JP2000313793A - Aqueous dispersion of polyester resin and coating film formed product made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous dispersion capable of forming coating films excellent in water resistance and chemical resistance (in particular, alcohol resistance), and to obtain such a coating film formed product by using the above aqueous dispersion. SOLUTION: This aqueous dispersion of polyester resin is obtained by formulating the components A to C as described below: (A) a polyester resin composed of polybasic acid component and polyhydric alcohol component, having an acid value of 8-40 mgKOH/g, glass transition temperature of >=40 deg.C or number- average molecular weight of >=9,000, (B) a basic compound, and (C) an organic solvent at 0.5-50 wt.% based on this aqueous dispersion, selected from ketones, alcohols and glycol derivatives, and having a boiling point of <=150 deg.C; wherein the polyester resin microparticles are homogeneously dispersed in an aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of a polyester resin and a polyester resin film-forming product useful as a binder component for various coating agents such as an adhesive, an ink or a film coating agent, a fiber treatment agent, and a paper coating agent. It is about.

[0002]

2. Description of the Related Art High molecular weight polyester resins (so-called oil-free alkyd resins) composed of a polybasic acid component and a polyhydric alcohol component are used as fibers, films and various molding materials. Also, in the fields of paints, inks, adhesives, coatings, etc., it shows good pigment dispersibility, and the formed film has good workability, chemical resistance, weather resistance, adhesion to various substrates, etc. Because it ’s good,
It is used in large quantities as various binder components. In such a high molecular weight polyester resin, when the polybasic acid component contains an aromatic polybasic acid, particularly a terephthalic acid component, without sacrificing other physical properties of the film formed from this resin, It is well known that processability, water resistance, chemical resistance, and weather resistance can be improved. However, in the polyester resin, the aromatic polybasic acid occupying the entire acid component constituting the polyester resin,
In particular, as the proportion of the terephthalic acid component increases, it cannot be stably dissolved in a general-purpose organic solvent at a high concentration, so that it cannot be prepared in a liquid state, which significantly restricts the use of such a resin. Was causing it. Therefore, the development of a "liquefaction" technique at a high concentration of such a resin has been desired for many years.

On the other hand, from the viewpoints of recent environmental protection, resource saving, regulation of dangerous substances by the Fire Service Law, and improvement of workplace environment, "liquefaction" of various resins with an organic solvent is called "liquefaction" with an aqueous medium, There is an active movement to replace water.
Such a situation is the same for the polyester resin, but the aromatic polybasic acid as the acid component, especially a high molecular weight polyester resin containing a large amount of terephthalic acid, not only forms a coating having excellent performance, Since such a resin skeleton is excellent in hydrolysis resistance, it is expected that the resin skeleton is also excellent in storage stability when it is made aqueous.

[0004] In order to cope with such a situation, the present inventors have previously described that if the polyester resin has a specific amount of acid value,
Even if this is subjected to aqueous treatment in the form of pellets to granules without liquefaction, the amphiphilic organic compound (organic solvent) and the basic compound having a plasticizing ability for the polyester resin are used. Glass transition temperature of polyester resin or 6
It has been found that if the mixture is heated to a temperature higher than 0 ° C. or higher and is stirred under a predetermined condition, aqueous conversion proceeds at a surprising speed. Then, the particle size distribution of the resin fine particles in the obtained aqueous dispersion of the polyester resin is optimized, and the molecular weight distribution of the polyester resin is further controlled, or a compound having a specific protective colloid action at the time of aqueous conversion is extremely reduced. It has also been found that, when used in a small amount, the storage stability of the aqueous dispersion is remarkably improved, and that a film formed by using the aqueous dispersion exhibits the inherently excellent performance of the polyester resin. JP-A-9-296100).

