JPS62129360A - Production of solventless water-based binder - Google Patents

Abstract

PURPOSE:To obtain the titled binder for protecting metal surface and having excellent storage stability, etc., by separately dispersing two kinds of specific maleinized alkyd resin in water in the presence of a dispersion assistant and removing the dispersion assistant before or after the mixing of the resultant two kinds of emulsions. CONSTITUTION:A solventless water-based binder is produced by mixing (A) 9-90wt% (solid basis) emulsion produced by neutralizing a maleinized alkyd resin having an acid value of 10-60 and an oil length of 30-70 and dispersing the neutralized product in water in the presence of a dispersion assistant consisting of 2-3C alcohol (e.g. ethyl alcohol) and (B) 95-10% emulsion produced by neutralizing a maleinized alkyd resin having an acid value of 30-100 and an oil length of 30-70, dispersing the neutralized product in water in the presence of a dispersion assistant consisting of 2-3C alcohol and polymerizing a radically polymerizable monomer by emulsion polymerization. In the above process, the dispersion assistant is removed from the system before of after mixing the emulsions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a disease-free aqueous Vicidar.

In general, coating films formed from water-soluble paints containing a water-soluble alkyd resin as a vehicle component generally have excellent density, but are inferior in drying properties. Coating films formed from emulsion paints in which an emulsion is used as a vehicle component have excellent drying properties, contrary to the properties of coating films formed from water-soluble paints, but have the disadvantage of poor density. As a representative example of improving the drawbacks of both of them, JP-A-53-773
A mixture of a water-soluble resin and a polymerized emulsion using a maleated alkyd resin as a dispersion stabilizer, as disclosed in Japanese Patent No. 48, has been proposed. However, this method requires a large amount of organic solvent to help dissolve or disperse the water-soluble resin and maleated alkyd resin in water, and the solvent deteriorates the storage stability of the paint and also causes pollution and fire. It has the disadvantage that it poses a danger and also has an adverse effect on the drying properties of the coating film.

Zero Hatsu 8A is non-polluting, has no fire hazard, has excellent storage stability and drying properties, and is particularly effective at protecting metal surfaces. ! It is an object of the present invention to provide a solvent-free aqueous binder suitable for forming a coating film.

The present inventors have conducted extensive research to develop a method for producing a solvent-free aqueous binder that does not have the drawbacks of conventional methods. By mixing the mold emulsion in a specific ratio and then using a goo component, and making the component contain a specific alcohol dispersion aid, allowing it to dissolve in water, and further removing the dispersion aid. This is a method for obtaining a solvent-free aqueous binder.

That is, a maleated alkyd resin (r+ neutralized product having 2 or 3 carbon atoms) having an acid value of 10 to 60 and an oil length of 30 to 70
An emulsion (A) obtained by dispersing in water using an alcohol dispersion aid (hereinafter referred to as "dispersion aid"), an O'O value of 3o to 100, and an oil length of 3o to 7o.
An emulsion (B) obtained by dispersing the neutralized product of the yarn-formed algide resin (II) in water using the dispersion aid and emulsion polymerizing a radically polymerizable monomer in the presence of the neutralized product, Next, component (A) and (BJ acid component solid content weight ratio of the former 5 to 90% and the latter 95 to 10%)
%, the dispersion aid is removed before or after the mixing.

Emulsion (A) used in the present invention is prepared by neutralizing the maleated alkyd resin (II) with a neutralizing agent, and then dissolving it in a dispersion aid after neutralization, so that the maleated alkyd resin (II) is not neutralized. In some cases, water is added to the product after neutralization, but this can be done by dispersing the product in water. More preferably, the maleated alkyd resin (I) is carried out by adding water to a neutralized solution of I1 to cause phase inversion. It is obtained by reacting a polybasic acid, a -basic acid and a polyhydric alcohol, and further reacting with maleic anhydride.

