JPH04198257A - Water-base resin dispersion composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in storage stability and having excellent properties characteristic of a solvent-base alkyd resin by dispersing a mixture of a water-dispersible vinyl-modified alkyd resin having hydrophilic groups in its vinyl parts with an oil-sol. alkyd resin in water. CONSTITUTION:A mixture of a water-dispersible vinyl-modified alkyd resin having hydrophilic groups, such as (meth)acrylic acid groups or polyoxyethylene groups, in its vinyl parts (the ratio of an alkyd resin to a polymerizable vinyl monomer mixture being 90:10-10:90, pref. 80:20-40:60) with an oil-sol. alkyd resin is dispersed in water to give the title compsn. The vinyl-modified alkyd resin is prepd. by reacting the alkyd resin with a part, at least 1/3, of the monomer mixture, the part contg. no vinyl monomer having an acid group, and reacting with the rest of the monomer mixture, the rest contg. vinyl monomers having an acid group.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel and useful aqueous dispersion resin composition. More specifically, it is a novel co-dispersion method that uses a specific alkyd resin called a vinyl-modified alkyd resin, which does not contain normally used emulsifiers or protective colloids and can be water-dispersed exclusively due to the hydrophilic components of the vinyl portion. The present invention relates to an aqueous dispersion resin composition of the type.

(Prior Art) Alkyd paints have conventionally been used for the purpose of surface protection and beautification.

By the way, since conventional alkyd resin paints use organic solvents as a medium, the solvent volatilizes into the working atmosphere, worsening the working environment, which is undesirable from a health and safety standpoint, and always poses a risk of fire or explosion. It was something that was born.

In order to solve these problems, water-based alkyd resins have been developed.

As such water-based alkyd resins, amine neutralized type and emulsion type are known.

The amine neutralized type has a high acid value, and the emulsion type has a high acid value because of the emulsifier used, especially the air-dry type.
Its uses are limited because it is not sufficiently water resistant.

Furthermore, amine-neutralized water-soluble resins have a fatal drawback of reduced storage stability due to hydrolysis.

(Problems to be Solved by the Invention) As described above, conventional alkyd resin paints, especially water-based alkyd resin paints, have many drawbacks that need to be solved, such as water resistance and alkali resistance. Or there is a defect.

In order to improve this drawback, the present inventors have made extensive studies and have developed a mixture of a vinyl-modified alkyd resin that can be water-dispersed due to the hydrophilic component of the vinyl portion, and an oil-soluble alkyd resin. The inventors have now completed the present invention by discovering that an aqueous dispersed alkyd resin in a dispersed form has excellent storage stability and also has the excellent properties of a solvent-based alkyd resin.

(Structure of the present invention) That is, the present invention basically consists of: 1) a water-dispersible vinyl-modified alkyd resin having a hydrophilic component in the vinyl moiety, that is, water dispersion is possible due to the hydrophilic component in the vinyl moiety; This is an aqueous dispersion resin composition made by dispersing a mixture of a vinyl-modified alkyd resin and an oil-soluble alkyd resin in water.

More specifically, 2) a specific aqueous dispersion resin composition obtained using a water-dispersible vinyl-modified alkyd resin in which the hydrophilic component is an acid group-containing vinyl monomer;
) At that time, first, one-third or more of the total vinyl monomer mixture is reacted with another vinyl monomer mixture,
Then, an aqueous dispersion resin composition is obtained by reacting a vinyl monomer mixture containing the acid group-containing vinyl monomer, and 4) the hydrophilic component is a polyoxyethylene-containing vinyl monomer (PEG-containing vinyl monomer). This is a specific aqueous dispersion resin composition obtained using a water-dispersible vinyl-modified alkyd resin.

(Means for solving problems) The configuration of the present invention will be explained in detail below.

First, the alkyd resin used in preparing the vinyl-modified alkyd resin, which is the base resin component of the present invention and can be water-dispersed by the hydrophilic component of the vinyl moiety described above, is commercially available long oil, medium oil, or These are short oil alkyds or oil-free alkyds, and furthermore, so-called epoxy esters, which are reaction acid products of ebo-beef resin and fatty acids, are particularly representative.

