JPH0368063B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aqueous polyester dispersions.
More specifically, the present invention relates to an aqueous dispersion of polyester with a minute particle size that can form a film with excellent water resistance and heat resistance. Organic solvents have traditionally been used in large quantities in the fields of paints, inks, coating agents, adhesives, and various treatment agents for textile products, paper, etc., but in recent years organic solvents have been used from the perspective of saving petroleum resources and preventing environmental pollution. is becoming extremely difficult to use. Therefore, various methods such as (1) high solid type,
(2) non-aqueous dispersion type, (3) aqueous dispersion type, (4) emulsion type, and (5) solvent-free type, etc., have been proposed and many have already been implemented. Among these, the aqueous dispersion type is considered the most versatile and promising because of its ease of handling. On the other hand, many of the resins currently used are hydrophobic, and a major challenge is how to disperse them in water or make them water-soluble. Furthermore, it is also an important issue to impart water resistance and heat resistance to a film formed from a resin that has been imparted with an affinity for water by some method. These technical solutions are common to any resin, and polyester is no exception. Already, methods for dispersing polyester in water or making it aqueous include copolymerizing hydrophilic raw materials, such as copolymerizing raw materials containing sulfonic acid metal bases, polyalkylene glycols, aliphatic dicarboxylic acids, etc. alone or in combination. Methods are known. However, in either method, it is necessary to use a large amount of the above-mentioned hydrophilic raw materials in order to impart excellent water solubility or dispersibility, and the resulting film has very poor water resistance and heat resistance. becomes. For example, Special Publication No. 40873, Publication No. 40873, Special Publication No. 43-40873,
Publication No. 9076 describes the use of a large amount of a sulfonic acid metal base-containing compound, a polyalkylene ether glycol nitrogen-containing compound, or an aliphatic dicarboxylic acid in order to sufficiently dissipate it in water. It is easy to imagine that such polyesters have poor water resistance and heat resistance. That is, the fact that it can be sufficiently dissipated in water means that the water resistance of the film formed after drying is poor. in this case,
When the film comes into contact with water, not only does the adhesion decrease, but also a change in hue occurs, resulting in a loss of paint, ink,
Cannot withstand the use of coating agents, adhesives, etc. In this way, a film cannot be said to be of practical use unless it overcomes the contradictory problems of imparting properties such as imparting hydrophilicity and imparting water resistance and heat resistance. The present inventors have continued to conduct intensive research on aqueous polyester dispersions with excellent water resistance, heat resistance, weather resistance, etc., and have already proposed a portion of them in Japanese Patent Application No. 167002/1983. However, paints, adhesives,
Film performance required for ink or coating agent applications is becoming increasingly demanding. For paint, coating agent, and ink applications, performance such as coating film hardness, stain resistance, weather resistance, or boiling water resistance is required, and for adhesive applications, high adhesion, especially improved adhesion at high temperatures, is required. Based on conventional knowledge, the present inventors conducted research to obtain an aqueous dispersion with even higher water resistance and heat resistance. It has been found that when the compound is contained, it is uniformly dispersed in water or a mixture of water and an organic compound that is compatible with water. Furthermore, the present inventors have discovered that by applying and drying the resulting aqueous dispersion and then irradiating it with actinic rays, the film is crosslinked, resulting in a high degree of water resistance and heat resistance. That is, in the present invention, in the polycarboxylic acid component (A), 0.5 of the dicarboxylic acid containing sulfonic acid metal base is
