JPS62169870A - Water-based corrosion-resistant paint composition - Google Patents

Abstract

PURPOSE:To form a non-pollution type water-based corrosion-resistant paint which contains little org. solvents without causing lowering in storage stability and the performance of its coating film, by using a maleinized resin as a base resin and an acrylic resin as a dispersant for pigments. CONSTITUTION:This water-based corrosion-resistant paint contains the following components A-F. (A): 5-60wt% (on a solid basis) emulsion obtd. by dispersing a neutralized product of a maleinized resin having a low acid value in water, (B): 0.01-10wt% (meth)acrylic resin for use in dispersing pigments, which contains an unsaturated nitrogen-contg. monomer as a comonomer, (C): 0.01-70wt% corrosion-resistant pigment, (D): 0.01-70wt% pigment other than the component C, (E): 10-80wt% aq. medium and (F): 0-7wt% amphipathic org. solvent. The component B is obtd. by using a water-soluble unsaturated monomer and an unsaturated nitrogen-contg. monomer (e.g., an aminoalkyl (meth)acrylate) as essential components and copolymerizing them optionally with a long-chain unsaturated monomer and an alpha,beta-ethylenically unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an emulsion obtained by dispersing a neutralized maricinated resin in water, which is obtained by blending an aqueous anti-corrosion pigment dispersion, with excellent storage stability, corrosion resistance, and coating performance. The present invention relates to a water-based anticorrosive coating composition.

In recent years, research and development of water-based paints has been active in place of solvent-based paints from the viewpoint of resource saving and non-pollution. As for water-based anticorrosion paints, paints are coated with water-soluble alkyd resins, dispersed epoxy resins, vinyl chloride resins, etc. as base resins, and anticorrosive pigment dispersions mixed therein.

However, these water-based anti-corrosion paints are still inferior to solvent-based anti-corrosion paints in terms of anti-corrosion performance, coating performance, storage stability, etc., and there are still problems to be improved.

The reason for this is that conventional water-based anticorrosive paints use a water-soluble resin with a high acid value as one of the base resins. The use of such resins is necessary to provide water solubility and to maintain pigment dispersion stability and storage stability due to the use of active anticorrosion pigments, but on the other hand, they have a high acid value. There is a problem in that the corrosion resistance, water resistance, etc. of the coating film are reduced due to this. First, when using a low acid value type resin that does not have water dispersibility or material dispersion ability by itself, use a large amount of surfactant or high acid value resin. As a result, surfactants and high acid value resins remain in the coating film, which has a disadvantage in that it adversely affects coating film performance such as corrosion resistance and water resistance. Furthermore, in order to increase the resin's affinity for water, a large amount of hydrophilic organic solvent is usually mixed with water in the #paint, so it cannot be said that it is a completely pollution-free paint. do not have.

Therefore, the present inventors have developed a non-polluting type that does not have the above-mentioned intercalary point, has excellent storage stability, corrosion resistance, and coating performance, and is waterproof and waterproof.
! After conducting intensive research to develop the paint, we found that by using a maleated resin as the base resin and a specific acrylic resin as the paint dispersant, we were able to develop a paint without deteriorating the film performance or storage stability. However, they discovered that it was possible to obtain a pollution-free water-based anticorrosive paint that contained almost no organic solvents, and were determined to complete the present invention.

Thus, according to the present invention, an emulsion (solid content) of 5 to 60% by weight (solid content) obtained by dispersing a neutralized product of a low acid value maleated resin in water. (Meth)acrylic pigment dispersion resin contained together with polymerization components: 0.01 to 1O
Heavy background% (O anti-corrosion pigment 0.01~70wt% (RO)
There is provided an aqueous anticorrosive coating composition characterized in that it contains a pigment other than 0.01 to 70% by weight (D aqueous medium 10 to 80v, amount %) and (n an amphipathic organic solvent).

In the composition of the present invention, a low acid value, solvent-free maleated resin having an appropriate oil length and rigidity is used as the base resin (A> component. Having high rigidity and rigidity is necessary for drying properties and coating film performance, and secondly, having a low acid value is important for coating film performance, especially corrosion resistance, water resistance, etc. It is stable against hydrolysis because the carboxyl groups present are separated from the ester bonds in the skeleton, and the parent xylem and hydrophobic parts have a relatively clear structure. Forms stable ailsion particles in a precise manner.Furthermore, since it is a solvent-free type, the emulsion particles will not be swollen by the organic solvent in the system during storage, and will maintain their initial particle size for a long time. The presence of stable and active anti-I11m agents is unlikely to impair storage stability in any way.

For dispersing active anti-rust pigments, a (meth)acrylic polymer containing a t-containing cR1, elementary unsaturated monomer as a copolymerization component has excellent pigment dispersion properties even when used in small amounts. This polymer is in the form of a so-called "S pear polymer" in which a long chain group is bonded to the backbone polymer, so it is ideal for pigment separation. Because the nitrogen-containing groups of the pigment strongly adsorb to the pigment, the dispersibility of the pigment is very good even when used in small quantities, so it shows sufficient dispersibility even for active rust preventive pigments. It also prevents deterioration in paint storage stability due to elution into water.Furthermore, since the skeleton is a (meth)acrylic molecular chain, it also has strong low resistance to hydrolysis.

What should be noted in the present invention is that the (meth)acrylic polymer containing the 9-unsaturated monomer as a copolymerization component used as the resin for the separation of paper towels is a relatively hydrophilic nitrogen-containing compound. Because it has a secondary structure that maintains an appropriate balance between hydrophobic and long-chain compounds, it has good compatibility with a relatively wide range of drying oils, semi-drying oils, and their fatty acid-modified resins, and is especially compatible with maleated resins. Using this copolymer with good compatibility, it blends well with the base resin of FC Tonka Paste, and there are no phenomena such as shock during reggregation or color separation during paint storage.
A coating composition with good stability is obtained.

Each component used in the present invention will be described in detail below.