The (semi-)drying oils and/or fatty acids used include, for example, ada oil, safflower oil, soybean oil, sesame oil, poppy seed oil, eno oil, hempseed oil, pudoku kernel oil, and corn oil. , sunflower oil, cottonseed oil, walnut oil, rubber seed oil, tung oil, oicilla oil, turmeric oil, water and mustard oil, and fatty acids thereof, tall oil fatty acids, high diene fatty acids, and the like.

Among them, it is preferable to use linseed oil, which is easy to form into dhalein and has good water dispersibility. U (semi) drying oil and/or
Or the blending amount of the fatty acid can be adjusted according to the maleated alkyd resin (
rJ30 to about 70% by weight based on II1 solid content.

If the blending amount is less than 30% by weight, the marization reaction becomes difficult, the storage stability of the emulsion is poor, and the drying properties of the coating film formed are poor. On the other hand, if it is more than 70% by weight, there is a drawback that the coating film performance is poor.

The polybasic acid is a compound having 2 to 4 carboxyl groups in one molecule. Specifically, the following examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, co/·phosphoric acid, maleic acid, adipic acid, cepatic acid, azelaic acid, hymic acid, itacosic acid, and methylcyclo Hexcentric carboxylic 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 the monobasic acid include the above-mentioned monobasic acids, benzoic acid, para-tert-butylbenzoic acid, methylbenzoic acid, non-drying oil fatty acids, rosin, 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.

Examples of polyhydric alcohols include alcohols having 2 to 6 hydroxyl groups in the 11I'f molecules, and specifically include ethylene glycol, polyethylene glycol, propylene glycol, polypropylecylicol, Fukundio-I, Decanediol, diethylene glycol, pentacidiol, neopentylgelicol, glycerin, diglyceride, triglyceride, trimethylol etacy, trimethylol fluorocarbon, pentaeris! J
)-, cihentaerythritol, sorbitol, 1
．． Examples include 4cyclohexacidimethanol, tricyclodecane dimetatool, trisisocyanurate, and the like.

However, as alcohols other than those mentioned above, dimethylolpropiosic acid, lactose, and allyl alcohol copolymers can also be used.

The maleated alkyd resin (I) was produced by dehydrating and subdividing the above-mentioned components in an inert gas atmosphere at about 150 to 250°C for about 5 to 15 hours according to a known synthesis method. It is carried out by reacting a mixture of an alkyd resin and maleic anhydride at a temperature of about 150 DEG to 220 DEG C. for about 1 to 6 hours. The acid value of the maleated alkyd resin thus obtained is in the range of 10 to 60, and the acid value is 15.
It is necessary to be within the range of ~450 knots. If the acid value is less than 1o, it becomes difficult to indoctrinate the water, whereas if it is more than 60, it becomes water-soluble, impairing storage stability, water resistance of the coating film, etc.

In addition, the oil length of the maleated alkyd resin (II), 3
It is in the range of 0 to 70, preferably in the range of 20 to 60, more preferably in the range of 30 to 55. When the oil length is less than 30, the amount of maleic anhydride added becomes small and a stable maleic alkyd resin emulsion cannot be obtained. On the other hand, if it is more than 70, the water resistance of the coating film will be impaired.

The viscosity of the maleated alkyd resin (II) used in the present invention is in the range of, but not limited to, a Gardner foam viscometer value of ~z5 in a dilute solution of 60% butyl cellosolve. When the Gardner foam viscometer value is smaller than K, water dispersion becomes easy, but the stability of the emulsion deteriorates and it is difficult to maintain a balance between the two. -The water resistance of the primary coating film is also poor.

On the other hand, if the value is greater than 25, it is not preferable because water conversion becomes difficult and the amount of organic solvent required for water conversion becomes large.

Examples of the dispersion aid include alcohols having 2 or 3 carbon atoms, and specific examples include ethyl alcohol, n-propyl alcohol and isopropyl alcohol. Two or more of these dispersion aids can be used in combination. If the number of carbon atoms in the alcohol component is less than 2, the effect of increasing the moisture content of the maleated alkyd resin is small, and if the number of carbon atoms is more than 3, it is difficult to remove, and the storage stability of the emulsion is reduced, so it is preferable. It's not sweet.