[0005]

However, when the polyester resin aqueous dispersion is used as various coating agents such as an adhesive, an ink or a film coating agent, a fiber treatment agent, a paper coating agent, a curing agent is used. Not used together, and at low temperatures
In many cases, only a short-time drying is performed. In such a case, even with the above-mentioned aqueous dispersion of the prior application, the water resistance and chemical resistance of the coating are not necessarily sufficient,
In particular, when used as a binder component for inks and various coating agents, the resulting images and coatings sometimes have insufficient alcohol resistance. Therefore, an object of the present invention is to
Provided is an aqueous polyester resin dispersion capable of forming a film having excellent water resistance and chemical resistance (particularly, alcohol resistance) without impairing the merits of the above-mentioned prior invention at all, and a film formed product thereof. It is in.

[0006]

Means for Solving the Problems The present inventors have conducted further detailed studies on the prior invention, and as a result, when the molecular weight or the glass transition temperature of the polyester resin is increased to a certain value or higher, the alcohol resistance of the coating film is reduced. Is improved,
Further, at the time of drying when forming a film, azeotropically azeotropic water and organic solvent contained in the polyester resin aqueous dispersion, to significantly reduce the amount of water and organic solvent remaining in the film after drying. As a result, the water resistance and chemical resistance of the film were successfully improved, and the present invention was achieved.

That is, the gist of the present invention is, first, a polyester characterized by comprising the following components (A) to (C), and fine particles of a polyester resin being uniformly dispersed in an aqueous medium. It is a resin aqueous dispersion. (A) It is composed of a polybasic acid component and a polyhydric alcohol component, has an acid value of 8 to 40 mgKOH / g, has a glass transition temperature of 40 ° C. or more, or has a number average molecular weight of 9.0.
Polyester resin having a value of 00 or more. (B) Basic compound (C) 0.5 to 50 based on aqueous dispersion of polyester resin
% By weight of an organic solvent having a boiling point of 150 ° C. or lower selected from ketones, alcohols and glycol derivatives.

[0008] Second, a coating obtained from the above aqueous dispersion of polyester resin and having a thermal weight loss rate of 5% or less when subjected to a heat treatment in an atmosphere of 110 ° C. for 30 minutes. It is a formation.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The aqueous polyester resin dispersion of the present invention has the above (A) to
(C) An aqueous liquid material containing the component, which is suitable for obtaining a polyester resin film (hereinafter, referred to as a film-formed product) obtained by forming a film using a method such as coating and drying the film. It is a polyester resin aqueous dispersion. First, each component blended in the aqueous polyester resin dispersion of the present invention will be described. [Component (A)] The polyester resin in the present invention is composed of a polybasic acid component and a polyhydric alcohol component, and does not inherently disperse or dissolve in water. Further, it contains a carboxyl group as a hydrophilic group when forming an aqueous dispersion.

The polyester resin of the present invention can be synthesized using a polybasic acid and a polyhydric alcohol.
Examples of such polybasic acids include aromatic polybasic acids, aliphatic polybasic acids, and alicyclic polybasic acids. In specific compounds, aromatic polybasic acids include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as biphenyldicarboxylic acid, and aliphatic polybasic acids include oxalic acid,
(Anhydrous) Saturated dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane diacid, eicosane diacid, hydrogenated dimer acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, unsaturated aliphatic dicarboxylic acids such as dimer acid, and the like, as alicyclic polybasic acids,
1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, 2,2
Examples include alicyclic dicarboxylic acids such as 5-norbornene dicarboxylic acid, tetrahydrophthalic acid, and tetrahydrophthalic anhydride. In addition, a small amount of 5-sodium sulfoisophthalic acid or 5-hydroxyisophthalic acid can be used as needed as long as the water resistance of the resin is not impaired.

Among the above-mentioned polybasic acids, it is preferable to use an aromatic polybasic acid, and the ratio of the aromatic polybasic acid component to all the acid components constituting the polyester resin is 50 mol% or more. Is the hardness of the film formation,
It is preferable in terms of improving chemical resistance and water resistance, and more preferably 70 mol% or more, in order to increase the hydrolysis resistance of the resin and improve the storage stability of the aqueous dispersion.
Furthermore, the workability, water resistance, chemical resistance, weather resistance, etc. can be improved while balancing with other performances of the film-formed product. It is particularly preferred that 65 mol% or more is a terephthalic acid component.

