhexyl (meth) acrylate, from the viewpoint of being capable of easily forming a coating film excellent in water resistance.
Examples of the other monomer copolymerizable with the (meth) acrylic monomer include:
aromatic vinyl monomers such as styrene, α -methylstyrene, p-t-butylstyrene, and vinyltoluene;
nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
fatty acid vinyl ester monomers such as vinyl propionate;
Unsaturated polycarboxylic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic acid, and the like, or anhydrides thereof;
esters of unsaturated polycarboxylic acid derivatives such as dimethyl maleate and diethyl fumarate;
n-substituted maleimides such as N-phenylmaleimide;
olefin monomers such as ethylene and propylene.
These monomers may be used in an amount of 1 or 2 or more.
The other monomer is preferably an aromatic vinyl monomer, more preferably styrene, particularly preferably styrene, and is free of a nitrile group-containing monomer, particularly acrylonitrile, from the viewpoint that a coating film excellent in water resistance can be easily formed.
The acid value of the nonvolatile component of the resin (B) is preferably 10 to 70mgKOH/g, more preferably 20 to 60mgKOH/g.
By using the resin (B) having an acid value in the above range, a composition having more excellent drying properties can be easily obtained, and a coating film having excellent corrosion resistance can be easily formed.
The acid value may be based on JIS K0070: 1992.
The weight average molecular weight (Mw) of the nonvolatile component of the resin (B) as measured by Gel Permeation Chromatography (GPC) is preferably 50,000 ～ 200,000, and more preferably 80,000 ～ 160,000 in terms of obtaining a composition excellent in coating properties, easily obtaining a coating film excellent in coating film physical properties, and the like.
The content of the nonvolatile component of the resin (B) in the present composition is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, relative to 100% by mass of the nonvolatile component of the present composition, from the viewpoint that a composition having a long shelf life and excellent drying property can be easily obtained, a coating film having excellent water resistance can be easily formed, and the like.
For example, when the present composition is used as a primer coating material, a primer coating material or a top coating material, the content of the nonvolatile component of the resin (B) in the composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on 100% by mass of the nonvolatile component of the present composition, for the same reasons as those described above, and when the present composition is used as a zinc primer, for example, the content of the nonvolatile component of the resin (B) in the present composition is preferably 1 to 10% by mass, based on 100% by mass, based on the nonvolatile component of the present composition, for the same reasons as those described above.
For the same reasons as described above, the content of the nonvolatile component of the resin (B) in the present composition is preferably 20 to 95% by mass, more preferably 25 to 90% by mass, relative to 100% by mass of the total of the nonvolatile components of the curing agent (a), the resin (B) and the resin (C).
For example, when the present composition is used as a primer coating, or a topcoat coating, the content of the nonvolatile component of the resin (B) in the present composition is preferably 25 to 90% by mass relative to 100% by mass of the total of the nonvolatile components of the curing agent (a), the resin (B), and the resin (C) for the same reasons as described above, and when the present composition is used as a zinc primer, for example, the content of the nonvolatile component of the resin (B) in the present composition is preferably 20 to 60% by mass relative to 100% by mass of the total of the nonvolatile components of the curing agent (a), the resin (B), and the resin (C) for the same reasons as described above.
[ Water (D) ]
The curing agent (a) and the resin (B) may contain water, and it is preferable that the curing agent (a) and the resin (B) contain water. Therefore, although water contained in the curing agent (a) and the resin (B) may be used as water (D), the present composition is preferably blended with water (D) in addition to water contained in the curing agent (a) and the resin (B) in order to facilitate the preparation of the present composition and to obtain a composition having more excellent storage stability and coating workability.
The water (D) is not particularly limited, and tap water or the like may be used, and ion-exchanged water or the like is preferably used.
The content of water in the first agent (including water that can be contained in the curing agent (a) and the resin (B)) is not particularly limited, but is preferably 10 to 50 mass%.
In addition, the content of water in the first agent is preferably 50% by mass or more, more preferably 70 to 100% by mass, particularly preferably 80 to 100% by mass, relative to 100% by mass of the total amount of the dispersion medium and the solvent in the first agent, from the viewpoint that a desired aqueous coating composition can be easily obtained.
[ pigment (E) ]
The present composition preferably contains a pigment (except zinc powder and a flash rust inhibitor) in terms of imparting strength, corrosion resistance, color and the like to the coating film. Examples of the pigment include extender pigments, coloring pigments, rust-preventive pigments, and the like, and both organic and inorganic pigments may be used.
As the pigment (E), 1 kind may be used, or 2 or more kinds may be used.
Examples of the extender pigment that can be used include (precipitated) barium sulfate, (potassium) feldspar, alumina white, magnesium carbonate, barium carbonate, calcium carbonate, dolomite, silica, talc, mica, kaolin, glass flakes, and plastic flakes.
When the present composition contains an extender pigment, the content thereof is preferably 1 to 70 mass%, more preferably 1.5 to 60 mass% with respect to 100 mass% of the nonvolatile component of the present composition.
When the present composition contains an extender pigment, for example, when the present composition is used as a primer coating material, an intermediate coating material or a top coating material, the content of the extender pigment in the present composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, relative to 100% by mass of the nonvolatile component of the present composition, and when the present composition is used as a zinc primer, for example, the content of the nonvolatile component of the extender pigment in the present composition is preferably 1 to 10% by mass, relative to 100% by mass of the nonvolatile component of the present composition.
As the coloring pigment, conventionally known coloring pigments can be used, and examples thereof include: inorganic pigments such as carbon black, titanium dioxide (titanium white), iron oxide (red iron oxide), yellow iron oxide, ultramarine, etc.; organic pigments such as phthalocyanine blue and phthalocyanine green; flake iron oxide, stainless steel flakes, and other luster pigments.
