JPH0391558A - Aqueous polyester resin dispersion - Google Patents

Abstract

PURPOSE:To prepare an aq. polyester resin dispersion having a high solid content, an easily adjustable viscosity, and an excellent stability by compounding a polyester resin contg. a specified amt. of an org. dicarboxylic acid having a metal sulfonate group with a hydrophilic vinyl polymer having a specific functional group. CONSTITUTION:A polyester resin contg. 0.5-10mol% arom. dicarboxylic acid having a metal sulfonate group (e.g. sodium sulfoterephthalate) as a polycarboxylic acid component is compounded with a hydrophilic vinyl polymer (e.g. sodium p-styrenesulfonate/acrylic acid copolymer) having at least one functional group selected from the group consisting of metal sulfonate, carboxyl, and hydroxyl groups in an amt. satisfying the relations I and II [wherein a, b, and c are an amt. (mmol/g) of each of the metal sulfonate, carboxyl, and hydroxyl groups contained in the hydrophilic vinyl polymer] to produce an aq. polyester resin dispersion useful for an ink, coating material, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an aqueous polyester resin dispersion, and more specifically, it has a high solids content and a wide range of viscosity characteristics.
The present invention relates to an aqueous polyester resin dispersion that can be suitably used as an ink, a coating agent, a binder, etc.

(Conventional technology and problems) Aqueous dispersions of polyester resins have excellent film-forming ability such as water resistance, weather resistance, and gloss, and require only a small amount or no use of organic solvents. Therefore, it is preferable in terms of environmental pollution prevention, resource and energy saving, and ease of handling, and active efforts are being made to develop it.

However, the stability and resolubility of the dispersion (even if a film dries at room temperature is formed during painting, the ability to redisperse in an aqueous medium)
), increasing the amount of hydrophilic groups introduced such as sulfonic acid metal bases, carboxyl groups, and hydroxyl groups reduces water resistance and corrosion resistance, and also decreases the hydrophilic groups in the polyester resin main chain (end groups). If the amount is increased, the molecular weight will inevitably decrease, and the film performance itself will also decrease.

In addition, increasing the solid content concentration of the dispersion significantly increases the viscosity, so the production of products with a concentration of 80 to 85% by weight is the limit. It has inherent drawbacks such as application problems such as the need for multiple applications and transportation problems.

In addition, as the polycarboxylic acid component in the polyester resin, aromatic dicarboxylic acids, especially terephthalic acid, are usually selected as the main component due to various physical properties such as water resistance and hardness. It has poor compatibility with acrylic emulsion exchangers, and when the two are mixed for the purpose of modification, thickening, phase separation, and gelation may occur.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide an aqueous polyester resin dispersion that can be adjusted to a viscosity according to the application without changing the solid content concentration; and has excellent stability and resolubility. Another object of the present invention is to provide a polyester resin that does not substantially increase in viscosity even during polymerization and modification of vinyl hexamer in order to further improve water resistance and solvent resistance. An object of the present invention is to provide an aqueous dispersion.

(Means for Solving the Problems) The above-mentioned object of the present invention is to contain an aromatic dicarboxylic acid containing a sulfonic acid metal group as a polycarboxylic acid component in an amount of 0.5 to 1
A hydrophilic vinyl polymer containing at least one functional group selected from a sulfonic acid metal base, a carboquine N group, and a hydroxyl group within a range that satisfies the following formulas and (2) is blended into a polyester resin containing 0 mol%. This is achieved by using an aqueous polyester resin dispersion.

1, o≦a−)−b+c≦20・・・・・・・・・■
Contains 0.5 to 10 mol%, preferably 1 to 7 mol%, of aromatic dicarboxylic acid containing sulfonic acid gold R base as a ricaponic acid component. If necessary, stable if less than the lower limit of the range. If the upper limit of the above range is exceeded, the water resistance of the film will decrease.

Sulfonic acid metal base-containing aromatic dicarboxylic acids include sulfoisophthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 6 (4-sulfophenoxyfinphthalic acid, etc.) Gold IUII is mentioned, and the types of metal salts are Li, Na
, K, Mg, C&%Cu%Fe, etc.

Among them, the remaining polycarboxylic acid component is an aromatic dicarboxylic acid containing no sulfonic acid metal base m40 to 99.
5 mol%, aliphatic or alicyclic dicarboxylic acid 59.5-0
Examples of aromatic dicarboxylic acids that do not contain sulfonic acid metal groups and which are appropriately selected within the range of mol% include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, etc.; Examples of dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sepacic acid, dodecanedioic acid, dimer acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, and the like. Furthermore, p-hydroxybenzoic acid, p-(
(2-hydroxyethoxy)benzoic acid, hydroxypivalic acid, r-butyroctone, C-cabrolactone, etc. can be used as necessary, and as necessary, polycarboxylic acids with 8 or more functional groups such as citrimellitic acid and pyromellitic acid can be used. can be used in an amount of 10 mol% or less based on the total polycarbonate m component.