Further, polyhydric alcohols include those having 2 carbon atoms.
And aliphatic glycols having 6 to 12 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, and ether bond-containing glycols. In a specific compound, as the aliphatic glycol having 2 to 10 carbon atoms, ethylene glycol, 1,2-
Propylene glycol, 1,3-propanediol,
1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-
1,5-pentanediol, 1,9-nonanediol,
2-ethyl-2-butylpropanediol and the like, and examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,1.
4-cyclohexanedimethanol and the like. Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding one to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, for example, 2, 2-bis (4-hydroxyethoxyphenyl)
Although propane and the like are mentioned, since the ether structure reduces the water resistance and weather resistance of the film-formed product, the amount of the ether bond-containing glycol used as the polyhydric alcohol component constituting the polyester resin is the total polyhydric alcohol component. Is preferably not more than 10% by weight, more preferably not more than 5% by weight. In addition, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used as needed.

Among the above-mentioned polyhydric alcohols, it is preferable to use ethylene glycol, and the proportion of ethylene glycol in all the polyhydric alcohol components constituting the polyester resin is at least 40 mol%, especially at least 50 mol%. This is preferable in terms of balancing the various properties of the film-formed product and improving the water resistance and chemical resistance of the film-formed product. Ethylene glycol is preferred because it has the advantages of being industrially produced in large quantities and being inexpensive.

As the polybasic acid or polyhydric alcohol, a tribasic or higher polybasic acid or polyhydric alcohol may be used. Such trifunctional or higher polybasic acids include
Trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic anhydride, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) Tet), 1,2,3,4-butanetetracarboxylic acid and the like, and trifunctional or higher polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. However, the amount of the tribasic or higher polybasic acid or polyhydric alcohol to be used is limited to 10 mol% or less, and more preferably 5 mol% or less based on all the acid components or all alcohol components constituting the polyester resin. Is preferred in order to develop high workability of the film-formed product.

The acid component constituting the polyester resin in the present invention includes, in addition to polybasic acids, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid, and esters thereof. Forming derivatives, high-boiling monocarboxylic acids such as benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid and 4-hydroxyphenylstearic acid, ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxybenzoic acid, etc. May also be used. In addition, as the alcohol component constituting the polyester resin, a high-boiling monoalcohol such as stearyl alcohol or 2-phenoxyethanol may be used. However, it is preferable that the amount of the above-mentioned monocarboxylic acid component and monoalcohol component to be used is within a range in which the proportion of each of the total acid component and the total alcohol component constituting the polyester resin is 5 mol% or less.

The acid value of the polyester resin in the present invention needs to be 8 to 40 mgKOH / g, preferably 10 to 36 mgKOH / g, more preferably 10 to 36 mgKOH / g.
~ 28 mgKOH / g is more preferred. This acid value is 40
When the amount exceeds mgKOH / g, when a film is formed from the aqueous dispersion of the polyester resin and dried, water and an organic solvent hardly volatilize from the film-formed product, and the water resistance and chemical resistance of the film-formed product are reduced. On the other hand, when the acid value is less than 8 mgKOH / g, the amount of carboxyl groups contributing to aqueous conversion is not sufficient, and a good aqueous dispersion cannot be obtained.

The polyester resin of the present invention has a glass transition temperature of at least 40 ° C. as measured by DSC (differential scanning calorimetry) analysis or GPC (gel permeation chromatography, effluent: tetrahydrofuran, converted to polystyrene). ) Must satisfy any one of the conditions of number average molecular weight of 9,000 or more. When neither of these conditions is satisfied, that is, when the number average molecular weight is less than 9,000 and the glass transition temperature is less than 40 ° C., not only the water resistance and chemical resistance of the film-formed product decrease, but also In some cases, the workability is also poor. The glass transition temperature is preferably 43 ° C. or higher, particularly preferably 47 ° C. or higher. Further, the number average molecular weight is preferably 10,000 to 25,000,
1,000 to 20,000 is particularly preferred. However, there is no limitation on the molecular weight distribution. When the polyester resin does not dissolve in tetrahydrofuran and the number average molecular weight cannot be measured, the relative viscosity measured by a method described later can be used instead. In this case, the relative viscosity of 1.37 or more is substituted for the number average molecular weight of 9,000 or more, and the relative viscosity is preferably 1.38 to 2.30. 40 ~
2.00 is particularly preferred.