Of course, they may be synthesized using appropriate oils and fats, fatty acids, polyhydric alcohols, polybasic acids, etc., depending on the desired performance.

In such a case, there is an advantage that the diluting solvent can be freely selected.

In order to make these alkyd resins water-dispersible, it is necessary to copolymerize a polymerizable monomer containing a hydrophilic component such as an acid group-containing monomer and/or a polyoxyethylene-containing monomer. be.

Here, we will only exemplify particularly typical acid group-containing monomers that are one of the hydrophilic components.
These include unsaturated carboxylic acids such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid.

In copolymerizing such acid group-containing monomers, first, a monomer mixture in which one-third or more of the total vinyl monomer mixture is made up of other vinyl monomers is reacted, and then the acid group-containing vinyl monomers are copolymerized. It is important to react the vinyl monomer mixture containing.

If such a reaction method is not adopted, for example, if the acid group-containing monomer and other monomers are mixed from the beginning and reacted, the resulting vinyl-modified alkyd resin will be a water-dispersible type. However, it becomes water-soluble.

When such water-soluble alkyd resins are used, they have poor storage stability and poor mechanical stability, making it impossible to directly disperse pigments.

The PEG-containing monomer, which is another hydrophilic component, has the following formula: Rr, Rt are H or an alkyl group consisting of C1 to C4, or a phenyl group, and R1 is a hydrogen atom or a C8 to C3
゜ represents an alkyl group, and n is a positive integer representing the number of repeating units of oxyethylene.

Refers to something as shown in .

Among these, only the most representative examples are "Blemmer PME-4000" [product of NOF Corporation] or "NK-Ester M-230".
Products such as GJC Shin-Nakamura Chemical Co., Ltd.).

The acid group and/or polyoxyethylene-containing monomers listed here are generally used together with other copolymerizable polymerizable vinyl monomers.

Typical examples of such other polymerizable vinyl monomers that can be copolymerized include styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene, and chlorostyrene-based styrene monomers: acrylic. Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate,
Acrylic esters such as n-hexyl acrylate, 2-ethylhexyl acrylate, n-4-ctyl acrylate, decyl acrylate or dodecyl acrylate: methyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid Methacrylic acid esters such as isobutyl, n-amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate or dodecyl methacrylate; hydroxyethyl diacrylate, hydroxypropyl acrylate, methacrylate Hydroxyl group-containing monomers such as hydroxyethyl methacrylate or hydroxypropyl methacrylate; or N-methylol (
N-substituted (meth)acrylic monomers such as meth)acrylamide or N-butoxymethyl(meth)acrylamide.

Furthermore, only typical examples of monomers containing amide 7 groups include N, N-dimethylaminoethyl (meth)acrylate, and N.

N-diethylaminoethyl (meth)acrylate or N,N-dimethylaminopropyl (meth)acrylate
Examples include monomers containing 7 tertiary amide groups, such as notebook.

Here, the ratio of alkyd resin to polymerizable vinyl monomer is 90:10 to 10:90, preferably 80:10 to 10:90.
A range of :20 to 40 :60 is appropriate.

When the vinyl monomer degree is less than 10, it is difficult to obtain a good dispersion, and on the other hand, when the alkyd resin is less than 10, it is difficult to obtain a sufficient oxidation-cured film.

In the present invention, when copolymerizing the alkyd resin and the polymerizable monomer, any polymerization method can be applied.

For example, there is a method in which alkyd resin is dissolved in a polymerizable monomer and polymerization is proceeded in the presence of a polymerization catalyst, or alternatively, an alkyd resin is dissolved in a solvent and the polymerizable monomer and polymerization catalyst are added dropwise thereto. There is also a method in which polymerization is carried out simultaneously, and all of these methods are useful.

As such polymerization catalysts, known and commonly used catalysts can be used, but among them, only typical examples include potassium persulfate, ammonium persulfate, hydrogen peroxide, percarbonate, and persulfate. Inorganic peroxide compounds such as benzoyl oxide; or t-butyl hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, silver oxide, alkyl hydroperoxide or dialkyl hydroperoxide; Organic baro-gyuside compounds such as; furthermore, azobisisobutyronitrile compounds and the like.