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 bispherol A. Examples of aliphatic glycols having 2 to 8 carbon atoms include ethylene glycol, 1.2-propylene glycol% 1% 2-propylene glycol, 1.8-propanediol, 1.
4-butanediol, neopentyl glycol, l, 6
-bentanediol, 1,6-hexanediol, etc.
As an alicyclic glycol having 6 to 12 carbon atoms, 1,4-V
Examples include chlorhexanedimetatool and the like. In addition, if necessary, trimethylolpropane, trimethylolethane,
An octafunctional or higher functional polyol such as glycerin or pentaerythritol may be used in an amount of less than 5 mol % based on the total polyol component.

In the present invention, polyester resins can be used alone or in combination of two or more as necessary.

The polyester resin of the present invention has a softening point in the range of 40 to 200°C, which is essentially inferior.

Particularly preferred is 60 to 180°C. In the case of a crystalline polyester having a distinct crystalline melting point, the obtained aqueous dispersion has poor storage stability and phase separation easily occurs, making it impossible to obtain a stable aqueous dispersion. If the softening point of the polyester resin does not reach 406C, the resulting film will be highly adhesive and have poor water resistance. On the other hand, the softening point is 200°
If it exceeds C, the dispersibility in water becomes poor.

The molecular weight of the polyester resin of the present invention is 2500~aoo
oo range, particularly preferably 8000 to 2000
It is 0. If the molecular weight does not reach 2,600, the mechanical properties of the resulting film, particularly flexibility, are unfavorable.

Furthermore, if the molecular weight exceeds aooooo, the viscosity of the aqueous dispersion increases, making it difficult to increase the content of the polyester resin.

The polyester resin of the present invention can be produced by any known method. In addition, the polyester resin thus obtained can be used in a molten state or in a solution state with a water-soluble organic compound described below to form a 7-mino resin, an epoxy compound,
It can also be mixed with isocyanate compounds and the like. Alternatively, it is also possible to partially react with these compounds, and the resulting partial reaction product can similarly be used as a raw material for an aqueous dispersion.

As the hydrophilic vinyl polymer to be blended into the above polyester resin, a polymer containing at least one type of functional group selected from sulfonic acid metal bases, carboxyl groups, and hydroxyl groups within a range that satisfies the following formulas (1) and (2) is used. Need 6
4) Even if polymers other than such polymers are used, the objects and effects of the present invention cannot be achieved.

1.0≦a+b+c≦20 −−−−−−−−■ Vinyl monomers used for introducing a sulfonic acid metal base into the hydrophilic vinyl polymer include Teha, styrene sulfonic acid,
Vinyltoluenesulfonic acid, vinylethylbenzenesulfonic acid, isopropenylbenzenesulfonic acid, 2-chlorostyrene M fonic acid, 2,4-dichlorostyrenesulfonic acid, 2-methy/l/ = 4-chlorostyrenesulfonic acid, vinyl Oxybenzenesulfonic acid, vinylsulfonic acid, (meth)allylsulfonic acid, sulfoethylmodic hasulfoprobyl ester of (meth)acrylic acid, 2-
Examples include metal salts such as acrylamide-2-methylpropanesulfonic acid, and types of metal salts include Li, Na5K, Mg
s” etc.-t6ru.

Examples of the carboxyl group-containing vinyl monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumate acid, -y unit acid, citraconic acid,
Examples of the hydroxyl group-containing vinyl monomer include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and glycerin 7-(meth)acrylate. Can be mentioned.

Among them, the hydrophilic vinyl polymer of the present invention is limited to satisfying the above formulas (1) and (2), and contains vinyl monomers other than the above vinyl monomers,
For example, vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; esters such as methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl, and 8-methoxyethyl M of (meth)acrylate; ethylene glycol di(methane acrylate); , unsaturated carboxylic acid esters such as polyethylene glycol di(meth)acrylate; acrylamides such as (meth)acrylamide, methylol acrylamide, butoxymethylol acrylamide; (unsaturated nitriles such as methane acrylonitrile) Allyl compounds such as glycidyl (methane acrylate, glycidyl crotonate, monoglycidyl maleate, vinyl glycidyl ether, allyl glycidyl ether, styrene, vinyl toluene, vinyl naphthalene, 1-tadiene, isoprene, hexene, etc.) Copolymerization of vinylsilanes such as dimethylvinylmethoxysilane, dimethylethylethoxysilane, methylvinyldimethoxysilane, methylvinyldimethoxysilane, r-methacryloxypropyltrimethoxysilane, r-methacryloxypropylmethyldimethoxysilane, etc. It may be something.