As a method for synthesizing the polyester resin in the present invention, a known method may be applied. For example, (a) the esterification reaction is carried out by reacting all the monomer components and / or the low polymer thereof under an inert atmosphere at 180 to 250 ° C. for about 2.5 to 10 hours, and subsequently, the presence of a transesterification catalyst Under a pressure of 1 Torr or less
A method in which a polycondensation reaction is advanced at a temperature of 20 to 280 ° C. until a desired molecular weight is reached to obtain a polyester resin; (b) the polycondensation reaction is terminated at a stage before reaching a target molecular weight, and a reaction product is obtained. Is mixed with a chain extender selected from an epoxy-based compound, an isocyanate-based compound, a bisoxazoline-based compound, and the like in the next step, and allowed to react for a short time to increase the molecular weight. (C) Targeting the polycondensation reaction It is possible to use a method of obtaining a polyester resin having a target molecular weight by further adding a monomer component, performing depolymerization in an inert atmosphere, normal pressure to a pressure system, or the like. it can.

In the polyester resin, the carboxyl group necessary for obtaining an aqueous dispersion (hereinafter referred to as aqueous) is more localized at the terminal of the resin molecular chain than in the resin skeleton. It is preferable in terms of water resistance, chemical resistance and the like of the film to be formed. As a method for obtaining such a polyester resin without a side reaction, gelation, or the like, the method (a) described above includes, after the start of the polycondensation reaction, a tribasic or higher functional polybasic acid or an ester-forming derivative thereof. Or a method in which an acid anhydride of a polybasic acid is added immediately before the end of the polycondensation reaction. In the above method (b), a low-molecular-weight polyester resin in which most of the molecular chain terminals are carboxyl groups is used. A method of increasing the molecular weight with a chain extender, a method using a polybasic acid or an ester-forming derivative thereof as a depolymerizing agent in the above method (c), and the like can be used.

The content of the polyester resin in the aqueous polyester resin dispersion of the present invention is appropriately selected depending on the intended use, the desired thickness of the coating film, and the molding method. And more preferably 1 to 40% by weight. As described below,
The polyester resin aqueous dispersion of the present invention has an advantage that storage stability is excellent even at a high solid content concentration such as a polyester resin content of 20% by weight or more, but the polyester resin content exceeds 50% by weight. In addition, the viscosity of the aqueous dispersion of the polyester resin becomes extremely high, and it may not be usable, which is not preferable. On the other hand, if the content is less than 0.5% by weight, a uniform film may not be formed, which is not preferable. In addition, as long as other solid contents other than the polyester resin are not added to the aqueous polyester resin dispersion, the solid content concentration of the aqueous polyester resin dispersion is equal to the above-mentioned polyester resin content.

[Component (B)] In the aqueous polyester resin dispersion of the present invention, a basic compound is required as a component for neutralizing the polyester resin when the polyester resin is made aqueous. In the present invention, the neutralization reaction described above, that is, the neutralization reaction between the basic compound and the carboxyl group that is the hydrophilic group in the polyester resin is the driving force for aqueous conversion, and between the carboxyl anions generated by the neutralization reaction. Aggregation between the polyester resin fine particles can be prevented by the electric repulsion. When the basic compound remains in the film-formed product, its performance tends to be reduced. Therefore, as the basic compound in the present invention, a compound which can be easily evaporated by drying is preferable.