The formulation g of the dispersion aid is maleated alkyd tree + 11
i(II) in the range of about 5 to 100 9% by weight based on solid content;
A suitable weight range is about 10-60% by weight. If the amount of the solvent is less than about 5% heavy metal, it will have little effect on water dispersion, and conversely, if it is more than about 100% ERW, the solubility in water will be good, but water dispersion will be poor. , and the manufacturing cost also increases.

As the neutralizing agent, maleated alkyd resin (II)
Ammonia and organic amines that can be water-dispersed, such as primary, secondary or tertiary alkyl amines, representative examples being methylamine and ethyl amine.
, propylamine, butylamine, amylamine, dimethylamine, diethylamine, diethylamine, diptylamine, trimethylamine, triethylamine, trifluoropylamine, morpholine; primary, secondary or tertiary alkanolamines, representative examples include: Monoethanolamine, jetanolamine, dimethylethanolamine, etc. Among these neutralizing agents, diethylamine, triethylamine, and dimethylethanolamine are preferred because they have good dispersibility and are highly volatile and do not easily remain in the coating film. Further, the above neutralizing agents can be used alone or in combination of two or more. The amount of neutralizing agent used is generally 0.1 to 2.0 equivalents based on the carboxyl group in the resin.
Preferably it is between 0.3 and 1.0.

Next, emulsion 3 (B) used in the present invention is prepared by using the same amount of the dispersion aid as described above before or after neutralizing the maleated alkyd resin (A) with the neutralizing agent. 10) Dissolve.After neutralization or, if not, neutralization, the radically polymerizable monomer is heated at about 40 to about 100°C using the neutralized product of the maleated alkyd resin (II) as a dispersion stabilizer. Approximately 5 minutes to approximately 10 Kr at reaction temperature
It is possible to carry out the polymerization using 1t + polymerization.

The maleated alkyd resin (II) can be obtained using the same raw materials as those used for the maleated alkyd resin (II). Maleated alkyd resin (It)
The acid value is in the range of 30 to 1()O, preferably 40 to 8
Must be in the range 0. If the acid value is less than 30, blistering of the vinyl polymer will occur during emulsion polymerization, and conversely, if the acid value is more than 100, storage stability and water resistance of the coating film will deteriorate. To be sure, the oil strength of the maleated alkyd resin (It) is in the range of 30 to 70, preferably in the range of 20 to 60. If the oil length is less than 30, the amount of maleic anhydride added will be small and a stable emulsion will not be obtained, while if it is greater than 70, the water resistance of the coating film will be impaired.

The radically polymerizable monomer is one that is used in general emulsion polymerization and can be used without any particular limitations. As the radically polymerizable monomer, for example, the general formula CH2=C(R1)COOR2 (in the formula, R1
(meth)acrylic acid esters represented by hydrogen hydride or methyl group, 1<2 represents an alkyl group having 1 to 12 carbon atoms; (poly)ethylene glycol diacrylate, (poly)propylene glycol diacrylate, 1.
4-Butashijio! Polyfunctional acrylic heptamers such as resacrylate, l,6-hexanediol diacrylate, and trimethylolpropane triacrylate;
Vinyl aromatic monomers such as nutilin, α-methylstyrene, vinyltornidi-P-thalolstyrene; polyolefin monomers such as 7-tadiene, isoprecipitate, chlorophylline, etc.; vinylpyridine, vinylpyrrolidone, (meth)acrylamide, N-butoxymethylacrylamide Nitrogen-containing acrylic monomers such as (meth)acrylonitrile, vinyl acetate, Beopa monomer (Shell Chemical Products), vinyl globionate, vinyl pivalate, and the like. Each of these seven types may be used alone, or two or more types may be used in combination. Also, α,β-ethylene phosphorus saturated carboxylic acid,
Hydrophilic monomers such as hydroxyalkyl acrylates can also be used in combination with the above monomers. The amount of the heptamine is generally in the range of 95 to 20% by weight, preferably 90 to 25% by weight of the heptamine, and 5 to 80% by weight, preferably 10 to 75% by weight of the maleated alkyd resin (A). It is.