When the present composition contains a coloring pigment, the content thereof is preferably 0.01 to 30% by mass, more preferably 0.1 to 25% by mass, relative to 100% by mass of the nonvolatile component of the present composition.
Examples of the rust inhibitive pigment that is usable include conventionally known rust inhibitive pigments, such as aluminum phosphate compounds, zinc phosphate compounds, calcium phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, zinc molybdate compounds, aluminum tripolyphosphate compounds, zinc borate compounds, barium borate compounds, and metal ion exchanged silica compounds. Among these, aluminum phosphate compounds and zinc phosphate compounds are preferable from the viewpoint of being able to easily obtain a coating film having more excellent corrosion resistance, and metal ion-exchanged silica compounds and magnesium ion-exchanged silica compounds are more preferable from the viewpoint of being able to easily form a coating film having excellent adhesion to a nonferrous metal substrate and a stainless steel substrate.
Examples of commercial products of such rust inhibitive pigments include LF Bousei PW2 (manufactured by KIKUCHI COLOR Co., ltd.) as a zinc phosphate system, LF Bousei PM-303W (manufactured by KIKUCHI COLOR Co., ltd.) as an aluminum phosphate system, K-WHTE#140W (manufactured by Tayca Co., ltd.) as an aluminum tripolyphosphate system compound, sylomask 55 (manufactured by FUJI SILYSIA CHEMICAL Co., ltd.) as a calcium ion-exchanged silica system compound, and Sylomask 52 (manufactured by FUJI SILYSIA CHEMICAL Co., ltd.) as a magnesium ion-exchanged silica system compound.
When the composition contains a rust inhibitive pigment, the content thereof is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, relative to 100% by mass of the nonvolatile component of the composition.
Thixotropic agent (anti-sagging anti-settling agent)
The composition preferably contains a thixotropic agent in order to improve the thickness and sagging resistance during coating and to prevent sedimentation of components insoluble in water or organic solvents, such as zinc powder and pigments.
As the thixotropic agent, 1 kind may be used, or 2 or more kinds may be used.
Examples of thixotropic agents include: organoclay salts such as stearate, lecithin, and alkylsulfonate of Al, ca, and Zn; clays such as bentonite clay and hectorite clay, and organic modifications of the clays (e.g., organomodified hectorite clay); oxidized polyethylene wax, ethylene-vinyl acetate wax, polyamide wax, hydrogenated castor oil wax, and synthetic fumed silica. Among these, organic thixotropic agents such as organomodified hectorite clay, oxidized polyethylene wax, ethylene-vinyl acetate wax, and polyamide wax are preferable in that a coating film excellent in crack resistance can be easily formed.
When the thixotropic agent is contained in the composition, the content thereof is preferably 0.01 to 3.5% by mass, more preferably 0.05 to 3% by mass, relative to 100% by mass of the nonvolatile component of the composition, in view of the ease of forming a coating film excellent in crack resistance, and the like.
[ dispersant ]
The present composition preferably contains a dispersant in view of improving the dispersibility of zinc powder, pigment and the like in the composition, enabling easy formation of a coating film having a good appearance, enabling easy formation of a coating film having excellent crack resistance and the like.
As the dispersant, 1 kind may be used, or 2 or more kinds may be used.
Examples of the dispersant include, but are not particularly limited to, various dispersants such as a copolymer having a pigment adsorption group (pigment affinity group) such as a carboxyl group, a phosphate group, an amino group, a salt thereof, or an ammonium salt group, and having a soluble chain such as a fatty acid, a polyamino group, a polyether, a polyester, a polyurethane, or a polyacrylate.
When the present composition contains a dispersant, the content thereof is preferably 0.1 to 3% by mass, more preferably 0.1 to 2.5% by mass, relative to 100% by mass of the nonvolatile component of the present composition, in view of the ease of forming a coating film excellent in crack resistance, etc.
[ anti-flash rust agent ]
When an aqueous coating material is applied to an active steel surface, rust may be generated by elution of iron ions or the like from the steel surface during drying from just after the application, and flash rust may be formed by the rust or the like floating out of the coating film surface. Particularly under the condition of high temperature and high humidity, flash rust is sometimes generated remarkably.
For the purpose of suppressing such flash rust, a flash rust inhibitor is preferably used in the present composition.
As the flash rust inhibitor, 1 kind may be used, or 2 or more kinds may be used.
Examples of the flash rust inhibitor include: nitrite salts such as sodium nitrite, potassium nitrite, calcium nitrite, strontium nitrite, barium nitrite, ammonium nitrite and the like; benzoate salts such as sodium benzoate, potassium benzoate, calcium benzoate, ammonium benzoate, and the like; phytate such as sodium phytate and potassium phytate; salts of fatty acids such as sebacic acid and dodecanoic acid; phosphoric acid derivatives such as alkyl phosphoric acid and polyphosphoric acid; tannic acid salt; amine chelating agents such as N- (2-hydroxyethyl) ethylenediamine triacetic acid (HEDTA), ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA), propylenediamine tetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriamine pentamethylenephosphonic acid (DTPMP), and alkali metal salts thereof; an addition reactant of 4-methyl-gamma-oxo-phenylbutyric acid and N-ethylmorpholine; interlayer compounds obtained by inserting a monoalkylamine, polyamine, quaternary ammonium ion or the like into a layered phosphate such as aluminum dihydrogen tripolyphosphate; hydrazine derivatives such as hydrazide compounds, semicarbazide compounds and hydrazone compounds.