In addition, sulfonic acid metal bases are introduced by sulfonation of polymers, dicarboxyl groups are introduced by hydrolysis of (meth)acrylic esters, saponification of vinyl esters, and ring opening of epoxy groups. It may also be one in which a hydroxyl group has been introduced.

In order to more effectively achieve the objectives of the present invention, such as adjusting viscosity and improving stability and resolubility, a + b is applied to the above formula 0.
The range of +c is 1.6-14 mmoJ/f, the type of a added to the formula 0 is an aromatic sulfonic acid metal base, and the range of a is preferably 5 mmol A1 or less, particularly a water-soluble vinyl polymer.

As long as the requirements of the present invention are met, other vinyl monomers may be appropriately copolymerized.

Among them, as long as the predetermined vinyl monomer is contained within the range that satisfies the above formulas (1) and (2), there are no limitations on the manufacturing method of the hydrophilic vinyl polymer, but in the water-based plot, An industrial method is to carry out polymerization using a water-soluble redox initiator in which the equivalent ratio of reducing agent to oxidizing agent is within the range of LO to 1.9. Oxidizing agents include persulfates, hydrogen peroxide, permanganates, second metal salts, nitrites, peracetic acid, etc., and reducing agents include Rrl! Dan, biR salt, metasulfite,
And doroa fit #salt, first ijI! Examples include acid salts, iron salts, oxalic acid, silver nitrate, etc., especially combinations of persulfates and reducing sulfoxy compounds (and/or ferrous ions),
A redox initiator consisting of a combination of chlorate and a reducing sulfoxy compound is preferred.

In order to adjust the molecular weight of the hydrophilic vinyl polymer, there is no problem in coexisting a chain transfer agent such as carbon tetrachloride or mercaptans in the polymerization system as necessary. Although there is no restriction, within a practical molecular weight range, those with a small molecular weight, that is, those with a weight average molecular weight of 100,000 or less, preferably 80,000 or less, as determined by GPC (polystyrene standard), will achieve the purpose of the present invention. Desirable for the first time.

The amount of the hydrophilic vinyl polymer to be blended is determined as appropriate depending on the stability, water resistance/solvent resistance, resolubility, viscosity, etc. of the desired aqueous dispersion, but it is approximately 0.00% relative to the polyester resin. It is desirable to set the content within the range of 0.02 to 20% by weight, preferably O,OS to 15% by weight, and more preferably 0.1 to 10% by weight.

Although water is preferable as the dispersion line for producing an aqueous dispersion, the following water-soluble organic compounds may be added to the total weight of the dispersion unit in order to assist the dispersibility of the polyester resin in water. No. Such water-soluble organic compounds are 20
An organic compound with a C of 14 and a solubility in water of 201 or more, specifically aliphatic and alicyclic alcohols,
Examples include ether, ester, and ketone compounds. Specifically, for example, methanol, ethanol, n-glopanol, 1-glopanol, n-butanol, 1-
-hydric alcohols such as butanol, see-butanol, tert-butanol, glyco-1v such as ethylene glycol, propylene glycol, ethyl cellosolve, ethyl cellosolve, n-ethyl cellosolve, 8-methyl-8-methoxy 1-tanol, These include glycol derivatives such as n-1 tilcerone lupacetate, ethers such as dioxane, esters such as ethyl acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclooctanone, cyclodecanone, and isophorone, and tetrahydrofufun. Particularly preferred are n-butyl cellosolve, ethyl cellosolve, and isopropanol. These water-soluble organic compounds can be used alone or in combination of two or more. The boiling points of these water-soluble organic compounds are 60 to 200
It is necessary that the temperature be within the range of ℃. If the boiling point does not reach 606C, it is difficult to maintain a temperature sufficient to mix or dissolve the polyester resin in the organic compound. Furthermore, if the boiling point exceeds 200° C., the aqueous dispersion obtained will not dry quickly after being applied. Furthermore, when an amide or sulfonic acid ester compound is used as the water-soluble compound, the drying properties are poor and the storage stability of the aqueous dispersion is also poor.

