JPH03146549A - Water-based polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a water-based polyester resin composition exhibiting proper viscosity at high solid concentration, having excellent water-resistance, weather resistance, etc., and suitable for ink, paint, etc., by polymerizing a polymerizable monomer containing unsaturated group in the presence of a specific hydrophilic vinyl polymer. CONSTITUTION:An aqueous dispersion of a polyester resin having a molecular weight of 2,500-30,000 is compounded with 0.02-20wt.% (preferably 0.1-10wt.%) of a hydrophilic vinyl polymer containing functional groups selected from sulfonic acid metal salt group, carboxyl group and hydroxyl group in amounts satisfying the formula I and formula II [(a), (b) and (c) are amounts (m-mol/g) of sulfonic acid metal salt group, carboxyl group and hydroxyl group, respectively]. The system produced by the above process is compounded with 10-400wt.% (preferably 20-300 wt.%) of a polymerizable monomer (e.g. vinyl acetate) and the monomer is polymerized to obtain the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a water-based polyester resin composition. More specifically, the present invention relates to a water-based polyester resin composition that has a high solid content and a wide range of viscosity characteristics, and is suitable for inks, paints, coatings, and the like.

(Prior Art) Traditionally, large amounts of organic solvents have been used in the fields of inks, paints, coatings, adhesives, etc.
From the viewpoint of saving petroleum resources, environmental pollution, and safety, it is becoming difficult to use organic solvents, and there has been an active movement toward water-based solvents in recent years.

Already, methods for dispersing or making polyester resins water-soluble include copolymerizing hydrophilic raw materials, such as copolymerizing raw materials containing sulfonic acid metal bases and polyethylene glycol, etc. There is 0
For example, in Japanese Patent Publication No. 47-40873, it is necessary to use both a sulfonic acid metal base-containing compound in an amount of 8 mol% or more based on the total acid component and a polyethylene glycol in an amount of 20 mol% or more based on the total glycol component. However, such aqueous dispersions of polyester resins have problems in terms of weather resistance and water resistance.

As a solution to this point, it has already been proposed in Japanese Patent Publication No. 61-58092 that the polycarboxylic acid component is 40 to 99.5 mol% of aromatic dicarboxylic acid containing no sulfonic acid metal base, 59 mol% of aliphatic or alicyclic dicarboxylic acid, .5 to 0 mol% and sulfonic acid metal base-containing aromatic dicarboxylic acid 0
．． Aqueous dispersions of polyester resins comprising 5 to 10 mol% have been proposed.

The aqueous dispersion obtained above has excellent weather resistance (1), but is not necessarily satisfactory in terms of water resistance and dispersion stability, and has had to have limited uses. A further serious drawback is that when the solid content concentration of the aqueous dispersion is increased, the viscosity of the above-mentioned aqueous dispersion increases sharply and becomes paste or hook-like, and the solid content concentration is limited to about 30% by weight. One way to obtain a high solid content concentration is to reduce the molecular weight of polyester, but this is not necessarily an appropriate method to satisfy various physical properties such as adhesion, flexibility, and water resistance. .

(Problems to be solved by the invention) As mentioned above, from the viewpoint of environmental pollution and safety, it has a high solid content (high solids) and an appropriate viscosity, and also has water resistance and
There is a strong demand for the development of stable water-based polyester resins that have excellent weather resistance, adhesive properties, etc., and the present invention is an attempt to solve these problems.

(Means for Solving the Problems) In view of the above-mentioned problems, the present inventors have conducted intensive research and found that an aqueous dispersion of polyester resin contains at least one compound selected from a sulfonic acid metal base, a carboxy group, and a hydroxyl group.
By polymerizing unsaturated group-containing polymerizable monomers in a system containing hydrophilic vinyl polymers containing various types of functional groups, it is possible to achieve appropriate viscosity at a high solids concentration and to maintain various physical properties. It was discovered that an excellent water-based polyester resin composition can be obtained, and the present invention was achieved.

That is, the present invention provides an aqueous dispersion of polyester resin (1
) is blended with a hydrophilic vinyl polymer (II) containing at least one functional group selected from a sulfonic acid metal base, a carboxyl group, and a hydroxyl group within a range that satisfies the following formulas and (1), It is a water-based polyester resin m-acid obtained by polymerizing a polymerizable monomer ([[[)].