Among these, nitrite (for example, metal salts such as sodium, potassium, and calcium, and ammonium salts) and benzoate (for example, metal salts such as sodium, potassium, and calcium, and ammonium salts) are preferable from the viewpoint of excellent flash rust resistance and low cost, and nitrite is more preferable from the viewpoint that a composition exhibiting high flash rust resistance can be easily obtained even with a small amount of use, and sodium nitrite is particularly preferable.
When the composition contains a flash rust inhibitor, the content thereof is preferably 0.01 to 2% by mass, more preferably 0.03 to 1% by mass, relative to 100% by mass of the nonvolatile component of the composition, from the viewpoint of easily obtaining a composition excellent in flash rust resistance.
[ defoamer ]
The present composition preferably contains an antifoaming agent in view of suppressing the generation of bubbles during the production or coating of the composition, breaking bubbles generated in the present composition, and easily forming a coating film having desired physical properties.
The defoaming agent may be commercially available products, and examples thereof include "BYK-320", "BYK-066N", "BYK-1790" (manufactured by BYK Chemi Japan Co., ltd.) and "TEGO Airex 902W" (manufactured by Evonik Co.).
When the present composition contains an antifoaming agent, the content thereof is preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, relative to 100% by mass of the nonvolatile component of the present composition, from the viewpoint that the occurrence of bubbles can be sufficiently suppressed and a coating film having desired physical properties can be easily formed.
[ film-Forming auxiliary ]
Since the composition may freeze in winter due to the water content, the present composition preferably contains a film forming aid in terms of improving film forming property at low temperature, appearance of a finished product of the obtained coating film, and the like.
As the film forming aid, a compound generally used in an aqueous coating composition can be used, and examples thereof include: straight-chain or branched aliphatic alcohols having 5 to 10 carbon atoms; alcohols having an aromatic ring; monoethers such as (poly) ethylene glycol and (poly) propylene glycol; (poly) glycol ether esters; (Poly) propylene glycol ether esters.
When the present composition contains a film-forming auxiliary agent, the content thereof is preferably 1 to 10% by mass, more preferably 3 to 8% by mass, relative to 100% by mass of the nonvolatile component of the present composition, in view of the ease of forming a film excellent in film-forming property and appearance at low temperature, and the like.
Plasticizer (plasticizer)
When the composition is used as a primer coating for a nonferrous metal substrate or a stainless steel substrate, it preferably contains a plasticizer.
As the plasticizer, conventionally known plasticizers can be used, and examples thereof include plasticizers such as glycol ether polymers, phthalic acid esters, trimellitic acid esters, aliphatic dibasic acid esters, phosphoric acid esters, ricinoleic acid esters, polyesters, acetic acid esters, and sulfonamides.
When the present composition contains a plasticizer, the content thereof is preferably 0.1 to 3.0 mass%, more preferably 0.5 to 2.5 mass% relative to 100 mass% of the nonvolatile component of the present composition, in view of the ease of forming a coating film excellent in adhesion to nonferrous metal or stainless steel surfaces, and the like.
[ tackifier ]
The present composition preferably contains a thickener in view of suppressing sagging during coating.
The thickener may be any conventionally known thickener, and examples thereof include polysaccharides, alkali tackifiers, polyurethane associative type, polyether associative type, polyolefin type, cellulose type, and the like.
When the composition contains a thickener, the content thereof is preferably 0.1 to 0.4 mass%, more preferably 0.15 to 0.35 mass% relative to 100 mass% of the nonvolatile component of the composition, in view of sufficiently suppressing sagging and the like at the time of coating.
[ organic solvent ]
When the first agent contains water, an organic solvent that can be mixed with water may be used in any amount in order to suppress freezing in winter and to obtain a composition that is more excellent in coating workability.
As the organic solvent, 1 kind may be used, or 2 or more kinds may be used.
Examples of such organic solvents include alcohol solvents having 1 to 3 carbon atoms such as isopropyl alcohol and ethylene glycol, glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and the like.
The content of the organic solvent is preferably used in an amount such that the VOC content in the present composition falls within the above range.
< second dose >)
The second agent of the present composition is not particularly limited as long as it contains a nonaqueous epoxy resin (C) having an epoxy equivalent of 270 or less, and may be substantially composed of only the resin (C), and may contain components other than the resin (C) within a range that does not impair the effects of the present invention. The component other than the resin (C) may be zinc powder (F) in addition to the same components as those described in the column of the first agent.
The other components may be used in an amount of 1 or 2 or more.
In addition, the second agent preferably contains a film-forming auxiliary agent for the same reasons as those described above, and the film-forming auxiliary agent and the like which are the same as those listed in the column of the first agent can be cited as the film-forming auxiliary agent.
Epoxy resin (C) >, and process for producing the same
Examples of the resin (C) include polymers or oligomers having 2 or more epoxy groups in the molecule, and polymers or oligomers produced by ring-opening reaction of the epoxy groups.
The resin (C) may be used in an amount of 1 kind or 2 or more kinds.
The resin (C) is a nonaqueous epoxy resin, that is, an epoxy resin which is insoluble or dispersible in water, in view of the fact that a composition excellent in drying property at low temperature can be easily obtained, a coating film excellent in water resistance and corrosion resistance can be easily formed, and the like.
Specific examples of the nonaqueous epoxy resin include those having a light transmittance of preferably 1% or more, more preferably 10% or more, as measured by the method described in the examples below.
The epoxy equivalent of the resin (C) (the epoxy equivalent of the nonvolatile component of the resin (C)) is preferably 100 to 270, more preferably 100 to 200, from the viewpoint that a coating composition having a low VOC content can be easily obtained, and the like. The epoxy resin having an epoxy equivalent in such a range may be a liquid or semisolid epoxy resin.