Malayans used in the component of the present invention include chemical beak fat, maleated alkyd resins, maleated fatty acid-modified epoxy resins, maleated fatty acid-modified addition polymer resins, etc.; Maleated alkyd resins are particularly preferred.Maleated alkyd resins are mainly prepared by reacting (semi) alcohols, (semi) drying oil fatty acids, polybasic acids, -basic acids, and polyhydric alcohols. It is obtained by further reacting maleic anhydride.

The (semi-)drying oils and/or their fatty acids used include, for example, linseed oil, safflower oil, soybean oil, sesame oil,
Poppy seed oil, eno oil, hempseed oil, budok raft oil, corn sorghum oil, tall oil, sunflower oil, cottonseed oil, walnut oil, rubber seed oil, tung oil, oyster oil, dehydrated castor oil and other fatty acids, high diene fatty acids, etc. can be given. Among them, linseed oil, soybean oil, and their fatty acids and tall oil, which have good moisture composition, are maleic, clove, mustard, and grated. It is preferable to use

The polybasic acid is a compound having 2 to 4 carboxyl groups in one molecule. Specifically, for example, 7-talic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydroheptalic acid, succinic acid, maleic acid, adivicic acid, sepaticic acid, azelaic acid, hymic acid, itacosic acid, methylcyclohexene Tricarboxylic acid, crotonic acid, pyromellitic acid, anhydrides thereof, and the like can be used. Among these, phthalic acid, isophthalic acid, and terephthalic acid are preferred.

Examples of monobasic acids include benzoic acid, para-butylbenzoic acid, methylbenzoic acid, non-drying oil fatty acids, etc. which do not contain sub-fatty acids and are generally used in the production of alkyd resins.

Among these, benzoic acid is preferred because it is low cost and has high coating film hardness.

The polyhydric alcohol is an alcohol having 2 to 6 hydroxyl groups in one molecule, and specifically includes, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ptasidiol, decanediol, diethylene glycol, Pe〉Cunjiino Heneo Bench! Examples include reglycol, chrycerin, trimethylolethane, trimethylolpropane, becitaerythritol, sorbitol, 1,4-cyclohexane dimetatool, trisiflobucasidimethanol, trisisocyanurate, and the like. The above alkyd resin components can be used alone or in combination of two or more.

The alkyd resin can be produced by dehydrating and condensing each component in an inert gas atmosphere at about 150 to about 250°C for about 3 to about 10 hours according to the synthesis method known per se. .

Next, the maleated alkyd resin was synthesized as described above by mixing a mixture of the alkyd resin and maleic anhydride with a concentration of about 150 to about 230
tl: for about 1 to about 5 hours. The acid value of the maleated alkyd resin thus obtained ranges from about 7 to about 70, preferably f1 from 20 to 5o.
It is 1 circle. When the acid value falls within the above-mentioned range, moisture control and corrosion resistance and water resistance of the coating film are improved.

The oil resistance of the maleated alkyd resin used in the present invention,
It ranges from about 15 to about 75, preferably from 25 to 65. When the oil length of the resin falls within the above-mentioned range, a stable maleated alkyd resin emulsion can be produced, and the corrosion resistance, water resistance, and other performances of the coating film are improved.

The viscosity of the maleated alkyd resin used in the present invention is
Although not limited to, a dilute solution of 60% butyl cellosolve has a Gardner foam viscometer value in the range of 0 to Z21, preferably in the 5-Za range. When the value of the Gardner foam viscometer falls within the above-mentioned range, water dispersion, stability of the coating, corrosion resistance of the coating film, water resistance, etc. are improved.

The amphophilic organic detergent (F) optionally used in the present invention acts to help disperse the maleated alkyd resin in water, and dissolves the maleated alkyd resin and mixes it with water. It is an alcoholic solvent with a polar group that absorbs water.

Such solvents include, for example, the formula HO-CmH2m+1 (
In the formula, m is an integer from 2 to 6. ), e41
t-1' ethyl alcohol, n-propyl alcohol,
Isopropyl alcohol, n-7'f alcohol, isobutyl alcohol, 5ec-7' alcohol, t
ert-phthyl alcohol, isoamyl alcohol, 5
ec-7myl alcohol, tert-amyl alcohol, etc.2 formula HO(CnHzn)q -0 C9H2T)
+1 (in the formula, n and p represent an integer from 2 to 6, and q
represents an integer of 1 or 2. ), for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-butanol, ethylene glycol monomethyl ether, diethylene glycol monoprobi! and diethylene glycol monobutyl ether. In the above formula,
Preferably, it is a solvent having HO-CmHzm+1.

In the preparation of maleated alkyd resin emulsions,
When removing the alcoholic solvent contained in the emulsion under reduced pressure, the alcoholic solvent is preferably one with a low boiling point.

Here, the term "low boiling point" means that the boiling point temperature range is approximately 0℃.
~about 150°C.

The blending amount of the solvent varies depending on the blending amount of the resin and @ material contained in the water-based paint containing the maleated alkyd resin emulsion as a paint component, but is generally in the range of 0 to 7% by weight, preferably about 5% by weight or less, More preferably, it is about 2M view% or less. The blending amount of the solvent is 7% by weight.
If the amount is higher than that, the solubility in water becomes Q, which deteriorates storage stability and further causes contamination of the Sakai region. Please note that the above solvents can be used alone or in combination of two or more.

Neutralizing agents used for neutralizing maleated resins include ammonia and organic amines for water conditioning maleated alkyd resins. For example, primary and secondary alkyd resins are tertiary alkyl amines. Typical examples include methylamine, ethylamine, propifreamine, butylamine, amylamine, dimethylamine, diethylamine, dipropylamine, diethylamine, trimethylamine, triethylamine, tripropylamine, morpholine; primary, @secondary or Typical examples of tertiary alkanolamines include monoethanolamine, jetanolamine, dimethylethanolamine, and diethylethanolamine.Among the neutralizing agents, these have good dispersibility and are effective in coating film. Diethylamine, triethylamine and dimethylethanolamine, which are highly volatile and do not easily remain in the water, are preferred. Further, the above neutralizing agents can be used alone or in combination of two or more. Use of neutralizing agent fiχ
is generally from about 0.01 to the carboxyl group in the resin.
About 2.0 equivalents, preferably 0.3 to 1.0 equivalents.