1.0≦a+b+c≦20 ・・・・・・・・・ ■
a≦7 ...... ■ The polyester resin used in the present invention preferably contains a hydrophilic group, and examples of the hydrophilic group include a metal sulfonate base, a metal base sulfate, and a metal carboxylate base. Examples include bases, metal phosphate bases, metal phosphonate bases, amine bases, etc., but the metal bases that exhibit the most remarkable effect of the present invention are metal bases of sulfonate.

A polyester resin containing a sulfonic acid metal base can be obtained by copolymerizing a sulfonic acid metal base-containing aromatic dicarboxylic acid as a polycarboxylic acid component.

From the viewpoint of water resistance of the cured coating film, the copolymerization ratio should be 0.5 to all polycarboxylic acid components or all polyol components.
~10 mol% is preferred.

When the copolymerization component is an aromatic dicarboxylic acid containing a sulfonic acid metal group, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid , 5 [
Metal salts such as 4-sulfophenoxy]isophthalic acid can be mentioned.

Metal salts include Li, Na, K, Mg, Ca
Examples include salts such as 5Cu and Fe. Particularly preferred is 5-sodium sulfoisophthalic acid.

In the polyester resin used in the present invention, it is preferable to use the above-mentioned aromatic dicarboxylic acid containing a sulfonic acid metal base as the polycarboxylic acid component, but other aromatic dicarboxylic acids, aliphatic or alicyclic dicarboxylic acids may be used as appropriate. You can choose.

Examples of aromatic dicarboxylic acids that do not contain sulfonic acid metal groups include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid.

Examples of aliphatic or alicyclic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid,
Examples include hexahydroterephthalic acid.

Furthermore, if necessary, p-hydroxybenzoic acid, p-(2
-Hydroxyethoxy)benzoic acid, hydroxypivalic acid, T-butyrolactone, ε-caprolactone, etc., and if necessary, tri- or higher functional polycarboxylic acids such as trimellitic acid, pyromellitic acid, etc., to all polycarboxylic acid components, It can be used if it is 10 mol% or less.

Examples of the polyol component include aliphatic glycols having 2 to 8 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, diethylene glycol, and ethylene oxide or propylene oxide adducts of bisphenol A; Examples of aliphatic glycols include ethylene glycol, ■.

2-propylene glycol, 1.3-propanediol, 1.4-butanediol, neopentyl glycol,
Examples include 1.5-bentanediol, 3-methylbentanediol, and 1.6-hexanediol. As an alicyclic glycol having 6 to 12 carbon atoms, 1.4
-Cyclohexane dimetatool, etc. can be mentioned. In addition, if necessary, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, and other trifunctional or higher functional polyols may be added to the total polyol component.
It can be used within the range of mol% or less.

In the present invention, the polyester resin can be used alone or in combination of two or more types if necessary. The polyester resin used in the present invention is essentially non-quality and has a softening point in the range of 40 to 200°C. The temperature is preferably 60 to 180°C, particularly preferably 60 to 180°C. If the softening point of the polyester resin does not reach 40°C, the resulting film tends to be highly adhesive and have poor water resistance.

The molecular weight of the polyester resin used in the present invention is approximately 2'
, 500 to about 30,000. If the molecular weight is too low, the resulting film will have poor mechanical properties, especially flexibility, which is undesirable.If the molecular weight is too high, the viscosity of the aqueous dispersion will increase, making it difficult to increase the polyester resin content. become.

The aqueous dispersion (1) of polyester resin, which is an essential component of the present invention, can be produced by any known method. Add to water or with water boiling point 6
It is produced by adding the polyester resin to a mixture of water-soluble organic compounds at 0°C to 200'C, or by directly dispersing it in water. The water-soluble organic compound referred to here is an organic compound having a solubility in 1 l of water at 20°C of 20 g or more, and specifically, m alcohols such as methanol, ethanol, n-propanol, and n-butanol. Glycols such as ethylene glycol, propylene glycol, glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, 3-methyl-3-methoxybutanol, ethers such as dioxane, esters such as ethyl acetate, methyl ethyl ketone, methyl These include ketones such as mebutyl ketone, cyclohexane, and isophorone.