The procedure for producing an aqueous dispersion is to first stir and disperse the polyester resin in a dispersion medium at a temperature of 40°C or higher, then mix the hydrophilic vinyl polymer, or stir and disperse both in the dispersion medium at the same time. Examples of such measures include:

The concentration of the aqueous dispersion is appropriately set depending on the purpose, use, etc., but the concentration of the polyester resin is generally 5 to 70%.
It is desirable to set it within the range of 10 to 60% by weight, preferably 10 to 60% by weight.

If it is outside this range, the viscosity of the aqueous dispersion will be too low or too high to be practical.

Among these, as the vinyl monomer used to further modify the polyester resin, the above-mentioned vinyl monomers and the like are appropriately used.

The aqueous dispersion of the present invention is used after its casing has been modified by polymerization of a vinyl monomer, and is further treated with one selected from the group of crosslinking agents, such as an amino resin, an epoxy compound, and an isocyanate compound. The above compounds can be used in combination.

Examples of amino resins include formaldehyde adducts such as urea, melamine, and benzoguanamine, as well as carbon numbers!
-6 alkylated products with alcohols can be mentioned. In addition, favorable effects can be achieved by using ciformalin in combination, if necessary.

Epoxy compounds include diglycidyl ether of bisphenol A and its oligomer, hydrogenated diglycidyl ether of bisphenol A and its oligomer, diglycidyl orunphthalate, digly V isophthalate, digly V terephthalate,
p-oxybenzoic acid glycidyl ester ether, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester
Dyl ester, adipic acid diglycidyl ester, sepacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, l,4-butanediol diglycidyl ether, 1,6-hexanesiol cyclidyl ether and polyalkylene glycol Diglycidyl ethers, trimellitic acid triglycidyl ester, Tricri V
Dyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl dimethylhydantoin, diglycidyl ethylene urea, diglycidyl propylene urea, glycerol polyglyphdylether, trimethylolethane polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol Examples include polyglycidyl ether, polyglyphdyl ether of a glycerol alkylene oxide adduct, and the like.

Furthermore, as isocyanate compounds, aromatic, aliphatic,
The aromatic aliphatic diincyanate and the polyisocyanate having a valence of 8 or more may be any of a resin, a low molecular compound, and a high molecular compound. For example, tetramethylene diisocyanate,
Eels such as hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, inphorone diisocyanate, isophorone diisocyanate octamer, propylene glycol, trimethylopropane, glycerin, Obtained by reacting low-molecular active hydrogen compounds such as sorbitol, ethylenediamine, monoethanolamine, jetanolamine, and triethanolamine, or high-molecular active hydrogen compounds such as various polyether polyols, polyester polyols, and polyamides. Examples include compounds containing terminal isocyanate groups.

The isocyanate compound may be a blocked incyanate. Examples of incyanate blocking agents include phenols such as phenol, thiophenol, methylthiophenol, ethylphenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, methanol, Alcohols such as ethanol, propatool, butanol, ethylene chlorohydrin, 1.8
-Halogen-substituted alcohols such as 1'chloro-2-propatol, 8th class 7/I/cols such as t-ftanol, t-pentanol, t-butanethiol, 6-cabroctam, δ- Valerofuctum, r-Putilooctum,
Examples include tscutams such as I-provirlactam, as well as aromatic amines, imides, acetylacetone,
Active methylene compounds such as acetoacetate and malonic acid ethyl ester, mercaptans, imines, ureas,
Also included are diaryl compounds, sodium bisulfite, and the like. The blocked isocyanate can be obtained by subjecting the above-mentioned isocyanate compound and an inocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

A curing agent or an accelerator can also be used in combination with these crosslinking agents. Methods for blending the crosslinking agent include (A) mixing it with the polyester resin, directly blending it into the aqueous dispersion, and further dissolving or dispersing it in advance in (B) a water-soluble organic compound or (C) a mixture with water. It can be selected arbitrarily depending on the type of crosslinking agent.

(Effects of the Invention) In the polyester resin aqueous dispersion of the present invention, the specific hydrophilic vinyl polymer wraps around the surface of the polyester resin dispersed particles, and the particles with a narrow structure are densified, and the particles have mutual interaction. It is thought that the tangles are also broken, and by this effect, it is possible to provide a dispersion with extremely low viscosity even at a high solids content of 80% by weight or more, and the type and amount of the hydrophilic vinyl polymer can be adjusted. By changing the dispersion, the viscosity can be adjusted to any desired value depending on the application without changing the solid content concentration, which is a noteworthy effect of the present invention.In addition, the dispersion of the present invention has a high stability. It has excellent resolubility and does not cause thickening, phase separation, or gelation when mixed with acrylic emulsion for the purpose of EL modification, and further improves water resistance and solvent resistance. Therefore, there is no substantial increase in viscosity even when vinyl monomers are polymerized or modified.
These points are also advantages of the present invention.