Preparation of solvent-free aqueous binder used in the present invention i. J:
The dispersion aid is reduced to about 5% by weight or less based on the resin solid content by distillation under reduced pressure at a temperature of about 100°C or below, preferably about 70°C or below. The emulsion (A) obtained by removing the emulsion (A) and the emulsion (B), preferably about 3% by weight or less, more preferably about 1% by weight or less, may be mixed together. After mixing, the dispersion aid can be removed under the above conditions to the same content as above.

The mixing ratio of the emulsion and emulsion (B) is preferably 1 to 10% by weight (solid content) to 95 to 10% by weight of emulsion (E) to 5 to 90% (solid content) of emulsion (A). Emulsion (B) has an ffi range of 90 to 20% by weight relative to A) 10 to 0 weight% (solid content).If the weight ratio of emulsion (A) is less than 5% by weight, the formed coating Properties such as water resistance due to the denseness of the film are poor, and if the amount of Manen Emulsion (A) is more than 90% by weight, the drying properties of the coating film will be poor.

The solid content concentration of the solvent-free aqueous binder obtained in this manner is not particularly limited, but is approximately 15 to 65%.
Weight%.

In addition, it is also possible to add conventionally known coloring pigments, extenders, pigment dispersants, antifoaming agents, plasticizers, dryers, antifreeze agents, etc. to the solvent-free aqueous binder, if necessary. be.

Next, the present invention will be further explained by manufacturing examples and examples. In the Examples, parts and % indicate parts by weight and % by weight.

Production Example of Maleated Alkyd Resin A mixture of 516 parts of isophthalic acid, 588 parts of pesitaerythritol, 1647 parts of linseed oil fatty acid, and 548 parts of benzoic acid was added to 100 parts of the mixture in 6 5-ton containers. of esterification catalyst was added, and a dehydration-feeding reaction was carried out at 240° C. for 6 hours with stirring under a nitrogen atmosphere to obtain an alkyd resin with an acid value of 4.8. Next, 133 parts of maleic anhydride was added to the alkyd resin, and 20 parts of
Malaise-forming reaction was carried out at 0°C for 3 hours to obtain an acid value of 45, a Gardner foam viscosity (60% butyl cellosorg solution, the same meaning hereinafter -j)X'', and an oil length of 55! Similarly, maleated resins were produced using the formulations shown in Table 1 below to obtain maleated alkyd resins (2), (3) and (bleed).

The maleated alkyd resin (II) obtained above was placed in a 2 ton container.
420 parts of isopropyl alcohol, 126 parts of isopropyl alcohol, and 34 parts of triethylamine were added and stirred at a liquid temperature of 40°C to obtain a neutralized maleated alkyd resin. Next, 684 parts of deionized water was added dropwise to the neutralized product over a period of about 1 hour at the same temperature as above to perform water buffing, and then isopropyl alcohol was removed from the water buffed product under one pressure to form an emulsion (A).
Good idea.

(B-1) 140 parts of the maleated alkyd resin (2) obtained above, 35 parts of isopropyl alcohol, and 17 parts of triethylamine were added to a container No. 21, and 752 parts of deionized water was added while stirring at a liquid temperature of 40°C. Be sure to use water-based products. Next, 23 parts of a 4.8% Acimonicum persulfate aqueous solution was added to the water dispersion, and then 132 parts of styrene and N-
A mixture of 245 parts of butyl methacrylate and 42 parts of 1,6-hexanediol diacrylate was added to the reaction vessel and stirred for 30 minutes to uniformly mix.