~20 mol%, and 0.01 to 50 mol% of photocrosslinkable dicarboxylic acid or photocrosslinkable hydroxymonocarboxylic acid to the polycarboxylic acid component and/or 0.01 to 50 mol% of photocrosslinkable glycol to the glycol component. polyester containing mol%, (B) a water-soluble organic compound with a boiling point of 70 to 200°C, and (C) water, and (A), (B) and (C) are of formulas (1), (2) and This is an aqueous dispersion characterized by satisfying the blending ratio (3). Formula (1) (A) + (B) + (C) = 100 (weight ratio) Formula (2)
(A)/(B)/(C)=5-70/0-50/95/20 (weight ratio) Formula (3) 0≦(B)/(C)≦0.66 (weight ratio) Polyester of the present invention consists of a polycarboxylic acid component mainly consisting of a dicarboxylic acid component and a polyol component mainly consisting of a glycol component. In the polyester of the present invention, 0.5 to 20 mol % of the polycarboxylic acid component is dicarboxylic acid containing a metal sulfonic acid group. Examples of sulfonic acid metal base-containing dicarboxylic acids include sulfoterephthalic acid, 5-sulfoisophthalic acid,
Metal salts of aromatic dicarboxylic acids such as 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5[4-sulfophenoxy]isophthalic acid, aliphatic dicarboxylic acids such as sulfosuccinic acid, and ester formation thereof sexual derivatives can be mentioned. Metal salts include Li, Na, K, Mg,
Examples include salts such as Ca, Cu, and Fe. Particularly preferred are 5-sodium sulfoisophthalic acid and its ester-forming derivatives. Furthermore, the polyester of the present invention contains a photocrosslinkable dicarboxylic acid, a photocrosslinkable hydroxymonocarboxylic acid, and/or a photocrosslinkable glycol as an essential component. Examples of the photocrosslinkable dicarboxylic acid, hydroxymonocarboxylic acid, or glycol include compounds represented by the following general formulas () to (). General formula (): (In the formula, X and Y are carboxyl groups or hydroxyl groups, and X and Y may be the same or different. R ₁ and R ₂ are monovalent organic groups, preferably having 1 or more carbon atoms, Usually 1 to 10 aliphatic, aromatic, or alicyclic monovalent residues, which may be the same or different. R ₃ and R ₄ have 1 or more carbon atoms,
Usually 1 to 20 aliphatic, aromatic, or alicyclic divalent residues, which may contain ether bonds, ester bonds, amide bonds, imide bonds, etc., and R ₃ and R ₄ may be the same or different.
k and 1 are integers from 0 to 3. ) General formula (): (In the formula, R ₃ and R ₄ are methoxy group, chlorine, fluorine, -
(CH ₂ ) x-OH, -O- (CH ₂ ) ₂ -OH or -
(CH ₂ )xCOOR, where x is 0 to 10, R
is hydrogen or a lower alkyl group. At least one of each of R ₃ and R ₄ is the above-mentioned substituent other than methoxy group, chlorine, or fluorine, and m and n are integers of 1 to 5. ) General formula (): (In the formula, R ₅ and R ₆ are methoxy group, chlorine, fluorine, -
( _CH2 )x-OH, -O-( _CH2 )x-OH or -
(CH ₂ )xCOOR, where x is 0 to 10, R
is hydrogen or a lower alkyl group. At least one of each of R ₅ and R ₆ is the above-mentioned substituent other than methoxy group, chlorine, or fluorine, and p and q are integers of 1 to 5. ) The compound represented by the general formula () contains benzophenonetetracarboxylic acid and/or its derivatives (preferably acid anhydrides) with or without substituents in the aromatic nucleus and one primary amino acid in the molecule. and a compound having at least one ester-forming functional group. Compounds having one primary amino group and at least one ester-forming functional group in the molecule have a carbon atom number of 2
~10 alkanolamines, such as monoethanolamine, propanolamine, butanolamine, etc., or amino acids having 2 to 10 carbon atoms, such as glycine, β-alanine, γ-amino-n-
Examples include butyric acid, p-aminobenzoic acid, m-aminobenzoic acid, and the like. Specifically, the compound represented by the general formula () is N,N'-bis(β-hydroxyethyl)
Benzophenonetetracarboxylic acid imide, N,
Examples include N'-bis(β-carboxyethyl)benzophenonetetracarboxylic imide, N-(β-hydroxyethyl)-N'-(β-carboxyethyl)benzophenonetetracarboxylic imide, and the like. Specifically, the compound represented by the general formula () is 4,4'-dicarboxybenzophenone,
Examples include 4,4'-dihydroxybenzophenone and 4-carboxy-4'-hydroxybenzophenone. Specifically, the compound represented by the general formula () is 4,4'-dicarboxynaphthyl ketone,