Moreover, these inorganic or organic peroxide compounds can also be used as a redox catalyst in combination with a reducing agent.

Two or more of these polymerization catalysts may be used in combination.

A water-dispersible vinyl-modified alkyd resin having a hydrophilic component in the vinyl portion obtained in this way, that is, a vinyl-modified alkyd resin that can be water-dispersed due to the hydrophilic component in the vinyl portion (hydrophilic vinyl-modified alkyd resin) The above-mentioned oil-soluble alkyd resins to be used in combination with are commercially available long-oil, medium- or short-oil alkyds, or oil-free alkyds, and furthermore, epochene resins and fatty acid reaction acid products, A portion of any of the so-called epoxy esters may also be present.

Of course, depending on the desired performance, oils and fats, fatty acids,
It may also be one synthesized by a combination with polyhydric alcohols or polybasic acids.

Here, the mixing ratio of the water-dispersible vinyl-modified alkyd resin described above and the oil-soluble alkyd resin used in combination therewith is 10:90-90:10, preferably 20:280-60:20. A range of 40 is appropriate.

When dispersing each alkyd resin thus obtained in water, if necessary, some or all of the acid groups in the resin, especially the carpoquine groups, may be neutralized with a neutralizing agent. Desirably, the pH after neutralization is generally 6.5 to 9.5.

Such neutralizing agents include, for example, inorganic alkalis such as potassium hydroxide or sodium hydroxide; ammonia; or monomethylamine, dimethylamine, triethylamine, monoethylamine, diethylamine, triethylamine, mono-n propylamine, dimethyl n-
Propylamine, monoethanolamine, jetanolamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyljetanolamine, monoisopropanolamine,
One or more amines selected from amines such as diisopropanolamine, triisopropanazine, hydroxylamine, NN-dimethylethanolamine, and N,N-dimethylpropanazine.

The water-dispersible resin composition of the present invention provides a water dispersion with excellent water dispersibility and stability without impairing the characteristics of alkyd resins, and has a wide variety of properties compared to conventional water-dispersible resins. It has the characteristics of

Firstly, it combines the advantages of alkyd resins such as flexibility, texture, adhesion, and water resistance with the high hardness, drying properties, weather resistance, and stain resistance of acrylic polymers.Secondly, The resin (composition) of the present invention has excellent water dispersibility and dispersion stability, and it is possible to directly disperse pigments therein.

The water-dispersible resin composition of the present invention is particularly useful for paints.

When used as a paint, it can be further modified by mixing a plasticizer, acrylic emulsion, various latexes, water-soluble resins, etc., if necessary.

When used for air drying or forced drying, it is preferable to add a metal dryer to accelerate air curing.

Typical examples of such metal dryers include cobalt naphthenate, lead naphthenate, zirconium naphthenate, manganese naphthenate, and calcium naphthenate, and these may be used alone or in combination of two or more types. Of course.

The amount of these used is preferably within the range of 0.05 to 0.5 part as the amount of metal per 100 parts by weight of resin solid content.

When baking is used as a paint, if necessary,
A curing agent such as an amino resin, blocked isocyanate or epoxy resin may also be blended.

Such curing agents are preferably used in the form of aqueous solutions or dispersions.

The amount of the curing agent to be used is preferably within the range of 2 to 50 parts by weight in terms of solid content per 100 parts of resin solid content.

The paint obtained using the composition of the present invention has excellent coating workability in brush coating, dip coating, air spray coating, airless spray coating, and the like.

Conventional emulsion paints tend to foam due to the influence of emulsifiers, and water-soluble paints tend to sag, both of which have drawbacks in the condition of the painted surface and the workability of the paint.

In contrast, the aqueous dispersion resin composition of the present invention does not contain an emulsifier and is water-dispersible, so it has the advantage of being less foamable and less likely to sag.

(Example) Next, the present invention will be specifically explained using a reference example, an example, a comparative example, an applied example, and a comparative applied example.