The reaction was carried out at 80° C. for about 2 hours with stirring.

After the reaction was completed, the isopropyl alcohol was removed by distillation under reduced pressure at a liquid temperature of 40°C to obtain emulsicon (B-1).

(B-2) Same as the production of emulsion (B-1) except that 377 parts of N-butyl methacrylate was used instead of 132 parts of styrene and 245 parts of N-butyl methacrylate in the production example of emulsion (B-1). An emulsion (B-2) was obtained.

(B-3) In the production example of emulsion (B-1), 101 parts of styrene (-1 γ' parts, 175 parts of methyl methacrylate and 2-ethyl hexyl acrylate) were used instead of 132 parts of styrene and 245 parts of N-butyl methacrylate. Emulsion (B-
Emulsion (B-3) was obtained in the same manner as in the production of 1).

Example 1 50 parts (solid content) of the emulsion (A) described above and 50 parts (solid content) of the emulsion (B-1) described above were mixed to obtain the emulsion of Example 1.

Example 2 The above emulsion (2 parts of As (solid content) and the previous emulsion)
The emulsion of Example 2 was obtained by mixing 50 parts (solid content) of Emulsion (B-2).

Example 3 50 parts (solid content) of the emulsion (A) described above and 50 parts (solid content) of the emulsion (B-3) described above were mixed to obtain the emulsion of Example 3. 4 nEZ Marushi 3> (A) 50 parts (solid content) of an emulsion from which teisoprobil alcohol has not been removed and 50 parts (solid content) from which isopropyl alcohol has not been removed in the emulsion (island) were mixed. After, 40
The emulsion of Example 4 was obtained by distilling under reduced pressure at a liquid temperature of 50°C to 50°C to remove isopropyl alcohol.

Comparative Example 1 After adding 420 parts of the above-mentioned maleated alkyd resin (3), 126 parts of butyl cellosolve and 34 parts of triethylamine, 684 parts of deionized water was added dropwise to the neutralized product over about 1 hour. and obtained emulsion (a). Next, 140 parts of the above-mentioned diluted maleic alkyd resin (A), 49 parts of butyl seronluz, and 15.6 parts of triethylamine were added and stirred at a liquid temperature of 40°C (after adding 752 parts of deionized water, the emulsion was Emulsion polymerization was carried out in the same manner as in the production example of (B) to obtain a 1% emulsion (b) containing butyljarosolp. 50 parts (solid content) of the emulsion (a) and 50 parts (
solid content) to obtain an emulsion of Comparative Example 1.

Comparative Example 2 50 parts (solid content) of the above Emulsion>(A) and 50 parts (solid content) of the Next Emulsion>(b) used in Comparative Example 1
Tables 2 and 3 show the properties and storage stability of the emulsion of Comparative Example 2.

Comparative Example 3 420 parts of the above maleated alkyd resin (II),
After neutralization by adding 126 parts of methyl alcohol and 34 parts of triethylamine, deionized water was added, but water dispersion was not possible.

Claims (1)

[Claims] 1. A neutralized product of maleated alkyd resin (I) having an acid value of 10 to 60 and an oil length of 30 to 70 is dispersed in water using an alcohol dispersion aid having 2 or 3 carbon atoms. emulsion (A), acid value 30-100 and oil length 30-70
An emulsion (B) is prepared by dispersing the neutralized maleated alkyd resin (II) in water using the dispersion aid, and emulsion polymerizing a radically polymerizable monomer in the presence of the neutralized maleated alkyd resin (II). When mixing components (A) and (B) at a solid content weight ratio of 5 to 90% for the former and 95 to 10% for the latter, it is recommended to remove the dispersion aid before or after the mixing. A method for producing a characteristic solvent-free aqueous binder. 2. Production of a solvent-free aqueous binder according to claim 1, wherein the alcohol dispersion aid having 2 or 3 carbon atoms is at least one selected from ethyl alcohol, n-propyl alcohol, and isopropyl alcohol. Method.