When the epoxy equivalent is within the above range, a coating composition having a low VOC content can be easily obtained, and the effect of the present invention is further exhibited, which is preferable. When the epoxy equivalent exceeds 270, a coating composition having a low VOC content tends to be not easily obtained.
For the nonvolatile components of the resin, the above epoxy equivalent is based on JIS K7236: 2001.
In addition, an epoxy resin having an epoxy equivalent of more than 270 may be used in the present composition in combination within a range that does not hinder the effect of the present invention, and the proportion of the epoxy resin having an epoxy equivalent of more than 270 is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the resin (C) from the viewpoint that a low VOC content coating composition can be easily obtained.
Examples of the resin (C) include bisphenol epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, novolac epoxy resins, cresol epoxy resins, dimer acid modified epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and epoxidized oil epoxy resins.
Among these, bisphenol type epoxy resins and novolak type epoxy resins are preferable, bisphenol a type or bisphenol F type epoxy resins are more preferable, and bisphenol a type epoxy resins are particularly preferable, because an anticorrosive coating film excellent in adhesion to a substrate can be easily formed.
Examples of the resin (C) include: epichlorohydrin-bisphenol a epoxy resin (bisphenol a diglycidyl ether type); epichlorohydrin-bisphenol AD epoxy resin; epichlorohydrin-bisphenol F epoxy resin; an epoxy novolac resin; alicyclic epoxy resins obtained from 3, 4-epoxyphenoxy-3 ',4' -epoxyphenylcarboxymethane and the like; a brominated epoxy resin in which at least 1 of hydrogen atoms bonded to benzene rings in an epichlorohydrin-bisphenol a epoxy resin is substituted with bromine atoms; aliphatic epoxy resins derived from epichlorohydrin and aliphatic diols; multifunctional epoxy resins derived from epichlorohydrin and tris (hydroxyphenyl) methane.
Examples of the bisphenol a type epoxy resin include polycondensates of bisphenol a type diglycidyl ethers such as bisphenol a diglycidyl ether, bisphenol a (poly) propylene oxide diglycidyl ether, bisphenol a (poly) ethylene oxide diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, and hydrogenated bisphenol a (poly) propylene oxide diglycidyl ether.
The resin (C) may be synthesized by a known method, or may be commercially available.
As the commercial products, examples of the commercial products which are liquid at ordinary temperature (15 to 25 ℃ C., the same applies hereinafter) include "EPOKUKDO YD-128" (manufactured by KUKDO Co., ltd., bisphenol A diglycidyl ether, nonvolatile components 100%, epoxy equivalent 184 to 190, viscosity 11,500 to 13,500 mPa.s/25 ℃), "E-028" (manufactured by Daphne chemical Co., ltd., bisphenol A diglycidyl ether, nonvolatile components 100%, epoxy equivalent 180 to 190, viscosity 12,000 to 15,000 mPa.s/25 ℃), "jER-807" (manufactured by Mitsubishi chemical Co., ltd., bisphenol F diglycidyl ether, epoxy equivalent 160 to 175, viscosity 3,000 to 4,500 mPa.s/25 ℃), "E-028-90X" (manufactured by Daphne chemical Co., ltd., bisphenol A diglycidyl ether xylene solution (828 epoxy resin solution, nonvolatile components 90%) and the like). Examples of the commercial products which are semisolid at ordinary temperatures include "jER-834" (manufactured by Mitsubishi Chemical corporation, bisphenol A type epoxy resin, epoxy equivalent of 230 to 270, nonvolatile content of 100%), "E-834-85X" (manufactured by Dairy Chemical corporation, xylene solution of bisphenol A type semisolid epoxy resin (834 type epoxy resin solution, nonvolatile content of 85%, nonvolatile content of about 255%), and the like, "D.E.N.425" (manufactured by DOW Chemical corporation, epoxy equivalent of 169 to 175, nonvolatile content of 100%), "D.E.N.431" (manufactured by DOW Chemical corporation, epoxy equivalent of 172 to 179, nonvolatile content of 100%) and "D.E.N.438" (manufactured by DOW Chemical corporation, epoxy equivalent of 176 to 181, nonvolatile content of 100%) of the novolak type epoxy resin.
The content of the resin (C) is preferably 0.5 to 25 mass%, more preferably 1 to 20 mass%, based on 100 mass% of the nonvolatile component of the present composition.
The content of the resin (C) in the second agent is preferably 1 to 95% by mass, more preferably 1.5 to 90% by mass.
When the content of the resin (C) is within the above range, an anticorrosive coating film having more excellent anticorrosive properties and adhesion to a substrate can be easily obtained.
For example, when the present composition is used as a primer coating material, a primer coating material or a top coating material, the content of the nonvolatile component of the resin (C) in the present composition is preferably 1 to 25% by mass, more preferably 1.5 to 20% by mass, relative to 100% by mass of the nonvolatile component of the present composition, for the same reason as described above; in the case of using the present composition as a zinc primer, the content of the nonvolatile component of the resin (C) in the present composition is preferably 0.5 to 10% by mass relative to 100% by mass of the nonvolatile component of the present composition for the same reason as described above.
[ Zinc powder (F) ]
For example, when the composition is used as a zinc primer, zinc powder (F) is blended into the composition.
The zinc powder (F) may be a powder of metallic zinc or a powder of an alloy mainly composed of zinc (zinc content is 90 mass% or more of the whole), for example, an alloy of zinc and at least 1 selected from aluminum, magnesium and tin, preferably a zinc-aluminum alloy or a zinc-tin alloy.
As zinc powder (F), 1 kind may be used, or 2 or more kinds may be used.