The maleated alkyd resin emulsion used as component (4) in the present invention can be prepared by neutralizing the maleated alkyd resin with the neutralizing agent and, if necessary, adding the alcoholic organic solvent to the aqueous coating composition. Water is gradually added to a neutralized resin solution containing 7% by weight or less, or the above-mentioned alcohol-based organic disease agent is added to a neutralized maleated alkyd resin solution at a concentration of 7% by weight or less in an aqueous paint composition. h1
Maleated alkyd 4' i. d+]'Fi is carried out by removing the alcohol-based organic solvent from the emulsion under normal pressure or reduced pressure until the alcohol-based organic solvent becomes less than the full amount within the scope of the present invention. The temperature of the emulsion during removal is not particularly limited, but it is preferably in the range of about 20 to about 60°C.

The solid fraction of the maleated alkyd resin emulsion is, but not limited to, in the range of about 10 to about 65% by weight, preferably in the range of 25 to 60% by weight.

1. The estimated average particle diameter measured by turbidity method is approximately 0.5μ
Hereinafter, it is preferably manufactured to have a thickness of 0.2μ or less. If the average particle size is larger than 0.5μ, the sedimentation stability of the maleated alkyd resin emulsion will be poor; Since the particles are not stable, the hydrolysis resistance is poor, and the water resistance and corrosion resistance of the coating film are also poor. The turbidity method involves measuring a water-diluted clear emulsion using a spectrophotometer, and calculating the absorption pressure using the following formula, as described in Reference C Bull. I
ndustria+Chemical Reaserc
h VoL. 42 p145 ~l 5 2 (19
The average particle diameter is determined using the calibration curve described in [64)].

Next, the maleated fatty acid-modified epoxy resin used as component (A) in the present invention is prepared by reacting a resin having an epoxy group in its main chain with a (semi-)drying oil fatty acid, and then carrying out a maleation reaction. For example, a reaction product of epichlorohydrin and/or methyl epichlorohydrin with bisphenol A1, bisphenol A and dicarboxylic acid, halogenated bisphenol, bispheno-7L/F1 resorcinol, tetra Hydroxyphenylmethane, polycarboxylic acids, novolac resins, polyalcohols, polyglycols, reaction products with glycerin, etc., polyolefin-type epoxy oils, epoxidized parts, vinylcyclohexene oxide, dicyclopentadiene dioxide, 3. 4-epoxy-6
-methylcyclohexylmethyl-3,4-epoxy-6
-Alicyclic epoxy resins such as methyl cyclohexane carboxylate. A typical example is Epicort resin (made by Shell Chemical, trade name) Epiclon II.
T fat (manufactured by Dainippon Ink, trade name), etc. These resins used have a number average molecular weight of about 150 to 7,000.

As the (semi-)drying oil fatty acid that reacts with the resin having an epoxy group, those mentioned above are used.

The production of maleated epoxy resins is carried out in the same manner as maleated alkyd resins. The acid value of the resulting maleated epoxy resin ranges from about 8 to about 100, preferably 20.
~80, the preset viscosity is not limited to 6nWfi
% butyl cellosolve solution, Gardner foam viscometer value is P
- Z6, preferably T-24. The preparation of the maleated epoxy resin emulsion is also the same as the maleated alkyd resin.

Next, the maleated fatty acid-modified addition polymer used as component (4) is, for example, a homopolymer of a vinyl monomer containing a hydrous acid group or a glycidyl group, or another vinyl monomer that does not contain a hydroxyl group or a glycidyl group (hereinafter referred to as a "non-containing vinyl monomer"). It is obtained by esterifying a copolymer with a functional vinyl monomer (abbreviated as "functional vinyl monomer") and the above-mentioned (semi-)drying oil fatty acid. When the above-mentioned copolymer is used here, it is preferable that the copolymer contains 5% by weight or more of a hydrous acid group or a glycidyl group vinyl monomer component. Another method is to add a (semi-)drying oil fatty acid to glycidyl methacrylate or glycidyl acrylate to form a homopolymer of the monomer or a copolymer with the non-functional vinyl monomer. In this method as well, when a copolymer is produced, it is preferable that the copolymer contains 5% by weight or more of the above-mentioned additional additive component.

Here, examples of the vinyl monomer containing a hydrous acid group or a glycidyl group include allyl alcohol, 2- and droxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, glycidyl methacrylate, glycidyl acrylate, and Metac-P (NOF (manufactured by Kagaku ■, product name), etc. Among these, when allyl alcohol is used, the obtained polymer has a high OH value and is suitable for producing a resin with a long oil length.

Examples of the non-functional vinyl monomers mentioned above include styrene, vinyltoluene, a-methylstyrene, acrylonitrile, mecrylonitrile, esters of alcohols having 1 to 26 carbon atoms with acrylic acid or methacrylic acid, and ethylene glycol. Monoalkyl ether young L
< n diethylene glycol monoalkyl ether (
Esters of acrylic acid or methacrylic acid with an alkyl group having 1 to 8 carbon atoms, propylene glycol monoalkyl ether or 7-carbon diethylene glycol monoalkyl ether (alkyl group having 1 to 8 carbon atoms) and acrylic acid or methacrylic acid. Examples include esters with methacrylic acid, addition monomers of #4-26 monocaleponic acid other than (semi-)drying oil fatty acids, and glycidyl dimethacrylate or it glycidyl acrylate, and the above-mentioned hydrous acid group or combined glycidyl group vinyl It is desirable to use monomers that have excellent copolymerizability with the monomers containing glycidyl methacrylate and glycidyl acrylate, and whose polymers are stable at high temperatures. Other monomers used for radical polymerization such as butadiene, isoprene, talolobrene, betadiene, vinyl acetate, vinyl chloride, and beopamonomer (manufactured by Shell Chemical Co., product name Ft1) can also be used.