In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 (Example of Preparation of Vinyl Modified Alkyd Resin) In a four-hole flask equipped with a thermometer, a stirrer, and a reflux condenser, 1. ,000 parts and 600 parts of butyl cellosolve were added and heated to 130°C,
As a polymerization catalyst, [Barbutyl ZJ]
200 parts of styrene and 200 parts of methyl methacrylate were added dropwise over 2 hours to polymerize.

"Add 70 parts of Bremmer PME-4000J (methyl etherified polyoxyethylene methacrylate manufactured by the aforementioned company), and further add 60 parts of styrene, 60 parts of methyl methacrylate, and 110 parts of methacrylic acid,
It was added dropwise over 2 hours to polymerize.

After the reaction was completed, the temperature was kept at 130°C for another 3 hours, and then cooled to below 70°C.
A water-dispersible vinyl-modified alkyd resin was obtained.

Reference Example 2 1,000 parts of Beccosol J-557J (alkyd resin manufactured by Dainippon Ink and Chemicals Co., Ltd.) and 155 parts of methyl ethyl ketone were placed in a four-loaf flask equipped with a thermometer, a stirrer, and a reflux condenser. In addition, the temperature was raised to 80℃,
After adding 20 parts of rNK-ester M-230GJ and polymerizing while dropping 130 parts of butyl methacrylate over 1.5 hours using "Barbutyl 0" (product of the previous company) as a polymerization catalyst, successively, Furthermore, 100 parts of butyl methacrylate and 50 parts of acrylic acid were added to 1
, polymerization was carried out by dropping the solution over a period of 5 hours.

After the reaction was completed, the mixture was kept at the same temperature for 3 hours and then neutralized by adding 60 parts of dimethylethanolamine to obtain a water-dispersible vinyl-modified alkyd resin.

Reference Example 3 In a four-loaf flask equipped with a thermometer, a stirrer, and a reflux condenser, 150 parts of linseed oil fatty acid and
Add 150 parts of 050J (epoxy resin manufactured by Dainippon Ink & Chemicals Co., Ltd.) and stir until the acid value reaches 10.
After reacting at 30°C and cooling to below 1106°C, 700 parts of butyl alcohol was added for dilution.

This reaction product was then treated with rNK-ester M-230G.
Add 25 parts of J5. At a temperature of 110'C, 250 parts of butyl methacrylate and 225 parts of methyl methacrylate were reacted dropwise over 3 hours using "Barbutyl Z" as a polymerization catalyst, and then 155 parts of butyl methacrylate was added. and 45 parts of methacrylic acid were added dropwise over 1 hour for polymerization.

After the reaction was completed, the mixture was held for another 3 hours and then neutralized by adding 55 parts of triethylamine to obtain a water-dispersible vinyl-modified alkyd resin.

Reference Example 4 (Example of preparation of vinyl-modified alkyd resin for control) Reference example except that the use of rNK-ester M-230GJ was changed to -cut or omitted, and a mixture of other fully polymerizable vinyl monomers was used. A vinyl-modified alkyd resin was synthesized and neutralized in the same manner as in Example 2 to obtain a control vinyl-modified alkyd resin.

Water was then added to the control resin, resulting in a clear solution.

Example 1 1,000 parts of the water-dispersible vinyl-modified alkyd resin obtained in Reference Example 1 and “Beccosol P-47
The mixture was heated to 60°C, and 1,250 parts of distilled water was added dropwise over 3 hours while thoroughly stirring and mixing to obtain the desired aqueous dispersion resin.

This material has a non-volatile content of 40.2% and a viscosity of 2.2% at 25°C. 750 c p s and pH 8
．． 3, which had excellent dispersion stability.

Example 2 550 parts of the water-dispersible vinyl-modified alkyd resin obtained in Reference Example 2 and [Beccosol J-557J] were placed in a four-loaf flask equipped with a thermometer, a stirring device and a reflux condenser.
1,400 parts of the resin was charged, the temperature was raised to 60°C, and 500 parts of distilled water was added dropwise over 3 hours while thoroughly stirring and mixing to disperse the resin in the water. The boiling point solvent was removed to obtain the desired aqueous dispersion resin.