The shape of the zinc powder (F) is not particularly limited, and it is desirable that the zinc powder (F) is a particulate zinc powder having a median particle diameter (D50) of preferably 2 to 15. Mu.m, more preferably 2 to 7. Mu.m, in view of easily forming a coating film having more excellent corrosion resistance.
The D50 can be measured by a laser scattering diffraction particle size distribution measuring apparatus, for example, "SALD2200" (manufactured by shimadzu corporation).
For example, when the present composition is used as a zinc primer, the content of zinc powder (F) is preferably 55 to 90 mass%, more preferably 60 to 85 mass% relative to 100 mass% of the nonvolatile component of the present composition, in view of the ease of forming a coating film having more excellent corrosion resistance and water resistance. Process for preparing anticorrosive coating composition
The first and second agents may be prepared by mixing (kneading) the components blended in these agents, and the components may be added and mixed at once or in multiple times during the mixing (kneading).
The present composition can be prepared by mixing (kneading) these first and second agents and other agents (for example, a third agent) as needed.
For the mixing (kneading), conventionally known apparatuses such as a mixer, a disperser, and a stirrer can be used, and examples of the apparatuses include a disperser, a mixer/disperser mill, a mortar mixer, a roll, a paint shaker, and a homogenizer. In addition, the mixing (kneading) may be performed while heating, cooling, or the like, depending on seasons, environments, or the like.
Coating film and substrate with coating film
The coating film according to the present invention (hereinafter also referred to as "present coating film") is formed using the present composition, and the substrate with a coating film according to the present invention (hereinafter also referred to as "substrate with a coating film") is a laminate comprising the present coating film and the substrate.
The material of the base material is not particularly limited, and examples thereof include steel (iron, steel, alloy iron, carbon steel, mild steel, alloy steel, etc.), nonferrous metals (zinc, aluminum, copper, brass, zinc plating, etc.), and stainless steel (SUS 304, SUS410, etc.).
When, for example, mild steel (SS 400 or the like) is used as the base material, it is desirable to perform, as needed, a matrix adjustment (for example, adjustment of the arithmetic average roughness (Ra) to about 30 to 75 μm) for polishing the surface of the base material by sand blasting or the like.
The substrate may be pretreated by a cleaning treatment or a sandblasting treatment to remove rust, stains, paint (old coating film) or the like adhering to the substrate.
The substrate is not particularly limited, and a substrate requiring corrosion resistance can be used without limitation, but from the viewpoint of further exhibiting the effect of using the present composition, ships, marine structures, plants, bridges, tanks, containers, and other (steel) structures are preferable.
The dry film thickness of the present coating film is not particularly limited, and is usually 10 to 100. Mu.m, preferably 15 to 80. Mu.m, more preferably 20 to 60. Mu.m, in view of obtaining a coating film having sufficient corrosion resistance.
The substrate with a coating film is a laminate comprising the coating film and a substrate, and may have a primer coating film (primer coating film) for the purpose of improving adhesion to the substrate and corrosion resistance, an intermediate coating film for the purpose of improving corrosion resistance, and a top coating film excellent in weather resistance, appearance, and the like.
Specifically, when the present composition is used as a zinc primer, an intermediate paint coating film or a top paint coating film may be formed on the present coating film; when the composition is used as an intermediate paint coating, a primer coating film may be formed between the present coating film and the substrate, or a topcoat coating film may be formed on the present coating film; when the composition is used as a top coat paint (inner surface top coat paint), a primer coating film and an intermediate coating film can be formed between the coating film and a substrate; when the composition is used as a primer coating for a nonferrous metal substrate or a stainless steel substrate, an intermediate paint coating film or a top paint coating film can be formed on the composition.
Examples of the primer coating film include coating films formed from various primer compositions such as epoxy resin systems. Examples of the intermediate paint coating include coating films formed from various intermediate paint coating compositions such as (meth) acrylic resin-based, epoxy resin-based, and urethane resin-based. Examples of the topcoat coating film include coating films formed from various topcoat coating compositions such as (meth) acrylic resin-based, (meth) acrylic silicone resin-based, urethane resin-based, silicone resin-based, and fluororesin-based. In addition, the composition of the present composition may be changed, for example, to form a primer coating film, an intermediate coating film, and a top coating film from the present composition.
Method for producing substrate with coating film
The method for producing a coated substrate according to the present invention (hereinafter also referred to as "the present method") includes the following steps [1] and [2].
Step [1]: a step of coating the composition on a substrate;
step [2]: and a step of drying the present composition applied to the substrate to form a coating film.
< procedure [1] >, a process for producing a semiconductor device
The coating method in the step [1] is not particularly limited, and examples thereof include conventionally known methods such as spraying, brushing, and rolling without air spraying, and the like. Among these, spray coating is preferable in that it is possible to easily coat a large-area substrate such as the above-described structure.
In such coating, it is preferable to apply the coating so that the dry film thickness of the obtained coating film falls within the above-described range.
The conditions for the spraying may be appropriately adjusted according to the thickness of the dry film to be formed, and for example, in the case of airless spraying, the primary (air) pressure is preferable: about 0.3 to 0.6MPa, and a secondary (paint) pressure: about 10-15 MPa, and the moving speed of the spray gun is about 50-120 cm/s.
In addition, when the present composition is applied, the viscosity of the coating composition can be adjusted to be suitable as required. As a diluent for such viscosity adjustment, water is preferably used.
In this case, the diluent is preferably used so as to have a viscosity suitable for the coating material used in each coating method, and for example, in the case of airless spraying, the diluent is preferably used in an amount of 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the present composition.