The addition polymerization reaction is carried out by a commonly known radical polymerization method, and the maleation reaction is carried out in the same manner as in the case of the maleated saisai described above. The resin acid value is in the range of about 8 to 70, preferably 20 to 60, and the resin viscosity is not limited to 6.
0if1% butyl cellosolve solution has a Gardner viscometer value in the range of Nz, preferably from 0 to Z4.

Emulsion N'3! is done in the same way as the first two.

Next, the (meth)acrylic deposited teaching resin (■) containing a nitrogen-containing unsaturated monomer as a copolymerization component is a water-soluble unsaturated monomer (a) and a nitrogen-containing unsaturated monomer (1)). is an essential component, and if necessary, a long chain unsaturated monomer (C) and an α,β-ethylenically unsaturated monomer (d) other than the above (a,) to (c) are appropriately combined. and has an average molecular weight of 500 to 100,000. Next, we will clarify these monomers.

The water-soluble unsaturated monomer (a) is a water-soluble monomer having a carboxyl group and a sulfonic acid (salt) group,
Representative examples are as follows.

(1) Carboxyl group-containing unsaturated monomer: for example (
meth)acrylic acid, 2-carboxyethyl(meth)acrylic acid, maleic anhydride, crotonic acid, hexamaric acid, etc.

(2) Sulfonic acid (salt) unsaturated monomer: For example, sodium ethylsulfonate (meth)acrylate, (meth)acrylate
Sodium propyl sulfonate acrylate, sodium styrene sulfonate, 2-acrylamido-2-methyl-propanesulfonivucic acid, Elminol JS-2 (manufactured by Sanyo Chemical Industries, Ltd., trade name, expressed by the formula % formula %, (represents an alkyl group of C12H25), sodium allylsulfonate, etc.

These water-soluble unsaturated monomers may be used alone or in combination of two or more.

The 9 element-containing unsaturated monomer (b) includes monomers containing one or more basic nitrogen atoms and one ethylenically unsaturated bond in one molecule. Representative examples of such monomers are as follows.

(1) Aminoalkyl (meth)acrylates: N
, N-dimethylaminoethyl (meth)acrylate), N
, N-diethylamide/ethyl (meth)acrylate, N
-t-butylaminoethyl (meth)acrylate, N,
N-dimethylaminopropyl (meth)acrylate, N
, N-dimethylamine butyl (meth)acrylate, N
-Propylaminoethyl (meth)acrylate, N-butylaminoethyl (meth)acrylate, etc.

(2) (Meth)acrynodes: (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-butyl (meth)acrylamide, N,N-dimethyl (meth)
Acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N
-Methylol (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N,N-dimethylaminopropylacrylamide, etc.

(3) Vinylpyrrolidones: For example, 1-vinyl-2-pyrrolidone, 1-vinyl-3
-Pyrrolidone etc.

(4) Vinylpyridines: For example, 2-vinylpyridine, 4-vinylpyridine, 5
-/Circy 2-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. 2 (5) Vinylimidazoles: For example, 1-vinylimidazole, 1-vinyl-2-methylimidazole, etc.

(6) Vinyl carbazoles: For example, N-vinylcarbazole and the like.

(7) Vinylquinolines: For example, 2-vinylquinoline and the like.

(8) Vinylpiperidines: peeled pork, 3-vinylquinolines, N-methyl-3-vinylpiperidine, etc.

(9) Mollephorins: For example, N-(meth)acryloylmorpholins (10)
Pyrrolidines: For example, N-(meth)acryloylpyrrolidine (11)
Others: For example, the aminoalkyl (meth)acrylates described in (1) above, and the reaction products of (meth)acrylamides described in (2) above and monohalogenated fatty acids such as sodium monochloroacetate. -Second aminoalkyl (meth)acrylates-! 6 is the (meth)acrylamide and 1.
Reactants with sultones such as 3-propion sultone, etc.

These nitrogen-containing monomers may be used alone or in combination of 28r or more.

Long-chain unsaturated monomer (O, radically polymerizable 2 in 1 molecule)
It is a lipophilic long-chain unsaturated monomer with one type bond and a molecular weight of approximately 150 to 1,000. Examples of such monomers include (1) hexyl (meth)acrylate, (meth)
0 of (meth)acrylic acids such as octyl acrylate, dicryl (meth)acrylate, stearyl (meth)acrylate, etc.
Alkyl esters of 7 to 24: (2) drying oil fatty acid,
Monocarboxylic acids such as semi-drying oil fatty acids, non-drying oil fatty acids, synthetic saturated fatty acids, etc. and hydroxyaminekyl (meth)acrylates. ) Reaction products with acrylate or epoxy group-containing allyl ether, etc.: (3) Oxyacids having one hydroxyl group and one carboxyl group in the molecule are referred to as condensates of the oxyacids, and hydroxyalkyl (meta)
(4
) n-off-4-alcohol, oleyl alcohol, butyl cellosolve, butyl calpitol, pesidyl alcohol, C2-24 aliphatic monocarpodiacid and 1.2
- 1 in the molecule represented by adducts with epoxy compounds, etc.
Compounds having 2 hydroxyl groups, or compounds having 1 primary hydroxyl group, 1 secondary hydroxyl group, and 1 tertiary hydroxyl group in the molecule, and inocyanate ethyl (meth)acrylate, 2,2-dimethyl-m-improbenyl be〉dylincyanate , NF3 products, etc. with an isocyanate group-containing acrylic monomer represented by the above-mentioned adduct of a hydroxyalkyl (meth)acrylate and a diisocyanate, or an incyanate group-containing styrene monomer, or (iso)butyl A C4-1B saturated alkyl monoisocyanate compound represented by isocyanate, lacryl isocyanate, phenyl isocyanate, etc. ta is an aromatic monoisocyanate compound, etc., and hydroxyalkyl (meth)
Reaction products with acrylate, etc. or diptylamin, N
-A reaction product of a C6-24 higher amine compound represented by methyl-stearylamine, stearylamine, etc. and the above-mentioned incyanate group-containing acrylic monomer!! etc. (5)
Vinyl ether of Ca ~24, (6) V e o
Examples include C6-24 vinyl ester monomers typified by Valo.