Examples of such a basic compound include ammonia and organic amine compounds having a low boiling point, and the boiling point of the organic amine compound is preferably 160 ° C. or lower. Those which can be azeotropic with water are particularly preferred.
Specific examples of the basic compound preferably used in the present invention include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, and dibutylamine. , Isobutylamine, diisobutylamine, sec-butylamine, tert-butylamine, pentylamine, N, N-dimethylethanolamine, N-methyl-N-ethanolamine, propylenediamine, morpholine, N-methylmorpholine,
N-ethylmorpholine, piperidine and the like can be mentioned. In addition, as the basic compound, a single compound or a mixture of plural compounds may be used.

The content of the basic compound in the aqueous dispersion of the polyester resin of the present invention depends on the amount of the carboxyl group contained in the polyester resin. It is preferably 0.2 to 1.5 equivalents, and 0.1 equivalent.
4-1.3 equivalent is more preferable. If less than 0.2 equivalents, the effect of adding the basic compound may not be recognized,
On the other hand, if it exceeds 1.5 equivalents, the aqueous dispersion of the polyester resin may significantly increase in viscosity, which is not preferable. In addition, the content of the basic compound referred to here is a value calculated including the amount consumed to form the carboxylate by the above-described neutralization reaction. That is, the value is calculated from the amount of the basic compound added when the coating composition is obtained.

[Component (C)] The aqueous polyester resin dispersion of the present invention must contain an organic solvent as a component for promoting the aqueous conversion of the polyester resin. In addition, it is easy to volatilize from the film formation itself,
Moreover, ketones, alcohols, and the like as the organic solvent having a function of promoting the volatilization of water by azeotropic distillation with water.
It must be an organic solvent having a boiling point of 150 ° C. or lower selected from glycol derivatives. The organic solvent is selected from ketones, alcohols and glycol derivatives 1
If it is not an organic solvent having a boiling point of 50 ° C. or lower, repelling or bubbles may be generated when coating the aqueous dispersion, or the stability of the aqueous dispersion may be impaired. Among the above, alcohol is particularly preferably used. The boiling point of the organic solvent is preferably 130 ° C. or lower, particularly preferably 110 ° C. or lower. The content of the above-mentioned organic solvent is 0.1% with respect to the aqueous dispersion of the polyester resin.
5 to 50% by weight, preferably 5 to 50% by weight.
To 45% by weight, particularly preferably 10 to 40% by weight.
It is. If the content of the organic solvent is less than 0.5% by weight, it is difficult to make the polyester resin aqueous, and even when the polyester resin can be made aqueous, cissing and bubbles tend to occur during coating. On the other hand, if the content exceeds 50% by weight,
Not only may the stability of the dispersion be impaired, but it may not be compatible with the original purpose of aqueousization.

Specific examples of the organic solvent that can be used in the present invention include alcohols such as methanol and methanol.
Ethanol, n-propanol, isopropanol, n
-Butanol, isobutanol, sec-butanol,
tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert
-Amyl alcohol, 1-ethyl-1-propanol,
2-methyl-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxybutanol and the like,
As the ketone, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone,
Methyl isobutyl ketone, diethyl ketone and the like, glycol derivatives, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Examples thereof include propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. In addition, as an organic solvent, even a single
Further, a plurality of types may be mixed and used.

Next, a method of blending the above-described components in an aqueous medium to obtain the polyester resin aqueous dispersion of the present invention will be described. The method for obtaining the polyester resin aqueous dispersion is not particularly limited, and a method widely known to those skilled in the art can be applied. For example, a method in which a solution or melt obtained by dissolving a polyester resin in a general-purpose organic solvent is added little by little into an aqueous medium to which a surfactant is added and which is stirred at a high speed (forced emulsification). It can be carried out by applying a method in which an aqueous medium is added little by little to the solution or the melt under stirring and inverting the phase to obtain a stable aqueous dispersion (phase inversion emulsification method).