This product has a nonvolatile content of 47.7% and a viscosity of 2.1%.
The dispersion stability was 70 cps and the pH was 8.7.

Example 3 1,000 parts of the water-dispersible vinyl-modified alkyd resin obtained in Reference Example 3 and [Beccosol P-78
6-50J [Algydo resin manufactured by Dainippon Ink and Chemicals Co., Ltd.] and 800 parts of the mixture were heated to 60°C, and 500 parts of distilled water was added dropwise over 3 hours while thoroughly stirring and mixing. After dispersing the resin in water, the low boiling point solvent was removed under reduced pressure to obtain the desired aqueous dispersion resin.

This product has a nonvolatile content of 54.6% and a viscosity of 1.3
The dispersion stability was 20 cps and the pH was 7.6.

Comparative Example l 550 parts of the water-soluble control vinyl-modified alkyd resin obtained in Reference Example 4 and “Beccosol J-55
7J, the temperature was raised to 60°C, and 500 parts of distilled water was added dropwise over 3 hours while thoroughly stirring and mixing to disperse the resin in water, and then under reduced pressure. A control aqueous dispersion resin was obtained by removing the low boiling point solvent.

This product has a nonvolatile content of 45.2% and a viscosity of 5.1%.
30 cps and pH was 8.9.

Next, when this aqueous dispersion resin was stored in a dryer at 50° C., separation of the aqueous dispersion was already observed within three days.

Application Examples 1 to 3 and Comparative Application Example 1 and Standard Example
1 The coating performance of the aqueous dispersion resin composition and aqueous resin solution obtained in Example 1.2.3 and Comparative Example 1 was measured, and the results are shown in Table 1.

In addition, [BECCOSOL P] as a solvent-based alkyd resin
-470J [Dainippon Ink & Chemicals Co., Ltd. product] was also used as Standard Example 1, and the coating film performance was as follows.
Shown in the same table.

Test conditions: PWC: 50% white coating material ("Tiebake R-930" manufactured by Ishihara Sangyo Co., Ltd. is used as the pigment) Base material: Untreated steel plate (Bright) Painting: Brush coating Drying: 5 days at room temperature As is clear from the table, it is known that the paint obtained using the aqueous dispersion resin composition of the present invention is particularly excellent in storage stability, and is also excellent in water resistance and corrosion resistance.

(Effects of the Invention) The present invention provides an aqueous alkyd resin and an aqueous dispersion resin composition thereof, which have the excellent properties inherent to solvent-based long oil and medium oil alkyd resins, and which can be obtained as described above. The resin composition of the present invention has particularly excellent storage stability, as well as excellent water resistance and corrosion resistance.

In contrast, conventional emulsion types tend to foam due to the influence of emulsifiers and have a significant drop in water resistance, while conventional water-soluble types tend to drip easily and
Poor alkali resistance.

Thus, conventional water-based resins have drawbacks in terms of coating surface condition, coating workability, and coating film performance, but the resin according to the present invention does not contain an emulsifier and is water-dispersible. It has the advantage of not easily foaming and sagging, and also shows good coating performance.

Claims (1)

[Scope of Claims] 1. An aqueous dispersion resin composition prepared by dispersing in water a mixture of a water-dispersible vinyl-modified alkyd resin having a hydrophilic component in the vinyl portion and an oil-soluble alkyd resin. 2. The aqueous dispersion resin composition according to claim 1, wherein the hydrophilic component is an acid group-containing vinyl monomer. 3. The water-dispersible vinyl-modified alkyd resin having a hydrophilic component in the vinyl moiety described above is first reacted with a vinyl monomer mixture other than the acid group-containing vinyl monomer, which is one-third or more of the total vinyl monomer mixture, The aqueous dispersion resin composition according to claim 1, which is obtained by subsequently reacting a vinyl monomer mixture containing an acid group-containing vinyl monomer. 4. The aqueous dispersion resin composition according to claim 1 or 3, wherein the hydrophilic component is a polyoxyethylene-containing vinyl monomer.