The viscosity of the present composition (diluted composition as needed) suitable for the spraying is preferably 500 to 5,000 mPas, more preferably 1,000 to 3,000 mPas, as measured under a measurement condition of 23℃using a type B viscometer (manufactured by Rion Co., ltd., model VT-06) as a measuring instrument.
< procedure [2] >, a process for producing a semiconductor device
The drying conditions in the step [2] are not particularly limited, and may be appropriately set according to the method of forming the coating film, the type of the substrate, the use, the coating environment, etc., and the drying temperature is usually 5 to 35 ℃ when the substrate is dried at normal temperature; when forced drying is performed by a hot air dryer or the like, the temperature is usually 30 to 90 ℃, and more preferably 40 to 80 ℃. The composition can be dried and cured even by such normal temperature drying.
The drying time varies depending on the method of drying the coating film, and in the case of drying at room temperature, the same time as in the conventional coating material may be about 1 to 7 days, and the present composition can be dried and cured for preferably 1.5 to 6 hours, more preferably 1.5 to 3 hours. In the forced drying, the same time as the conventional paint is about 5 to 60 minutes, and the present composition can be dried and cured preferably for 5 to 30 minutes, more preferably for 10 to 20 minutes.
[ example ]
The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
Example 1
24 parts by mass of ion-exchanged water, 1 part by mass of dispersant 1, 0.1 part by mass of flash rust inhibitor, 0.1 part by mass of defoamer, 4 parts by mass of coloring pigment, 34 parts by mass of extender pigment and 0.2 part by mass of thixotropic agent were added to a vessel, and dispersion was carried out by a high-speed disperser to a fineness gauge of 40 μm or less, to prepare a polishing substrate. To the obtained polishing substrate, 32 parts by mass of acrylic resin 1, 2.6 parts by mass of curing agent a-1, 1.2 parts by mass of film forming auxiliary agent, 0.3 part by mass of antifoaming agent and 0.5 part by mass of tackifier were added, and then mixed by a high-speed disperser to prepare a first agent.
After 70 parts by mass of the epoxy resin 1 and 30 parts by mass of the film-forming auxiliary agent were added to the container, they were mixed by a high-speed disperser to prepare a second agent.
Thereafter, 95 parts by mass of the first agent obtained as described above and 5 parts by mass of the second agent were mixed to homogeneity using a high-speed disperser to prepare a coating composition.
Examples 2 to 17 and comparative examples 1 to 9
Coating compositions were prepared in the same manner as in example 1, except that the respective materials shown in tables 1 to 5 were used in the amounts (parts by mass) shown in the tables and mixed at the mixing ratios shown in tables 1 to 5.
Details of the raw materials in tables 1 to 5 are shown in table 6.
The coating compositions obtained in examples 1 to 8 can be suitably used as intermediate paint coatings, the coating composition obtained in example 9 can be suitably used as inner surface top paint coatings for storage tanks, containers and the like, the coating composition obtained in example 10 can be suitably used as zinc primer, and the coating compositions obtained in examples 11 to 17 can be suitably used as primer coatings for nonferrous metal substrates or stainless steel substrates.
< drying Property >)
The coating compositions of examples and comparative examples were applied using an applicator having a gap of 0.2mm according to ASTM D5895, and the coating compositions were applied and dried at 23℃or 5℃to measure the time for the dried coating film surface to reach a semi-cured state (Tack-free) and the time for the coating film surface to reach a fully cured state (Dry-Hard). The results are shown in tables 1 to 5.
[ method for producing test piece 1]
The viscosity of each of the coating compositions of examples 1 to 8 and comparative examples 1 to 9 was adjusted using ion-exchanged water so that the viscosity at 23℃of each of the coating compositions reached 1,000 mPas as measured using a type B viscometer (manufactured by Rion Co., ltd., model VT-06).
A water-based ZINC primer ("EKOMATE ZINC M", manufactured by Chinese paint Co., ltd.) was applied to a sandblasted steel plate (SS 400, size: 150 mm. Times.70 mm. Times.1.6 mm (thickness)) by air spraying to an average dry film thickness of 30 μm, and after drying at room temperature for 5 minutes, it was dried with hot air at 50℃for 15 minutes to form a primer coating film.
Next, the above-mentioned coating compositions having adjusted viscosities were applied onto the primer coating film by air spraying so that the average dry film thickness became 40 μm, and after drying at room temperature for 10 minutes, hot air drying was performed at 50 ℃ for 15 minutes to form an intermediate coating film.
Then, an acrylic resin-based aqueous top coat paint ("EKOMATE FINISH", manufactured by chinese paint corporation) was applied to the intermediate paint film by air spraying so that the average dry film thickness became 40 μm, and after drying at room temperature for 10 minutes, hot air drying was performed at 50 ℃ for 30 minutes to form a top coat paint film.
After forming the top coat film, the resultant was dried at 23℃under a relative humidity of 50% for 7 days to prepare a test body (a substrate with a coating film prepared by a forced drying process) for use in a water resistance and corrosion resistance test described later.
[ method for producing test piece 2]
The viscosity of each of the coating compositions was adjusted using ion-exchanged water so that the viscosity at 23℃of each of the coating compositions of examples 1 to 8 and comparative examples 1 to 9, as measured using a type B viscometer (manufactured by Rion Co., ltd., model VT-06), reached 1,000 mPas.
A water-based ZINC primer ("EKOMATE ZINC M", manufactured by Chinese paint Co., ltd.) was applied to a sandblasted steel plate (SS 400, size: 150 mm. Times.70 mm. Times.1.6 mm (thickness)) by air spraying to an average dry film thickness of 30 μm, and the steel plate was dried at 5℃for one day and night to form a primer coating film.