The aqueous dispersion of the present invention is used in the fields of paints, inks, coating agents, and treatment agents for products, paper, etc., and exhibits unprecedented water resistance and weather resistance. Pigments, dyes, various additives, etc. can be added to the aqueous dispersion of the present invention.

(Example) The present invention will be explained in more detail with reference to Examples below. It is not limited to the examples.

In the examples, parts simply indicate parts by weight.

Evaluation of various properties was performed according to the following methods.

1. Molecular weight It was measured using a molecular weight measuring device (Hitachi, Ltd. 1-Hyo 151). I2, softening point and crystal melting point Fully automatic melting point measuring device (PRrLh
'R company 931 MODEL FP-1) Use L [I
It was fixed at 1.

8. Particle size of dispersion Measured using a grindmeter and an optical microscope.

4. Viscosity Measured using a B-type viscometer at 25°.

Production of polyester resin 95 parts of 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 trioxide were placed in a reaction vessel at 140°C to 220°C.
The transesterification reaction was carried out for 8 hours. Then 6
- Adding 6.0 parts of sodium sulfoisophthalic acid,
After carrying out the esterification reaction at 20 to 260°C for 1 hour, the esterification reaction was carried out at 240 to 270'C under reduced pressure (10 to 0.2 f
A polyester resin (A) with a molecular weight of 19,500 and a softening point of 160'
-1) was obtained.

Polyester resins (A-2) to (A-8) were obtained in exactly the same manner except that the raw materials shown in Table 1 were used. Their characteristic values were as shown in Table 1.

Table 1 Determined from Torr measurement rc. 8 parts of ammonium persulfate was added to 100 parts of the monomer shown in Table 2.
parts, acidic sodium sulfite L, 8 parts, ferrous chloride 0.000
Add 16 parts of deionized water and 400 parts of deionized water, and add 70 parts of
'c for 1 hour to obtain a hydrophilic vinyl polymer (B-1
~B-18) was obtained. The catalyst was added all at once after the temperature was raised.

Their characteristic values are also listed in Table 2.

Example 1 860 parts of polyester resin (A-1) and 100 parts of n-butyl cellosolve were charged in a container and heated at 150°C to 170°C.
After stirring at ℃ for about 8 hours to obtain a homogeneous and viscous melt, 560 parts of water was gradually added while stirring vigorously, and after about 1 hour, a homogeneous pale bluish-white dispersion (C-1) was obtained. Obtained.

The particle size of the resin in the resulting dispersion was less than lμ, and the viscosity of the dispersion was 5,000 cps.

A hydrophilic vinyl polymer (B-1-B-
18) in the proportions shown in Table 8 to prepare an aqueous dispersion (D-
1 to D-18) were obtained. The measurement results of viscosity (eP4) are also listed in Table 8.

Table 8 shows that by blending a small amount of the hydrophilic vinyl polymer of the present invention, it is possible to provide an aqueous polyester resin dispersion with a low viscosity even at a high solids content. It is clear that an aqueous dispersion of any viscosity can be provided by adjusting the type and blending amount.

Example 2 A dispersion (
A dispersion (C-8) was prepared in the same manner as in Example 1 except that C-27 was replaced with 260 parts of polyester resin (A-8) and 660 parts of water.

The viscosity of dispersion (C-2) and (C-8) is 6
．． 000 cps and 110.000 cps.

A hydrophilic vinyl polymer (
B-63 was blended in the proportions shown in Table 4 to make an aqueous dispersion (D
-14 to D-16) were obtained.

The measurement results of viscosity (cps) are also listed in Table 4.

No. table

Claims (1)

[Scope of Claims] A polyester resin containing 0.5 to 10 mol% of an aromatic dicarboxylic acid containing a sulfonic acid metal group as a polycarboxylic acid component, at least one type selected from a sulfonic acid metal group, a carboxyl group, and a hydroxyl group. The functional groups are shown below (
An aqueous polyester resin dispersion containing a hydrophilic vinyl polymer in a range that satisfies formulas 1) and (2). 1.0≦a+b+c≦20……(1) a≦7……(2) Here, a, b, and c each represent a sulfonic acid metal base, a carboxyl group, and a carboxyl group contained in the hydrophilic vinyl polymer. The amount of hydroxyl groups (mmol/g) is shown.