Semi-drying oil fatty acids and drying oil fatty acids are preferably used as these monocarboxylic acid compounds.

The cytometric weight of these long chain unsaturated monomers is preferably 170
~500 range.

These unsaturated compounds or unsaturated compounds may be used alone or in combination of two or more.

The a, β-ethylenically unsaturated monomer pile other than the above (a) to (c) can be selected from a wide range depending on the desired performance KE of the dispersant. Representative examples of such unsaturated monomers are as follows.

(]) Esters of (meth)acrylic acid: For example, C1-5 alkyl esters of (meth)acrylic acid, (meth)
02-8 argunyl ester of acrylic acid, 02-8 hydroxyalkyl ester of (meth)acrylic acid, 03-18 alknyloxyalkyl ester of (meth)acrylic acid, with the formula cH2=cHCOOCnH2nOR'
(wherein n is 2 to 6, R' is an alkyl group), an alkoxyalkyl acrylic ester represented by the general formula CT (2=CHCOO(-Cm)
+R// (where m is 2 to 3, R// is a hydrogen atom,
polyether acrylic esters represented by C1-C6 alkyl groups, etc.

(2) Vinyl aromatic compounds: e.g. styrene, α
- Methylstyrene, vinyltoluene, P-10 Rustyrene, etc.

(3) On-physics compounds: e.g. ethylene, propylene, diisobutene, phthalene, phytagene,
Isoprene, taloloprene, etc.

((1) Vinyl ether m: Example t is vinyl ether, ethyl vinyl ether, phthyl vinyl ether, etc.

(5) Vinyl esters: for example, vinyl propionate, vinyl bivalet, vinyl acetate, etc.

(6) Other heptanomers: For example, (meth)acrylonitrile.

These α,β-ethylenically unsaturated monomers may be used alone or in combination of two or more.

The method for producing the resin (B) is obtained by mutually copolymerizing the components (a), (b), (c), and (d). The copolymerization is produced by a method known per se. It is possible to do so.

The dispersant obtained by copolymerizing the above component (c) has a comb-shaped structure and clearly consists of a hydrophilic part and a lipophilic part, so it reliably adsorbs to the pigment and desorbs and deposits. The stability of the maleated resin emulsion is indicative of its excellent stability properties.

The above-mentioned blending ratio in copolymerization can be changed depending on the desired performance of the dispersant, but it is appropriate to blend them in the following ratios.

Water-soluble unsaturated monomer (al: 1 to 70% by weight, 3 to 50% by weight from the viewpoint of pigment dispersion) Nonsaturated monomer (b): 2 to 70% by weight From the viewpoint of material dispersion, 5 to 60% by weight long chain unsaturated monomer (c)
: 0 to 70% by weight, preferably 5 to 6% by weight based on the balance between hydrophilicity and hydrophobicity of the dispersant, α,β-ethylenically unsaturated monomer ((to): 0 to 90%) Weight M%, average molecular weight of caustic resin (R) for pigment dispersion used in the present invention is 500 to 100, preferably 1,000
~30,000, more preferably Vi2,000~I
It is in the range of 0,000.

1. The pigment modifier according to Criteria 1 is an aqueous dispersion using water as a medium, but the alcohol-based organic solvent can be used if necessary.

Next, (0-component corrosion-resistant pigments include commonly used pigments. For example, (1) lead-based pigments (lead powder, lead zinc oxide,
Resurge, lead red, lead white, cyanamide lead, lead acid calcium chloride (2) Chromium pigments (basic lead chromate, yellow lead, zinc chromate, stro〉chicum chromate, palicum chromate, etc.) (3) Molybdenum Acid-based materials (basic zinc molybdate, zinc molybdate calcium salt, etc.), (
4) Phosphate-based @ materials (bent lead phosphate, aluminum dihydrogen tripolyphosphate, zinc sulfate/paricum complex), (5)
In addition, there are horosilicate pigments, modified barium metaborate, organic nitro compounds, manganese oxide pigments, zinc dust, zinc ash, aluminum powder, red iron oxide, graphite, mica powder, kururi, and calcium carbonate salts.

(Pigments other than Q (D) can be commonly used inorganic and organic pigments, such as thermal pigments
(1) Oxide type (1,000 oxide dioxide, cobalt blue, iron black, etc.): (2) Hydroxide type (alumina white, yellow iron oxide, etc.): (31! Compound, selecide type) (
Zinc sulfide) (vermilion, cadmic yellow, cadmic red, etc.): (4) Ferrocyan compounds (prussian blue, etc.): (5) Sulfate-based (precipitated barium sulfate, etc.); (6) Sulfate-based (clay, ultramarine, etc.) ;(η Combined acid salt system (manganese violet, etc.): (8) +!l# Wheat yarn (carbon black, etc.): (9
) Metal powder type (bronze powder), etc. Item 9 Organic pigments include (1) Nitron pigment type (Naphthol Green B etc.): (2) Azo pigment type (Lysolette, Lake Red C, 7 Asto Yellow, (naphthol red, red, etc.): (3) Dyeing lake pigment system (alkali blue lake, rhodamyl lake, etc.): (4) 7-lysyanide pigment system (phthalocyanide blue, 7-asto sky blue, etc.)
:(5) M-polycyclic compounds (perylene red, quinacridone red, dioxadithi violet, isoindolinone yellow, etc.) are included.

The water-based anticorrosive coating composition of the present invention consists of the following formulation.