Then, each of the above-mentioned coating compositions having adjusted viscosity was applied to the primer coating film by air spraying so that the average dry film thickness became 40. Mu.m, and the coating film was dried at 5℃for one day and night to form an intermediate coating film.
Then, an acrylic resin-based aqueous top coat paint ("EKOMATE FINISH", manufactured by chinese paint corporation) was applied to the intermediate paint film by air spraying so that the average dry film thickness became 40 μm, and the film was dried at 5 ℃ for one day and night to form a top paint film.
After forming the top coat film, the resultant was dried at 5℃for one day and night to prepare a test body (a substrate with a coating film prepared by a 5℃drying process) for a corrosion resistance test to be described later.
[ method for producing test piece 3]
The viscosity of the coating composition of example 9 was adjusted using ion-exchanged water so that the viscosity at 23℃of the composition reached 1,000 mPas as measured using the above-mentioned type B viscometer.
The above aqueous zinc primer was applied to a sand blast treated steel sheet (SS 400, size: 150mm×70mm×1.6mm (thickness)) by air spraying to an average dry film thickness of 30 μm, and after drying at room temperature for 5 minutes, hot air drying was performed at 50 ℃ for 15 minutes to form a primer coating film.
Then, the above-mentioned coating composition having a viscosity adjusted was applied to the resulting primer coating film by air spraying to an average dry film thickness of 50 μm, and after drying at room temperature for 10 minutes, hot air drying was carried out at 50℃for 30 minutes to form a top coating film.
After the formation of the top coating film, the resulting film was dried at 23℃under a relative humidity of 50% for 7 days to prepare a test piece (substrate with coating film) for use in various coating film performance evaluation tests described later.
[ method for producing test piece 4]
The viscosity of the coating composition of example 10 was adjusted using ion-exchanged water so that the viscosity at 23℃of the composition reached 1,000 mPas as measured using the above-mentioned type B viscometer.
The viscosity-adjusted coating composition was applied to a sand blasted steel plate (SS 400, size: 150mm×70mm×1.6mm (thickness)) by air spraying to an average dry film thickness of 30 μm, dried at room temperature for 5 minutes, and then dried with hot air at 50 ℃ for 15 minutes to form a primer coating film.
An acrylic aqueous intermediate paint ("EKOMATE 100 prime", manufactured by chinese paint corporation) was applied to the PRIMER film by air spraying so that the average dry film thickness became 40 μm, and after drying at room temperature for 10 minutes, hot air drying was performed at 50 ℃ for 15 minutes to form an intermediate paint film.
Then, the acrylic resin-based aqueous top coat paint was applied to the intermediate paint film by air spraying to an average dry film thickness of 40 μm, and after drying at room temperature for 10 minutes, hot air drying was performed at 50℃for 30 minutes to form a top coat paint film.
After the formation of the top coating film, the resulting film was dried at 23℃under a relative humidity of 50% for 7 days to prepare a test piece (substrate with coating film) for use in various coating film performance evaluation tests described later.
[ method for producing test piece 5]
The viscosity of the coating compositions of examples 11 to 17 was adjusted using ion-exchanged water so that the viscosity at 23℃of the compositions became 1,000 mPas as measured using the B-type viscometer.
The viscosity-adjusted coating composition was applied to a stainless steel plate (SUS 410, size 150 mm. Times.70 mm. Times.1.6 mm (thickness)) by air spraying to an average dry film thickness of 40 μm, dried at room temperature for 10 minutes, and then hot air dried at 50℃for 15 minutes to form a primer coating film.
The acrylic resin aqueous top coating was applied to the primer coating film by air spraying to an average dry film thickness of 40 μm, and after drying at room temperature for 10 minutes, hot air drying was performed at 50℃for 30 minutes to form a top coating film.
After the formation of the top coating film, the resulting film was dried at 23℃under a relative humidity of 50% for 7 days to prepare a test piece (substrate with coating film) for use in various coating film performance evaluation tests described later.
< Water resistance >
Based on JIS K5600-6-2 regarding liquid resistance (water immersion method): 2016 the test piece prepared as described above was immersed in water at 23℃for 96 hours, and then subjected to a water immersion test, and the water resistance was evaluated according to the following evaluation criteria. The results are shown in tables 1 to 5.
(evaluation criterion)
O: the coating film after the water resistance test does not swell;
delta: the coating film after the water resistance test swelled, JIS K5600-8-2: 2008 is a molded article having a size of 2 and an amount (density) of 3 or less;
x: the coating film after the water resistance test swelled, JIS K5600-8-2: 2008 is a material having an expansion size of 2 and an amount (density) of 4 or more or an expansion size of 3 or more.
< Corrosion resistance >
A scratch (scribe line) of a depth of the exposed steel plate or stainless steel plate was made from a position of 5cm from the lower end of the long side and 1cm from the left end of the short side of the test body manufactured as described above to a position of 1cm from the lower end of the long side and 1cm from the right end of the short side, and similarly a scratch (scribe line) of a depth of the exposed steel plate or stainless steel plate was made from a position of 5cm from the lower end of the long side and 1cm from the right end of the short side to a position of 1cm from the lower end of the long side and 1cm from the left end of the short side.
Based on JIS K5600-7-1: 1999, the test piece was placed in a brine spray tester under brine spray conditions of a brine concentration of 5wt%, a temperature of 35 ℃ and a relative humidity of 98% so that the scribing side of the test piece faced downward, and was kept for 24 hours, whereby a brine spray test was performed, and the corrosion resistance was evaluated according to the following evaluation criteria. The results are shown in tables 1 to 5.
(evaluation criterion)
O: the coating film after the salt spray test did not rust and swell.