The hydrophilic vinyl polymer (n) used in the present invention is a polymer containing at least one functional group selected from a sulfonic acid metal base, a carboxyl group, and a hydroxyl group within a range that satisfies the following formulas. It is. Even if a polymer other than such a polymer is used, the object of the present invention cannot be achieved.

1.0≦a+b+c≦20 ・・・・・・・・・ ■
a≦7 ・・・・・・・・・ ■ Vinyl monomers used for introducing the sulfonic acid metal base into the hydrophilic vinyl polymer (It) include styrene sulfonic acid, vinyltoluenesulfonic acid, Vinylethylbenzenesulfonic acid, isopropenylbenzenesulfonic acid, 2-chlorostyrenesulfonic acid, 2,4-dichlorostyrenesulfonic acid, 2-methyl-4-chlorostyrenesulfonic acid, vinyloxybenzenesulfonic acid, vinylsulfonic acid, (meth) ) allylsulfonic acid, (meth)acrylic acid sulfoethyl or sulfopropyl ester, 2-acrylamido-2-methylpropane sulfone, etc., and the types of metal salts include Li, Ha.
, K, Mgs Ca, etc.

Examples of carboxyl group-containing vinyl monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, aconitic acid, citraconic acid, and mesaconic acid; examples of hydroxyl group-containing vinyl monomers include: Examples include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerin mono (meth)acrylate, etc.In order to more effectively achieve the object of the present invention, The range of a+b+c in the above formula is 1
．． 5 to 14 m+mol/g is also [
1 is an aromatic sulfonic acid metal base, and the range of a is 5.
m+*ol/g or less is particularly desirable for water-soluble vinyl polymers. Within the scope that satisfies the requirements of the present invention,
It is also possible to copolymerize other vinyl polymerizable monomers.

There is no limitation on the method for producing a hydrophilic vinyl polymer as long as it contains a predetermined vinyl polymerizable monomer within a range that satisfies formulas (1) and (2) above. An industrial method is to carry out polymerization using a water-soluble redox initiator having an equivalent ratio within the range of 1.0 to 1.9.

Oxidizing agents include persulfates, hydrogen peroxide, permanganates, second metal salts, nitrites, peracetic acid, etc.; reducing agents include sulfites, bisulfites, metasulfites, and hydrosulfites. salts, thiosulfates, iron salts, oxalic acid, silver nitrate, etc., especially persulfates and reducing sulfoxy compounds and/or
Alternatively, a redox initiator consisting of a combination with ferrous ion or a combination of chlorate and a reducing sulfoxy compound is desirable. It is also possible to coexist a chain transfer agent such as carbon tetrachloride or mercaptans in the polymerization system.

There is no particular restriction on the degree of polymerization of the hydrophilic vinyl polymer (II), but within a practical molecular weight range, polymers with a small molecular weight (1), that is, GPC (polystyrene standard)
It is desirable to have a weight average molecular weight of 100,000 or less, preferably 80,000 or less, as determined by the above method, in order to achieve the purpose of the present invention.

The blending amount of the hydrophilic vinyl polymer (■) is determined based on the desired stability of the aqueous dispersion, water resistance, solvent resistance, resolubility,
It is determined appropriately depending on the viscosity etc., but it is approximately 0.02 to 20% by weight, preferably 0.0% by weight based on the polyester resin.
5 to 15% by weight, more preferably 0.1 to 10% by weight
The polymerizable monomer (1) used in the present invention, which is preferably set within the range of , vinyl esters such as vinyl stearate, methyl (meth)acrylate,
Ethyl (meth)acrylate, n-propyl (meth)acrylate, butyl (meth)acrylate, octyl (
Monofunctional acrylates such as meth)acrylate, 2-ethyl-hexyl (meth)acrylate, lauryl (meth)acrylate, glycidyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, Polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, (meth)acrylamide, methylol(meth)acrylate, etc. ) acrylamide, (meth)acrylamides such as butoxymethylol acrylamide, unsaturated nitriles such as (meth)acrylonitrile, allyl glycidyl ether, (
Allyl compounds such as allyl meth)acrylate and itacone diallyl, unsaturated hydrocarbons such as styrene, vinyltoluene, vinylnaphthalene, butanediene, isoprene, and hexene, dimethylvinylmethoxysilane, dimethylethylethoxysilane, methylvinyldimethoxysilane, methylvinyl Vinyl silanes such as jetoxysilane and γ-methacryloxypropylmethyldimethoxysilane, vinyl monomers containing the aforementioned sulfonic acid metal bases, vinyl monomers containing carboxyl groups or their salts with alkali metals, ammonium, amines, etc., containing hydroxyl groups Vinyl monomers etc. can be used.