Converted to solid content of maleated alkyd resin emulsion: 5~60T! i amount%, preferably 10 to 50% by weight from the viewpoint of coating film performance and coating appearance 1, corrosion-resistant pigment (0
: 0.01 to 70% by weight, preferably 0.1 to 50% by weight based on the above meaning, determined depending on the use of the paint of the present invention or the required coating performance; Other pigments. (mouth: (1,01-70% by weight) 0.1-50% by weight, resin for pigment dispersion (Japan: 0.01-10% by weight depending on the type and amount of pigment used) , from the viewpoint of storage stability, coating film performance, coating cost, etc.
．． 01 to 3% by weight, aqueous medium (10 to 80% by weight, preferably 20 to 70% by weight from the viewpoint of paint storage stability, painting workability, etc.).

The aqueous anticorrosive paint composition obtained by blending as described above contains substantially no organic solvent, and is therefore suitable for use as a pollution-free paint.

The preparation of the paint of the present invention involves first blending the pigment dispersing resin and the pigment within the scope of the present invention, and then using a ball mill, roll mill, homomixer, sand grinder, shaker, attrition mill, etc., which are commonly used in the paint industry. An aqueous pigment dispersion is prepared by dispersing with a dispersion device such as a lighter. It is then obtained by mixing the aqueous pigment dispersion and the maleated resin emulsion that is substantially free of organic solvents.

The aqueous anticorrosive paint composition of the present invention may optionally contain a dryer, an antifoaming agent, a thickener, a preservative, an aqueous preservative other than the above, and a moisture conditioner that helps pigment dispersion. is not preferable because it impairs water resistance.

In addition, the aqueous pigment dispersant used in the present invention (Nichisei's aqueous pigment dispersant) is a maleated + f
The purpose of this method is to make it possible to stably mix and disperse pigments in lubricant emulsions, and the resulting coatings have excellent coating appearance and water resistance.

In the coating composition of the present invention, the maleated resin emulsion has a structure in which a carboxyl group is directly attached to the fatty acid, which is a fatty acid, as shown in rrrI, and since no organic solvent is added, the maleated resin emulsion can be obtained from it. The particle surface of the emulsion has a sharp interface with the aqueous phase, and has excellent licking and hydrolyzability to prevent invasion by water or a neutralizing agent. However, unlike other emulsions that are protected by hydrophilic groups other than anion, such a structure is sensitive to shock, and the emulsion is coated with ms ester salt, a common pigment dispersant. Mixing activators with strong acid groups such as activators causes shock and cannot be used. On the other hand, polyoxyethylene type nonionic surfactants, nonionic-anionic surfactants, carboxylate type anionic surfactants, etc. are known to alleviate the shock caused by mixing, so they are used in some cases with component (13). You may. It has been found that oligomeric or polymeric surfactants have a slow rate of adsorption and desorption to emulsion particles, which results in poor mixing stability with the emulsion.

Water-based anti-corrosion coating of the present invention! The coating film formed from the '1 composition uses an oxidized cross-linked resin emulsion as a vehicle, making it a dense coating film that does not allow the pigment dispersant to come out, so it has excellent water resistance, and the coating film that is formed is quite dense. is sufficiently crosslinked and cured at room temperature, but if heated in the presence or absence of an amino resin etc., it cures in a short time and a coating film with good water resistance, corrosion resistance, etc. can be obtained.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Hereinafter, parts and % indicate parts by weight and % by weight.

Production example of tall oil fatty acid (trade name manufactured by Arayo Forestry Industry Co., Ltd., "Etol FAX" 40% linoleic acid, 3.2% linolic acid, 32% oleic acid, 24.8% others, iodine value 151) 4
97 parts of pentaerythritol, 204 parts of inktaric acid, and 229 parts of benzoic acid were stirred in the presence of an esterification catalyst and subjected to a dehydration bonding reaction at about 240°C for about 10 hours to obtain an alkyd resin with an acid value of 1.5. Just in case. Subsequently, the temperature was cooled to about 200° C., 42 parts of maleic anhydride was added, and the maleation reaction was carried out for about 3 hours to obtain a maleated alkyd resin having a Gardner viscosity of Z4 (75% butyl cellosolve solution). Furthermore, this mixture was cooled to room temperature and water was added to carry out the g@ring reaction. 30 parts of isopropyl alcohol was added to 100 parts of the maleated alkyd resin to obtain a maleated alkyd resin solution having a total acid value of 37.1 and a gas donor viscosity of v (60% butyl cellosolve solution). Next, the tallow solution adjusted to 40°C was neutralized with 1.0 equivalent of triethylamine, and then deionized water was added dropwise to perform emulsification, and the aqueous solution was further distilled under reduced pressure to remove isopropyl alcohol at 40°C. By distilling the maleated alkyd, the emulsion containing the beak was obtained. The resulting emulsion (A-1) had a heating residue of 40.0%, an amount of isopropyl alcohol relative to the resin solid content of 1.0%, a viscosity of 1.0.85 voids, a pH of 8.59, and an average particle diameter of 0.
．． Next time it will be 14μ.

Production example of maleated alkyd resin Emma I Retion (A-2) 449 parts of linseed oil fatty acid, 212 parts of pentaerythritol
6 parts, 184 parts of ink tar acid, and 260 parts of benzoic acid at about 240°C with stirring in the presence of an esterification catalyst.
An alkyd resin with an acid value of 2.9 was obtained by performing a time dehydration reaction. Subsequently, the temperature was lowered to about 200° C., 39 parts of maleic anhydride was added, and maleation reaction was carried out for about 3 hours to obtain a maleated alkyd resin of Gardner Viscous & Z3 (75% butyl cellosolve solution). This product is then cooled to room temperature and subjected to a ring-opening reaction with water. 30 parts of isopropyl alcohol was added to 100 parts of the maleated alkyd resin to obtain a total acid value of 35.7 and a Gardner viscosity U-V (60
% butyl cellosolve solution) to obtain a maleated alkyd resin solution. Next, a maleated alkyd resin emulsion (A-2) was obtained in the same manner as in the preparation of the maleated alkyd resin emulsion (A-1) described above. The resulting emulsion (A-2) had a weight of f6a'd 40.6
%, m1lR Amount of isopropyl alcohol to solid content Qτ*1 1.2%, Viscosity 11 poise, PH8.54, Average particle diameter f1. It was Qlμ.