Delta: the coating film after the salt spray test became rusted or swelled, JIS K5600-8-3: 2008 is set to be Ri1 or less (Ri 1, ri 0), or JIS K5600-8-2: 2008 is a molded article having a size of 2 and an amount (density) of 3 or less.
X: the coating film after the salt spray test became rusted or swelled, JIS K5600-8-3: 2008 is set to be a rust grade of Ri2 or more (Ri 2, ri3 …), or JIS K5600-8-2: 2008 is a material having an expansion size of 2 and an amount (density) of 4 or more or an expansion size of 3 or more.
< pot life >)
1000g of each of the coating compositions of examples and comparative examples was measured and held in a container having an inner diameter of 11cm and a height of 12.5cm at a constant temperature of 35℃to determine the time for precipitation or aggregation of the compositions. The results are shown in tables 1 to 5.
< secondary adhesion >)
[ checkerboard adhesion test ]
The test piece after the corrosion resistance test was washed with water, and then dried in an atmosphere of a temperature of 23 ℃ and a humidity of 50% for 1 day, and the position of the dried test piece where the salt water was sprayed and the scribe line was not formed was set according to JIS K5600-5-6: 1999 a 25-cell adhesion test (cross-cut method) of 2mm×2mm was performed, and adhesion was evaluated based on the ratio (%) of the area of the coating film peeled from the stainless steel sheet to 100% of the area of the coating film occupied by the 25 cells. The results are shown in Table 5.
(evaluation criterion)
O: the area of the stripped coating film is below 15%;
x: the area of the peeled coating film was more than 15%.
[ creep Width measurement ]
The test piece after the corrosion resistance test was washed with water, and then dried at 23 ℃ under a humidity of 50% for 1 day, and the creep width (the length between the position farthest from the scribing portion and the scribing portion among the positions after the coating film and the stainless steel sheet were peeled off) was measured in the evaluation target portion of the dried test piece. Here, the "evaluation target portion" refers to a portion of the test piece from which a range of 1cm from the end portion has been removed. The results are shown in Table 5.
[ Table 1 ]
[ Table 2 ]
[ Table 3 ]
[ Table 4 ]
[ Table 5 ]
[ Table 6 ]
In example 1, epoxy resin 1 was used, but the same results as those described above were shown even if #834 epoxy resin such as "jER-834" (manufactured by mitsubishi chemical Co., ltd., bisphenol a type epoxy resin, epoxy equivalent of 230 to 270, nonvolatile component of 100%), "E-834-85X" (manufactured by dazomet chemical Co., ltd., xylene solution of bisphenol a type semi-solid epoxy resin (834 type epoxy resin solution, nonvolatile component of 85%, nonvolatile component of about 255%) was used instead of epoxy resin 1).
However, if the #834 type epoxy resin is used, the VOC content increases by about 10g/L as compared to the above example 1.
< Properties of epoxy resin >
The properties of the epoxy resins used in the above examples and comparative examples were measured as follows.
In a sample bottle, 0.1g of the epoxy resin used in examples and comparative examples (as-is) was added to a mixed solution of 90g of pure water and 10g of butyl carbitol, and the sample bottle was thoroughly mixed with shaking to obtain a measurement solution.
Wherein, 0.1g of epoxy resin (as-is state) means: when 0.1g of an epoxy resin having a nonvolatile content of a% is used as the epoxy resin, the epoxy resin (as it is) is 0.1g, not 0.1 Xa/100 g.
After baseline measurement was performed using the above mixed solution, the transmittance of the obtained measurement solution was measured under the following measurement conditions. Reference is made to the use of the above-described mixed solution. The transmittance of light having a wavelength of 600nm is shown in Table 7 below.
(measurement conditions)
Device: solidSpec-3700 (manufactured by Shimadzu corporation);
measurement wavelength range: 200-800 nm;
scanning speed: 300nm/min;
sampling interval: 0.5nm;
slit width: 5nm;
light source: deuterium lamps (200-310 nm) and halogen lamps (310-1400 nm);
The optical path length (cell thickness) is 1cm.
[ Table 7 ]
Sample name Epoxy resin 1 Epoxy resin 2 Epoxy resin 4 Epoxy resin 5
Transmittance [%] 68.378 0.048 0.093 0.121
Further, since the epoxy resin 3 is an emulsion as in the epoxy resin 2, it is considered that the same result as in the epoxy resin 2 is obtained.

Claims (5)

1. An anticorrosive coating composition comprising:
a first agent containing an epoxy resin curing agent A, (meth) acrylic resin B and water D; and
a second agent containing a non-aqueous epoxy resin C having an epoxy equivalent of 270 or less,
the epoxy resin curing agent A comprises more than 1 selected from aqueous amine curing agent A1 and aqueous amine modified epoxy resin A2,
the content of the nonvolatile component of the (meth) acrylic resin B is 20 to 95% by mass relative to 100% by mass of the total of the nonvolatile components of the epoxy resin curing agent a, (meth) acrylic resin B and the nonaqueous epoxy resin C.
2. The corrosion resistant coating composition of claim 1, wherein:
the content of volatile organic compounds is 200g/L or less.
3. A coating film characterized in that:
formed from the corrosion-resistant coating composition of claim 1 or 2.
4. A substrate with a coating film, characterized in that:
A coating film according to claim 3, comprising a substrate and the coating film.
5. A method for producing a substrate with a coating film, characterized by comprising:
comprises the following steps [1] and [2]:
[1] a step of applying the anticorrosive coating composition according to claim 1 or 2 to a substrate;
[2] and a step of drying the anticorrosive coating composition applied to the substrate to form a coating film.
CN202110894817.8A 2020-08-07 2021-08-05 Corrosion resistant coating composition Active CN114058237B (en)

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