The aqueous polyester resin of the present invention, the t[I acid compound, is an aqueous dispersion of a polyester resin (r
) is mixed with the hydrophilic vinyl polymer (1), and then the polymerizable monomer (III) is charged into the system and polymerized. There is no particular restriction on the polymerization initiator used to initiate the polymerization. , for example, organic peroxides such as benzoyl peroxide and acetyl peroxide, inorganic peroxides such as potassium persulfate and ammonium persulfate, and ab compounds such as 2,2°-azobisisobutyronitrile and azobisvaleronitrile. can be mentioned.

The amount of the polymerizable monomer (Ill) is 10% to 400% by weight, preferably 20% to 300% by weight, based on the polyester resin. If it is less than 10% by weight, there will be no improvement effect on weather resistance, etc., and if it exceeds 400% by weight, the good properties of the polyester resin such as flexibility and adhesiveness will be impaired.

The solid content concentration of the aqueous polyester resin composition of the present invention is selected depending on the intended use, but usually the solid content concentration is 5 to 80% by weight, preferably 10 to 70% by weight. Outside this range, the suitability for painting or coating is poor.

The aqueous polyester resin composition of the present invention may be used as it is, or may be blended with a crosslinking agent for the purpose of further improving performance.

As the crosslinking agent, one or more compounds selected from the group of amino resins, epoxy compounds, and isocyanate compounds can be blended and used.

Examples of the resins include formaldehyde adducts such as urea, melamine, and pendiguanagon, and alkylated products with alcohols having 1 to 6 carbon atoms. Further, if necessary, a preferable effect can be achieved by using formalin in combination.

Epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof,
Orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, P-oxybenzoic acid glycidyl ether ester,
Tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester,
Sebacate diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, l,4-butanediol diglycidyl ether, 1,6-hexanesiol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ether, Examples include glycidyl, triglycidyl isocyanurate), 1,4-diglycidyloxybenzene, diglycidyldimethylhydantoin, diglycidylethylene urea, diglycidylpropylene urea, glycerol polyglycidyl ether, trimethylolethane polyglycidyl ether, etc. can.

Furthermore, the isocyanate compound includes aromatic, group, and aliphatic diisocyanates, and polyisocyanates having a valence of 3 or more, and may be either a low-molecular compound or a high-molecular compound.

For example, isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, isophorone diisocyanate tripartite, or these. An excess of isocyanate compounds and low-molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenecyamine, monoethanolamine, jetanolamine, triethanolamine, or various polyethers. Examples include terminal isocyanate group-containing compounds obtained by reacting with polymeric active hydrogen compounds such as polyols, polyester polyols, and polyamides. The isocyanate compound may be a blocked isocyanate. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, ethylphenol, and cresol, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, and methanol. , alcohols such as ethanol and propatool, lactams such as ε-caprolactam and γ-valerolactam, and aromatic amines, imides, active methylene compounds such as acetylacetone and ethyl acetoacetate, and mercaptans. , and ureas.

A curing agent or an accelerator can also be used in combination with these crosslinking agents.

In addition to the above-mentioned crosslinking agent, the water-based polyester resin &lI compound of the present invention may also contain known thixotropy imparting agents, surface smoothing agents, antifoaming agents, pigments, and coupling agents.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the Examples.

In the examples, parts simply indicate parts by weight. Evaluation of various properties was carried out according to the following methods.

1. Molecular weight: Molecules! Measuring device (Hitachi model 115)
Measured using.

2. Softening point and crystal melting point: Fully automatic melting point measuring device (open T
-Measurement was carried out using MODEL FP-1) manufactured by TLER.