However, in the present invention, the method described in JP-A-9-296100 is particularly recommended for the following reasons. That is, 1) an aromatic polybasic acid component,
In particular, even for a polyester resin having a high terephthalic acid content and a relatively high molecular weight, any special monomer component or a structure in which an ionic group remains in the film-forming product is completely introduced into the polyester resin. In addition, it can be made water-soluble without externally adding a low molecular weight hydrophilic compound such as a surfactant. 2) Component (C) is contained in an amount of 0.5 to 50% by weight based on the polyester resin aqueous dispersion. And 3) storage stability even at a high solid content, and mixing stability when other components are added later. 4) Production of the polyester resin aqueous dispersion of the present invention because it is a method capable of producing a polyester resin aqueous dispersion having extremely excellent properties and with stable quality without using special equipment and in a relatively simple process. Method and Te is suitable. Further, in this method, even if the process is performed using a coarse polyester resin powder or granular material as a starting material, a finely divided aqueous polyester resin dispersion can be obtained. When the size of the polyester resin powder or granular material used as a starting material in this method is represented by the length of one side converted into a cubic shape, the length is preferably 8 mm or less, and is preferably 1 to 5 mm. Is more preferable, and 1.5 to 3
mm is particularly preferred.

The above method will be described in more detail. A dispersion step of mixing and coarsely dispersing a polyester resin powder or granules in an aqueous medium at around room temperature, and a heating step of heating this to a predetermined temperature with stirring. The glass transition temperature of the polyester resin or the higher temperature of 60 ° C. to 9
It is composed of four steps, namely, an aqueous step of stirring the polyester resin at 0 ° C. under predetermined conditions to form fine particles of the polyester resin, and a cooling step of cooling the polyester resin to 40 ° C. or lower, and these steps are continuously performed. . As an apparatus for performing these steps, a tank into which a liquid can be charged is provided, the mixture of the aqueous medium and the resin powder or the granular material charged into the tank can be appropriately stirred, and the inside of the tank is heated to 60 to 90 ° C. Any device that is widely known to those skilled in the art as a solid / liquid stirring device or an emulsifier can be used. Specific examples of such a device include a single-shaft stirrer such as a propeller mixer and a turbine mixer, and a turbine-stator type high-speed rotary stirrer (TK Homo-Mixe, manufactured by Tokushu Kika Kogyo Co., Ltd.).
r "," TK Homo-Jettor ", IKA-M
"Ultra-Turr" manufactured by ASCHINENBAU
ax ”etc.), and a compound stirrer using a high-speed shearing mixer and a low-speed sliding kneading paddle with a scraper that scrapes the tank wall and an anchor mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.,“ TKA ”).
gi-Homo-Mixer "," TK Combi
mix ”). The system of the apparatus may be a batch system or a continuous production system in which the input of the raw material and the removal of the processed material are continuously performed. The tank of the apparatus is preferably of a type that can be sealed.

In the above four steps, the component (A) (polyester resin) among the components to be added to the aqueous polyester resin dispersion must be added to the system by the end of the dispersion step. The component (B) (basic compound) and the component (C) (organic solvent) are blended in any step from the dispersion step to the aqueous solution step. The dispersion step performed for the purpose of preventing agglomeration of the polyester resin is usually performed by stirring at room temperature. However, when a long time is required for the next heating step, the dispersion is performed while heating the inside of the tank. A step may be performed. However, in that case, it is desired that the polyester resin powder or the particulate matter is dispersed in the aqueous medium in the following completely suspended state before the temperature in the tank reaches 40 ° C.
The end point of the dispersion step, that is, the state in which the polyester resin powder or granules are dispersed in a completely suspended state, is described in T.I.
N. Zwietering (Chemical Eng
innering Science, 8, 244 pages,
1958) defined "perfectly suspended,"
It is a state in which even a single particle does not stay at the bottom of the tank for 1 to 2 seconds or more, and it is preferable that the inside of the tank is stirred at a speed higher than a completely floating stirring speed to achieve this “completely floating state”. . The system kept in this state is transferred to a heating step, which is heated to the glass transition temperature of the polyester resin or the higher temperature of 60 ° C. to 90 ° C., and in the subsequent aqueousization step, usually stirred for 15 to 120 minutes. By continuing, the polyester resin is made aqueous. Then, the stirring speed is reduced, and a desired polyester resin aqueous dispersion is obtained through a cooling step of cooling to 40 ° C. or lower while being gently stirred. The component (C) may be further added to the obtained aqueous dispersion of the polyester resin within the scope of the present invention, in addition to being added in the above-described dispersion step to aqueous conversion step. However, in that case and when mixing the polyester resin aqueous dispersion of the present invention and other components,
It is preferable to perform these operations at 40 ° C. or lower. 40
When performed at a temperature exceeding ℃, depending on other conditions, phase separation may occur or the system may be significantly thickened.