Production example of the maleated alkyd resin emulsion (A-2)
) A maleated alkyd resin emulsion (A-3) was obtained in exactly the same manner except that the degree of vacuum distillation was changed. The obtained emulsion (A-3) of t1 has a heating residue of 4
4.3%, the amount of isopropyl alcohol based on the resin solid content is 1% or less, and the average particle size is 0.01μ.

Example of manufacturing (A-4) In a reaction vessel, 1,000 parts of Epicor 1001 (manufactured by Shell Chemical, trade name), 1,866 parts of linseed oil fatty acid, 1 part of sodium benzoate, 6 parts of dibutyltin oxide, 150 parts of toluene. 240°C under nitrogen flow for 12 hours. An adduct with an acid value of 5.0 was obtained. Solid content is 9
Next is 2%.

In a reaction vessel, 1,320 parts of the above adduct and 8 parts of maleic anhydride were added.
5 parts of xylene and 25 parts of xylene were added and allowed to react at 180°C for 3 hours under nitrogen flow. A maleated resin with a Gardner viscosity of z3 (75% butyl cellosolve solution) and a total acid value of 51 was obtained.

Furthermore, this product was cooled to room temperature and water was added to perform a ring-opening reaction. The maleated fatty acid modified epoxy 1jli15
To 100 parts, 30 parts of isopropyl alcohol was added to neutralize 1.0 equivalent of triethylamine, and then deionized water was added dropwise to perform emulsification and dispersion.
Isopropyl alcohol was distilled off under reduced pressure at ℃ to obtain a malicated fatty acid modified epoxy resin emulsion. The resulting emulsion had a heating residue of 40.2%,
Amount of isopropyl alcohol relative to resin solid content: 0.2
%, viscosity 12.5 voids, PH 8.7, average particle size 0.
It is 13μ.

Malaysified fatty acid modified addition polymerization resin emulsion (A
-5) Production example RJ-101 (number average molecular weight 1150.0H content 7.
7% styrene-allylic alcohol, lk aggregate Monsanto Chemical Company 1641r, soybean oil fatty acid 2
080 F, xylene 200? and 3.3f of dibutyltin oxide were placed in four 5t flasks and reacted at 230°C for 10 hours while dehydrating to form a tree with an acid value of 5.47.
Get a finger. Add maleic anhydride 181f to this and make 19
The maleicization reaction is carried out at 0 to 200°C for 7 hours. Xylene and unreacted maleic anhydride were removed by vacuum distillation, followed by ring opening with water to obtain a maleated resin having a Gardner viscosity z (75% n-butyl cellosolve solution) and a total acid value of 40. Next, an emulsion was obtained using exactly the same method as for producing the maleated fatty acid-modified epoxy m-fat emulsion (A-4). The resulting emulsion had a heating residue of 39.9%.
, fio of isopropyl alcohol to resin solids content
, 8%, % [8.7 voids, PH 8.4, average particle size 0
．． 10) It was 1.

Put xylene 17609 into four 5t flasks and add 1
While stirring at 30°C, n-butyl methacrylate 990f and 2-hydroxyethyl methacrylate 4
A mixture of 509 and 400 f of xylene and 100 f of azobisdimethylvaleronitrile were mixed, and the following were added dropwise from separate dropping funnels over a period of 2 hours. 1 from the end of dripping
After 1 hour, azobisisobutyronitrile 2 of 1
f-1 Maintain at 130°C for further 3 hours. Next, 960 f of linseed oil fatty acid and 42 g of dibutyltin oxide were added to this, and an esterification reaction was carried out at 230° C. for 6 hours while dehydrating to obtain a resin with an acid value of 1.6. This 4! J fat 6
Add 80P of maleic anhydride to 00t to make ester PJI.
170~ in a mixed solvent of J300f, xylene>200f
React at 180°C for 7 hours.

After the reaction, the solvent and unreacted maleic anhydride were removed by distillation under reduced pressure, followed by ring opening with water. Gardner viscosity Z3
(75% n-butyl cellosolve solution λ A maleated resin with a total acid value of 41 was obtained.Next! An emulsion was obtained in exactly the same way as for the production of the maleated fatty acid modified epoxy N% emulsion (A-4). The obtained emulsion had a heating residue of 40.5%, an amount of isopropyl alcohol relative to the resin solid content of 1.1%, a viscosity of 13.2 boids, and a pH of 8.
, 3, the average particle diameter is 0.11 μ.

350 parts of n-phthyl cellosolve was placed in a reaction vessel and heated to 120°C. Next, 113 g of glycidyl methacrylate-safflower fatty acid addition monomer was added to this solution.
A mixture of 126 parts of N-vinylpyrolide, 11 parts of acrylic acid, and 17.5 parts of azobisdimethylvaleronitrile was then added dropwise over about 2 hours.

1 hour after completion of dropping, add azobisisobutyronitrile 2.
5 parts of azobisisobutyronitrile were added to the reaction vessel after 1 hour, and after heating for an additional 2 hours,
Unreacted monomers and n-butyl cellosolve were distilled off by vacuum distillation, resulting in a resin with an acid value of 35.8 and a Gardner viscosity of 0 to 1.
A copolymer of P (40% butyl cellosolve solution) for use as a pigment dispersant was obtained. Furthermore, the copolymer is triethylamine 1
．． Neutralization was carried out with a neutralization equivalent of 0 to obtain a pigment separating teaching agent (B-1) with a heating residue of 50% f.

325 parts of n--f til cellosolve was placed in a reaction vessel and heated to 20°C. Next, to this solution was added 2-(1-aziridinyl)ethyl methacrylate, 113 parts of 7-rawa mono-oil fatty acid addition monomer, and 12 parts of N-vinylpyrrolidone.
6 parts of butylcellosorg, 11 parts of acrylic acid, and 17.5 parts of azobisdimethylvaleronitrile.
One part was dissolved and the next one was simultaneously dripped from another dripping port over a period of about 2 hours. 30 minutes after completion of the dropwise addition, 1.25 parts of azobisisobutyronitrile was added and heated for an additional 30 minutes.