3. Particle diameter of the dispersion was measured using a Nigerien indometer and an optical microscope.

4. Viscosity: Measured with a B-type viscometer at 25°C.

95 parts of polyester dimethyl terephthalate, 95 parts of dimethyl isophthalate, 71 parts of ethylene glycol, 110 parts of neopentyl glycol, 0.1 part of zinc acetate and 0.1 part of antimony dioxide were charged into a reaction vessel, and the mixture was heated at 140'C to 22°C.
A transesterification reaction was carried out at 0"C for 3 hours. Next, 6.0 parts of 5-sodium sulfoisof')) Lt was added, and an esterification reaction was carried out at 220°C to 260°C for 1 hour. After that, a polycondensation reaction was carried out at 240°C to 270'C under reduced pressure (10 to 0.2 anl 1g) for 2 hours to obtain a polyester resin (A-1) with a molecular weight of 19,500 and a softening point of 160°C. Further, a polyester resin (A-2) was obtained in exactly the same manner except that the raw materials shown in Table 1 were used.The characteristic values thereof are shown in Table 1.

350 parts of Table 1 polyester resin (A-1) and 100 parts of n-butyl cellosolve were placed in a container, and
After stirring at 0°C for about 3 hours to obtain a homogeneous and viscous melt,
Gradually add 550 parts of water with vigorous stirring until approx. xn
The viscosity of the 0 dispersion (C-1), from which a pale bluish-white dispersion (C-1) uniform in r, yuk was obtained, was 5.0 OO cps.

In addition, 250 parts of polyester resin (A-2) and n-
After charging 100 parts of butyl cellosolve into a container and obtaining a uniform and viscous melt in the same manner, 650 parts of water was gradually added while stirring vigorously, and after about 1 hour, a uniform dispersion (C-2 ) The viscosity of the obtained dispersion (C-2) is l 1
It was 0.000 cps.

3 parts of ammonium persulfate to 100 parts of the monomer shown in Table 2 of the vinyl heavy body.
part, acidic sodium sulfite, 1.8 parts, chloride chloride 0.00
015 parts and 400 parts of deionized water and heated at 70° while stirring.
Polymerize with C for 1 hour to obtain water-soluble vinyl polymer (B-1)
~(B-9) was obtained. Note that the catalyst was added all at once after the temperature was raised. The properties of the obtained polymer are shown in Table 2.

Table Example 1 417 parts of dispersion (C-1), 1 part of benzoyl peroxide, 7.5 parts of methyl methacrylate, hydrophilic vinyl polymer (B
-5) (solid content 20%) 1.8 parts, ion exchange water 17.
Pour 8 parts into a separable flask and add IO to the stirrer nitrogen.
After deoxidizing by blowing for 1 minute, the temperature was raised to 80°C.Next, 21 parts of methyl methacrylate, 6.5 parts of glycidyl methacrylate, and 15 parts of butyl acrylate were added dropwise over 40 minutes with stirring at 80°C.6 Dropwise addition completed. After, 8
The mixture was stirred at 0°C for 160 minutes to obtain a water-based polyester resin composition (D-1) of the present invention. p of the resulting resin composition
H was 4.8 and viscosity was 96 cps.

The obtained water-based polyester resin & lImono (D-1) was applied onto a 6.8 mm thick glass plate to a coating thickness of 20 μm, dried at 160°C for 20 minutes, and the coating film was coated. Performance was evaluated. The results are shown in Table 3.

Comparative Example 1 A procedure was carried out in exactly the same manner as in Example 1, except that 1.8 parts of a phosphoric acid ester surfactant Plysurf A217E (manufactured by Daiichi Kogyo Seiyaku ■) was used instead of the hydrophilic vinyl polymer (B-5). , a water-based polyester resin composition (D-2) was obtained. The pH of the obtained resin was 4.5, and the viscosity was 94.50.
It was 0 cps.

From the results shown in Table 3, it can be seen that the water-based polyester resin composition of the present invention has an extremely low viscosity.

Example 2 Water-based polyester Resin compositions (D-3) to (D-10) were obtained. The properties of the obtained resin composition are shown in Table 4.