The aqueous dispersion of the polyester resin obtained by the above method is one in which the polyester resin is sufficiently finely divided. However, in order to further reduce the particle size as required, the following jet pulverization treatment is carried out. May be performed. The jet pulverization treatment referred to in the present invention means that a fluid such as the above-mentioned polyester resin aqueous dispersion is jetted from a fine hole such as a nozzle or a slit under high pressure, and the resin particles or the resin particles and the collision plate and the like are ejected. Collision is to further fine the resin particles by mechanical energy. As an example of an apparatus used for performing a jet pulverizing treatment, a pulverizer (for example, AP.RTM.) Which jets a fluid from a nozzle under high pressure and collides it with an impingement plate or the like to make resin particles finer. V.
GAULIN “homogenizer”, Mizuho Industry Co., “Microfluidizer M-110E / H”
Etc.), a fluid is ejected from a nozzle under high pressure, and a crusher (for example, "TK Micromizer" manufactured by Tokushu Kika Kogyo Co., Ltd., SONI
C CORPORATION “Sonolator” etc.),
A pulverizer (for example, “Nanomizer PEN” manufactured by Nanomizer Co., Ltd.) that gives kinetic energy to the fluid under high pressure to cause high-speed fluids to collide with each other to make resin particles finer, and the like.

The aqueous polyester resin dispersion of the present invention is one in which fine particles of the polyester resin are uniformly dispersed in an aqueous medium. Uniform dispersion here means that
It means that a portion where the resin concentration is locally different from other portions, such as precipitation, phase separation, or skinning, is not found in the polyester resin aqueous dispersion. Also,
The fine particles of the polyester resin are obtained by filtering the aqueous dispersion of the polyester resin with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) under pressure (air pressure 2 kg / c).
m2) means polyester resin particles that do not remain on the filter when m2). It is desirable that the polyester resin aqueous dispersion of the present invention does not contain coarse polyester resin particles such as those remaining on the filter in the above-described pressure filtration. The particles may be removed.

The light transmittance (light wavelength: 750 nm) of the aqueous dispersion of the polyester resin of the present invention is improved in terms of improving the storage stability, the mixing stability with other components, the dilution stability and the like. ) Is preferably 5 to 85%, more preferably 10 to 75%, and more preferably 15 to 7%.
0% is particularly preferred. Such a value of the light transmittance is measured without any dilution of the aqueous dispersion, and if this value is less than 5%, the aqueous dispersion is liable to form agglomerates and precipitates during storage, and In addition, the mixing stability with other components is inferior, and the gloss and various resistances of the formed film tend to be inferior. On the other hand, 8
If it exceeds 5%, not only the particle size of the polyester resin fine particles in the aqueous dispersion is too small, so that the resin is liable to be hydrolyzed and the storage stability of the aqueous dispersion tends to be inferior. In addition, the drying speed when forming a film from such an aqueous dispersion is reduced, and as a result, the water resistance, chemical resistance, workability, and the like of the film-formed product may be reduced.