Examples include 4,4'-dihydroxydinaphthyl ketone and 4-carboxy-4'-hydroxydinaphthyl ketone. Other dicarboxylic acids, glycols, lactones or oxycarboxylic acids constituting the polyester of the present invention include the following. Examples of other dicarboxylic acids include terephthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, and diphenoxyethane dicarboxylic acid; aliphatic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid; Examples include dicarboxylic acids, but dicarboxylic acids containing an imide ring in the molecule can also be used. Other glycols include ethylene glycol,
trimethylene glycol, 1,2-propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol (molecular weight 10,000 or less), polytetramethylene glycol (molecular weight 10,000 or less)
aliphatic glycols such as 1,4-cycloxanediol, 1,4-cyclohexanedimethanol, resorcinol, hydroquinone, 2,2-bis-(4,4'-hydroxyphenyl)propane, etc. Examples thereof include aromatic diols, and the aromatic diols may be further added with ethylene oxide and/or propylene oxide. Examples of lactones or other oxycarboxylic acids include .beta.-propiolactone, .gamma.-butyrolactone, .epsilon.-caprylactone, m- or p-hydroxybenzoic acid, N-hydroxyethyl trimellitimide, and the like. Further, the polyester used in the present invention can contain a trifunctional or higher functional polycarboxylic acid and/or a polyol within a performance-permissible range. Trimellitic acid, pyrimellitic acid, butanetetracarboxylic acid, etc. can be mentioned as trifunctional or higher functional polycarboxylic acids, and polyols can be mentioned, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. Within the permissible range, preferably 10 mol % or less based on the total polycarboxylic acid and/or total polyol. The polyester of the present invention is prepared by using a dicarboxylic acid containing a sulfonic acid metal group, a photocrosslinkable dicarboxylic acid, a photocrosslinkable hydroxymonocarboxylic acid and/or a photocrosslinkable glycol, and another dicarboxylic acid and/or another glycol, etc. manufactured by any method. For raw materials such as dicarboxylic acid, hydroxycarboxylic acid, or glycol, ester-forming derivatives thereof may be used. For example, a dicarboxylic acid lower alkyl ester and an alkylene glycol are heated together with a catalyst to form a glycol ester, which is further heated at a high temperature and, if necessary, under a high vacuum. The photocrosslinkable compound can be added and reacted at any stage of the above reaction. However, when the photocrosslinkable compound contains a carboxyl group, it is preferably added after the transesterification reaction between the carboxylic acid dialkyl ester and the alkylene glycol is completed. Alternatively, instead of using the photocrosslinkable compound, a mixture or addition compound of benzophenonetetracarboxylic acid, which is a raw material thereof, and a compound having one primary amino group and at least one ester-forming functional group in the molecule. It is also possible to react an amic acid which is , during the polymerization process. The polyester (polyol) used for producing the polyester of the present invention contains 0.01 to 50 mol% of the photocrosslinkable dicarboxylic acid or hydroxycarboxylic acid based on the polycarboxylic acid component. The photocrosslinkable glycol is contained in an amount of 0.01 to 50 mol% based on the polyol component. If the amount of photocrosslinkable dicarboxylic acid, hydroxycarboxylic acid, or glycol is less than 0.01 mol% based on the polycarboxylic acid or polyol component, no crosslinking or high Molecular weighting is difficult to occur, and therefore the performance of the film, such as water resistance and heat resistance, is not sufficient. On the other hand, if it exceeds 50 mol%,
Films produced by light irradiation lack flexibility and are not suitable for applications such as paints, adhesives, and coatings. Preferably it is 0.1-20 mol%, particularly preferably 0.5-10 mol%. The polyester (polyol) used for producing the polyester of the present invention contains 0.5 to 20 mol %, preferably 1 to 10 mol % of the dicarboxylic acid containing a sulfonic acid metal group based on the polycarboxylic acid. 0.5 mol% dicarboxylic acid containing sulfonic acid metal base
If it is less than 20 mol %, it will be difficult to uniformly disperse it in a medium mainly composed of water, and if it is more than 20 mol %, the resulting film will have poor water resistance. As other dicarboxylic acids in the polyester (polyol) used in the production of the polyester of the present invention, the above-mentioned compounds can be arbitrarily selected and used, but aromatic dicarboxylic acids are preferably used.