Table 4 Example 3 Dispersion (C-2) 400 parts, azobisisobutylnitrile 0.8 parts, methyl methacrylate 5.3 parts, hydrophilic vinyl polymer (B-5) (solid content 20%) 35 A separable flask was charged with 12.7 parts of ion-exchanged water, and nitrogen was blown in for 10 minutes with stirring to remove oxygen.
The temperature was raised to 0°C, then methyl methacrylate 1
5 parts of glycidyl methacrylate, 4.7 parts of butyl acrylate were added dropwise over 30 minutes while stirring at 80" C1. After the completion of the dropwise addition, the water-based polyester resin of the present invention was stirred at 80°C for 180 minutes. 1111 (D-1
1) was obtained. The resulting resin has a pl+ of 4.4 and a viscosity of 1
, 200 cps.

Table 5 Example 4 Water-based polyester resin composition 2 of the present invention obtained in Example 1
50 parts of hexamethoxymethylolmelane, 100 parts of titanium oxide, and 0.25 parts of para-toluenesulfonic acid were mixed and dispersed in a paint shaker for 10 hours to form a paint. The obtained paint was coated with a #36 bar coater for 0.3
After coating on a mm galvanized iron plate, it was baked at 230°C for 30 seconds. The physical properties of the resulting coating film were as follows.

Adhesion 100/100 gloss (601 reflection) 80% Pencil hardness 3H Xylene rubbing (times) 50 times or more Example 5 Dispersion (C-1) 417 parts, azobisdimethylvaleronitrile 0.4 part, hydrophilic vinyl polymer Combined (B-5) (solid content 20%) 3.5 parts and 17 parts of ion-exchanged water were charged into a separable flask, deoxidized and heated in the same manner as in Example 1, and then 12 parts of methyl methacrylate, 6 parts of butyl acrylate and 2 parts of allyl methacrylate at 80"
C, 13 parts of methyl methacrylate, which was added dropwise over 20 minutes with stirring and the reaction was continued for an additional 40 minutes;
7 parts of butyl acrylate, 7 parts of hydroxyethyl methacrylate and 3 parts of methacrylic acid were mixed at 80°C with stirring for 30 minutes.
It was added dropwise over a period of minutes, and stirring was continued for an additional 160 minutes.
Water-based polyester resin 11 precepts of the present invention (D-12:
pH 4.2 viscosity 92 cps) was obtained.

Resin & Animal D-12) was neutralized to pH 8 with dimethylaminoethanol (viscosity 1200 cps) L, and Sumimaru M-40H was added to 100 parts of solids in the composition.
After adding 20 parts (manufactured by Sumitomo Chemical Industries, Ltd.) and 0.4 part of P-)luenesulfonic acid, a coating film was prepared according to the recipe described in Example 1.

The evaluation results are shown in Table 6.

From the upper table of Table 6, it can be seen that the water-based polyester resin M paraboloid of the present invention forms an excellent coating film.

(Effects of the Invention) The water-based polyester resin and acid product of the present invention is obtained by polymerizing a polymerizable monomer in the presence of a specific hydrophilic vinyl polymer, so that it has (1) a relatively low viscosity; In addition, it is possible to make a composition with a high solid content concentration, and it is possible to make a so-called high solid composition.

(2) A water-based polyester resin composition with good water resistance and solvent resistance can be obtained without impairing the properties of the polyester resin.

(3) It is easy to select the composition of the polymerizable monomer, and it is also possible to impart resolubility to the water-based polyester resin.

It has many advantages such as:

Taking advantage of these advantages, the aqueous polyester resin composition of the present invention can be used in the fields of paints, inks, coating agents, and treatment agents for textile products, paper, and the like.

Claims (1)

[Scope of Claims] At least one functional group selected from a sulfonic acid metal base, a carboxyl group, and a hydroxyl group is added to the aqueous dispersion (I) of a polyester resin as shown in (1) and (2) below.
) Hydrophilic vinyl polymer (I
A water-based polyester resin composition obtained by polymerizing polymerizable monomer (III) in a system containing I). 1.0≦a+b+c≦20 (1) a≦7 (2) where a, b and c are each a sulfonic acid metal base or a carboxyl group contained in the hydrophilic vinyl polymer (II). The amount of groups and hydroxyl groups (mmol/g) is shown.