This operation of adding azobisisobutyronitrile was repeated 4 times, and a total of 5 parts of azobisisobutyronitrile was added.
Heat for another 2 hours. Next, after the above operations are completed,
Unreacted sulfur and n-butyl cellosolve were distilled off by vacuum distillation, resulting in a vI acid value of 53.7 and a Gardner viscosity of 0 (
A copolymer for a pigment dispersant (40% butyl cellosolve solution) was obtained, and the copolymer was further mixed with triethylamine 1.
Neutralization was carried out at a neutralization equivalent of 0 to obtain a pigment dispersant (B-2) with a heating residue of 50%.

350 parts of n-phthyl cellosolve was placed in a reaction vessel and heated to 120°C. Next, 113 parts of monomer (monomer obtained by adding 1 mole of 2-hydroxyethyl methacrylate and 1 mole of oleyl alcohol to 1 mole of tolylene diisocyanate) and 126 parts of N-vinylpyrrolibisyl to the solution. , a mixture of 11 parts of acrylic acid;
A solution of 17.5 parts of azobisdimethylvaleronitrile dissolved in 60 parts of butyl cellosolve was simultaneously added dropwise from another dripping port over a period of about 2 hours. One hour after the completion of the dropwise addition, 2.5 parts of azobisvaleronitrile was added, and after another hour, 2.5 parts of azobisvaleronitrile was added, and after further heating for 2 hours, unreacted monomers and n-butyl cellosolve were distilled off under reduced pressure. A copolymer for a pigment dispersant having a resin acid value of 39.1 and a Gardner viscosity of 0-P (40% butyl cellosolve solution) was obtained. Furthermore, the copolymer was neutralized with 1.0 neutralization equivalent of triethylamine to obtain a pigment dispersant (B-3) with a heating residue of 50%.

A mixture of anti-corrosion pigment, other materials and pigment dispersion resin
Dispersion was carried out for 60 minutes using an ed Devi1 dispersion machine to obtain aqueous pigment dispersions ■～■ with the formulation shown in Table 1 below.
Got 7'? ,.

A water-based paint was prepared by mixing the aqueous pigment dispersions (1) to (2) obtained in the above production examples and the Malayan beak emulsion shown in Table 2, and 1% of the water-based anticorrosive paint of Examples 1 to 7 was added. The t0 performance wiping results are shown in Table 2 below.

Comparative Example 1 40 parts of maleated alkyd oval emulsion (A-1), 8 parts of n-butyl cellosolve organic solvent, and 16 parts of the same pigment mixture as the aqueous pigment dispersion (■) were mixed, and the mixture was mixed using the same dispersion machine as above. A water-based paint of Comparative Example 1 was obtained by performing dispersion.

Comparative Example 2 Maleated fatty acid modified addition polymerization resin emulsion〉(A
-5), the maleic anhydride used in maleation 51 was increased to 420 parts, and the Gardner viscosity Z4 (
75% n-butyl cellosolve solution), a maleated resin having a total acid value of 91 was obtained.

Next, 35 parts of 1, n-butyl cellosolve, triethylamine equivalent to 1.0% of neutralization, and deionized water were added to 100 parts of the prefixed solid content to obtain a 1% aqueous solution with a heating residue of 3o.

To 60 parts of the above aqueous solution, 18 parts of the same pigment mixture as the aqueous pigment fraction solution (2) was added and dispersed using the same dispersing machine as above to obtain a water-based paint of Comparative Example 2.

(*1) Ratio value (02
) Butrol-22 (modified metaboric acid, Buckman Laboratories, Inc.)
) K-845 (Aluminum dihydrogen tripolyphosphate manufactured by Teikoku Kako Co., Ltd.) Siccr-NOP (Multi-phase pigment consisting of an organic nitro compound and zinc phosphate, Shiraki Tsusan) MC-300W (Calsium cum molybdate Kikuchi pigment ■
) ZnO (zinc white) Stroklo T (strontium chromate) (*3) Oxide Yellow L-1 (iron oxide, manufactured by Toyo Shokuryo Co., Ltd.) Talc SSS (hydrous magnesium silicate, manufactured by Nippon Talc Co., Ltd.) Titanium White R-5N (Titanium oxide, manufactured by Sakai Chemical Co., Ltd.) Carbon MA (Carbon, manufactured by Mitsubishi Chemical Corporation) (*4)
Paint condition after storage at 30℃ for 2 months (*5) Example 1
7 and Comparative Example 1.2 and 2 parts of a water-based dryer (trade name: "Deiknate" cobalt metal, manufactured by Dainippon Ink Co., Ltd.) were blended and painted on a polished mild steel plate (polished with sandpaper≠320). 9020℃, relative humidity 75%
It was dried and then used for subsequent testing.

(*6) After drying and molding for 7 days, the coated surface condition was examined by immersing it in tap water at 20°C for 1 day.

(*7) After drying for 7 days, cross-cut the coating film with a razor to reach the substrate, and test it with a Tsuruto spray tester.
After testing for 68 hours, we checked the condition of the painted surface (the extent of rust from the crosscap area).

Claims (1)

[Claims] (A) An emulsion (solid content) of 5 to 60% by weight obtained by dispersing a neutralized product of a low acid value maleated resin in water (B) Contains a nitrogen-containing unsaturated monomer as a copolymerization component (meth)acrylic pigment dispersing resin 0.01 to 10% by weight (C) Corrosion-resistant pigment 0.01 to 70% by weight (D) Pigment other than (C) 0.01 to 70% by weight (E) Aqueous medium 1. A water-based anticorrosive coating composition containing 10 to 80% by weight and (F) 0 to 7% by weight of an amphipathic organic solvent.