It is desirable to contain 40 mol% or more. Furthermore, crystalline polyesters, such as polyesters containing 80 mol% or more of ethylene terephthalate units or tetramethylene terephthalate units, cannot be used alone because they are difficult to disperse in water. However, by blending such crystalline polyesters with other non-crystalline polyesters, water dispersion becomes possible and there is no practical problem. The molecular weight of the polyester of the present invention is from 2000 to
100,000, and can be dissolved in water alone or in the coexistence of an organic compound compatible with water, or a good aqueous dispersion can be obtained. However, the drying properties of the resulting film,
Considering water resistance, it is preferable to use it as an aqueous dispersion rather than as an aqueous solution. The water-soluble organic compound used in the present invention is an organic compound having a solubility in water of 20 g or more at 20°C, and specific examples thereof include aliphatic and alicyclic alcohols, ethers, esters, and ketone compounds. It will be done. Specifically, for example, ethanol,
n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol,
Monohydric alcohols such as tert-butanol, glycols such as ethylene glycol and propylene glycol, methyl cellosolve, ethyl cellosolve,
Isopropyl cellosolve, n-butyl cellosolve, tert-butyl cellosolve, 3-methyl-3-
These include glycol derivatives such as methoxybutanol and n-butyl cellosolve acetate, ethers such as dioxane, esters such as ethyl acetate, and ketones such as methyl ethyl ketone, cyclohexanone, cyclooctanone, cyclodecanone, and isophorone. Particularly preferred are n-butyl cellosolve, tert-butyl cellosolve, ethyl cellosolve, isopropyl cellosolve, isopropanol and the like. These water-soluble organic compounds can be used alone or in combination of two or more. The boiling point of these water-soluble organic compounds needs to be in the range of 60 to 200°C. If the boiling point does not reach 60°C, it is difficult to maintain a temperature sufficient to mix or dissolve the polyester 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 aqueous dispersion in the present invention includes (A) polyester and
(B) A water-soluble organic compound is mixed in advance at 50 to 200°C, and (C) water is added to this, or a mixture of (A) and (B) is added to water and stirred at 50 to 120°C. Manufactured by. Alternatively, (A) polyester is added to a mixed solution of (C) water and (B) a water-soluble organic compound,
It can also be produced by stirring and dispersing at 60 to 100°C. Alternatively, (A) can be directly mixed into warm water at 50 to 100°C to dissolve or disperse it. The aqueous polyester dispersion of the present invention can be used as such, but in order to improve water resistance and heat resistance, it is desirable to crosslink and/or increase the molecular weight by light irradiation after forming a film.
Light irradiation can be performed by a method known per se,
For example, a high-pressure mercury lamp, a low-pressure mercury lamp, a Canon lamp, sunlight, etc. are used as a light source, and ultraviolet rays with a wavelength of 200 mμ to 400 mμ (especially preferably
310-400 mμ) is preferred, but other electromagnetic waves can be used as well. There are no particular limitations on the conditions for light irradiation in the present invention, ie, irradiation time, irradiation atmosphere, etc. The irradiation time depends on the physical properties required for the product.
It can be set arbitrarily between 0.1 seconds and 30 minutes.
Even in an oxygen atmosphere, the crosslinking and/or
Or the polymerization reaction is not inhibited. In terms of irradiation efficiency, it is higher than the glass transition temperature of the film before irradiation.
Preferably, the reaction is carried out at a temperature below the melting point. The irradiation amount is usually about 10-500w/m ² , preferably 50-500w/m 2
It is 300w/ ^m2 . The aqueous dispersion of the present invention can be used as it is, and excellent water resistance and heat resistance can be obtained by irradiation with light. The above compounds can be used in combination. Examples of amino resins include formaldehyde adducts of urea, melamine, and benzoguanamine, and alkylated products with alcohols having 1 to 6 carbon atoms. Further, if necessary, a favorable 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 ester ether, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacate acid diglycidyl ester, ethylene Glycol diglycidyl ether, propylene glycol diglycidyl ester, 1,4-
Butanediol diglycidyl ether, 1,6-
Hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyldimethylhydantoin, diglycidyl ethylene urea, diglycidyl propylene urea, glycerol Examples include polyglycidyl ether, trimethylolethane polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and polyglycidyl ether of a glycerol alkylene oxide adduct. Furthermore, as isocyanate compounds, aromatic,
There are aliphatic and araliphatic isocyanates, and polyisocyanates having a valence of 3 or more, and they may be either low-molecular compounds or high-molecular compounds. Isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, isophorone diisocyanate trimer,
Alternatively, an excess amount of these isocyanate compounds and a low-molecular active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or various polyether polyols. Examples include terminal isocyanate group-containing compounds obtained by reacting polymer active hydrogen compounds such as polyester polyols, polyamides, and the like. The isocyanate compound may be a blocked isocyanate. Examples of isocyanate 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, and ethanol. , alcohols such as propanol, butanol, halogen-substituted alcohols such as ethylene chlorohydrin, 1,8-dichloro-2-propanol, t-butanol, t-butanol,
-Tertiary alcohols such as pentanol and t-butanethiol, lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propyllactam, as well as aromatic amines and imides. , active methylene compounds such as acetylacetone, acetoacetate, and ethyl malonate, mercaptans, imines, ureas, diaryl compounds, and sodium bisulfite. The blocked isocyanate can be obtained by subjecting the above-mentioned isocyanate compound and an isocyanate 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 polyester or polyurethane resin, directly blending it into an aqueous dispersion, and dissolving or dispersing it in advance in (B) a water-soluble organic compound or (C) a mixture with water. There are methods, etc.
It can be arbitrarily selected depending on the type of crosslinking agent. The aqueous dispersion of the present invention is used in the fields of paints, inks, coating agents, adhesives, and treatment agents for textile products, paper, etc., and exhibits unprecedented water resistance and heat resistance. Pigments, dyes, various additives, etc. can be added to the aqueous dispersion of the present invention. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the examples, parts simply indicate parts by weight. Evaluation of various properties was performed according to the following methods. (1) Molecular weight Molecular weight measuring device (Hitachi 115
Measurements were made using a (2) Softening point Fully automatic melting point measuring device (METTLER)
Measurement was carried out using MODEL FP-1) (manufactured by Co., Ltd.). (3) Particle size of aqueous dispersion Measured using a grindmeter and an optical microscope. (4) Adhesion Compliant with ASTMD-3359. (5) Pencil hardness The surface of the film was measured according to JIS K-5400 using a high-grade pencil specified in JIS S-6006. (6) Gloss 60° reflectance was measured. (7) Erichsen value Compliant with JIS Z-2247. (8) Water resistance Conforms to JIS5400. (9) Stain resistance Oil-based ink was applied to a surface of 0.5 cm x 2 cm, left at 20°C for one day and night, and then wiped off with gauze impregnated with methanol to measure the degree of stain. (10) Peeling adhesive strength The adhesive strength was measured by peeling at 90°C using an Instron type peeling tester. (11) Heat resistance Evaluated by peel adhesion strength at 50℃. Production example 1 679 parts of dimethyl terephthalate, 262 parts of dimethyl isofretate, 44 parts of dimethyl 5-sodium sulfoisophthalate, 512 parts of ethylene glycol,
286 parts of neopentyl glycol, 0.44 parts of zinc acetate,
0.04 part of sodium acetate and 0.43 part of antimony trioxide were placed in a reaction vessel and the reaction was carried out at 140°C to 220°C for 4 hours. Next, 102 parts of N,N'-bis(β-hydroxyethyl)benzophenonetetracarboxylic acid imide (hereinafter abbreviated as HEBTI) was added, and 220 parts of
After carrying out the esterification reaction at ~260°C for 1 hour,
The pressure was gradually reduced to 270°C and a polycondensation reaction was carried out for 1 hour under reduced pressure of 0.05 to 0.2 mmHg to obtain polyester (A-1) having a molecular weight of 18,000 and a softening point of 154°C. Polyester (A-
A compositional analysis of 1) revealed that 70 mol% of terephthalic acid, 27 mol% of isophthalic acid, 3 mol% of 5-sodium sulfoisophthalic acid, 5 mol% of HEBTI,
The contents were 63 mol% ethylene glycol and 32 mol% neopentyl glycol. Polyesters (A-2) to (A-9) shown in Table 1 were obtained in the same manner.

【table】

[Table] Example 1 300 parts of polyester (A-1) and 140 parts of n-butyl cellosolve were placed in a container and heated to 150°C to 170°C.
After stirring for about 3 hours to obtain a homogeneous and viscous melt, 560 parts of water was gradually added while stirring vigorously.
After about 1 hour, a uniform pale blue-white aqueous dispersion (C-
1) was obtained. The particle size of the obtained aqueous dispersion is 1μ or less,
No change in appearance was observed even after being left at -5°C for 30 days. The obtained aqueous dispersion was coated on a 125μ polyethylene terephthalate film using a bar coater #26 to a film thickness of 5 to 6μ, and then heated at 100℃.
Dry for 20 minutes. Next, irradiation was performed for 5 minutes with a 450W high-pressure mercury lamp from a position 10cm above the coated surface.
The resulting film has excellent adhesion and has a pencil hardness
3H, and had excellent water resistance without whitening even after being immersed in warm water at 60°C for one day and night. Example 2 An aqueous dispersion (C-2) was obtained in the same manner as in Example 1 using the formulation shown in Table 3. Table 3 shows the performance of the aqueous dispersion obtained and the performance of the film formed on the 125μ polyethylene terephthalate film. Comparative Examples 1 to 3 Aqueous dispersions (C-3) to (C-5) were obtained in the same manner as in Example 1 using the formulations shown in Table 3.
Table 3 shows the performance of the aqueous dispersion obtained and the performance of the film formed on the 125μ polyethylene terephthalate film.

[Table] Example 6 Polyester (A
-2) After dissolving 300 parts in 70 parts of cyclohexanone and 70 parts of n-butyl cellosolve, 560 parts of water was gradually added to obtain an aqueous dispersion (C-6). The resulting aqueous dispersion had a particle size of 1 μm or less, and no change in appearance was observed even after being left at −5° C. for 30 days. To 100 parts of the obtained aqueous dispersion (C-6) were added 10 parts of Sumimaru M-50W [manufactured by Sumitomo Chemical Co., Ltd.] and XF-
0.5 part of a 50% by weight ethanol solution of 3913 [manufactured by Toshiba Silicone Corporation] and titanium oxide [manufactured by Ishihara Sangyo Corporation]
R-930 ethylene glycol dispersion (solid content 50
After adding 20 parts (% by weight), it was mixed uniformly. The obtained white paint was applied onto a 0.3 mm thick galvanized steel plate using bar coater #36 to a film thickness of about 15 μm, dried at 100°C for 10 minutes, and then at 280°C for 2 minutes. Then, irradiation was performed for 10 minutes from a height of 10 cm using a 450 W high-pressure mercury lamp. The resulting coating has an excellent appearance, pencil hardness 2H, adhesion 100/100, and gloss.
87, had an Erichsen value of 5 mm or more, and had excellent stain resistance. Example 3 Aqueous dispersion (C-2) was coated onto a 125μ polyethylene terephthalate film using bar coater #36 to a film thickness of 15μ, dried at 100°C for 20 minutes, and then laminated with another 125μ polyethylene terephthalate film. ℃, 1Kg/ ^cm2 under load 2
Gluing was carried out for minutes. Then on polyester film
Irradiation was performed for 10 minutes with a 450W high-pressure mercury lamp from a distance of 10cm. The resulting adhesive film was peeled off at 20° C. and 60° C. using an Instron tensile tester to measure its adhesive strength. The measurement results are shown in Table 4. Comparative Example 4 Lamination was carried out in the same manner as in Example 3 using an aqueous dispersion (C-5), and the peel adhesion strength was measured at 20° C. and 60° C. The results are shown in Table 4.

【table】

Claims (1)

[Scope of Claims] 1 (A) Of the polycarboxylic acid components, it contains 0.5 to 20 mol% of a dicarboxylic acid containing a sulfonic acid metal base, and a photocrosslinkable dicarboxylic acid or a photocrosslinkable hydroxymonocarboxylic acid is added to the polycarboxylic acid component. A polyester containing 0.01 to 50 mol% based on the acid component and/or 0.01 to 50 mol% photocrosslinkable glycol based on the glycol component, (B) a water-soluble organic compound with a boiling point of 70 to 200°C, and (C) Contains water, and (A), (B)
and (C) satisfy the compounding ratios of formulas (1), (2), and (3). Formula (1) (A) + (B) + (C) = 100 (weight ratio) Formula (2)
(A)/(B)/(C)=5~70/0~50/95~20 (weight ratio) Formula (3) 0≦(B)/(C)≦0.66 (weight ratio)