The light transmittance is determined by the acid value of the polyester resin in the production of the polyester resin aqueous dispersion,
It can be controlled by the type and amount of the basic compound and the organic solvent, the conditions at the time of production, etc., but the solid content concentration of the aqueous dispersion, the presence or absence of mixing with other components at the time of use, the film forming method, and further the film forming product Should be controlled in consideration of the required performance and the like. In addition, as a light transmittance of the polyester resin aqueous dispersion in the case where the polyester resin aqueous dispersion contains a pigment or a dye that hinders light transmission, a value measured and measured by one of the following two methods is employed. Shall be. (1) When a pigment having a large difference in specific gravity with respect to the polyester resin is contained, centrifugation is performed, and the content of the pigment with respect to the solid content is less than 1% by weight, and the solid content concentration other than the pigment is calculated from the compounding amount. A supernatant liquid which satisfies 98% or more of the obtained value is prepared, and the obtained value is used as a measurement. (2) When the method (1) contains a dye or the like that cannot be used, a decrease in the transmittance (absorbance) derived from the dye is measured in advance, and the polyester resin aqueous dispersion containing the dye is measured. The value obtained by removing this contribution from the obtained result is defined as the light transmittance.

The aqueous dispersion of polyester resin of the present invention can be used for applications such as adhesives, inks, fiber treatment agents, paper coating agents and various coating agents. When used, curing agents, pigments, dyes, other aqueous resins and various chemicals can be added to the polyester resin aqueous dispersion and mixed as necessary, and a film containing these additives can be formed. You can get things. Examples of such a curing agent include a phenol resin, an aminoplast resin, a polyfunctional epoxy compound, a polyfunctional isocyanate compound and various blocked isocyanate compounds thereof, and a polyfunctional aziridine compound. A reaction catalyst and a promoter can be used together if necessary. Examples of the drug include a repelling agent, a leveling agent, an antifoaming agent, an anti-penetrating agent, a rheology control agent, a pigment dispersant, and a lubricant.

The aqueous polyester resin dispersion of the present invention can be prepared by dip coating, brush coating, roll coating, spray coating, gravure coating, curtain flow coating, various printing methods, or the like. It can be uniformly coated on various substrates such as molded articles (including films, woven fabrics, yarns, etc.), paper, glass and the like, or can be impregnated into the substrates. Then, if necessary, the film is set at around room temperature and then subjected to a drying step to obtain a uniform and highly glossy film-formed product. This drying step is usually carried out by a hot air circulation type oven or an infrared heater or the like.
It is carried out at 160 ° C. for several seconds to 100 seconds. When the above-mentioned curing agent is used in combination, it is subjected to a heat treatment for further promoting the curing reaction.

The film-forming product of the present invention refers to a film-forming product obtained from the aqueous polyester resin resin dispersion of the present invention by the above-mentioned method and the like.
A film-forming product obtained from an aqueous dispersion of a polyester resin containing a dye, another aqueous resin, and various additives is also included in the film-forming product of the present invention. The thermal weight loss rate of the film formed product of the present invention is required to be 5% or less when a heat treatment is performed for 30 minutes in an atmosphere at 110 ° C., and 3% or less.
It is more preferred that: When the thermal weight loss rate exceeds 5%, water resistance and chemical resistance tend to decrease. In addition, the thickness of the film-formed product of the present invention varies depending on the coating method, application, and required performance,
It is preferably 0.01 to 50 μm, and 0.1 to 3 μm.
It is preferably 0 μm.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The characteristics of the polyester resin, the aqueous dispersion of the polyester resin, and the film-formed product were evaluated by the following methods.

(1) Composition of polyester resin 1 Determined by ¹ H-NMR analysis (Varian, 300 MHz). For the resin containing a constituent monomer having no peak that can be assigned or quantified on the ¹ H-NMR spectrum, methanol decomposition was performed at 230 ° C. for 8 hours in a sealed tube, and then subjected to gas chromatogram analysis. Was done. (2) Acid value of polyester resin 1 g of polyester resin was mixed with 50 ml of dioxane / water = 9.
/ 1 (volume ratio), completely dissolved in a mixed solvent, titrated with KOH using phenolphthalein as an indicator, and the number of mg of KOH consumed for neutralization was determined as an acid value. (3) Number average molecular weight and relative viscosity of polyester resin As described above, the number average molecular weight was determined by GPC analysis (using an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation, detection wavelength:
254 nm, solvent: tetrahydrofuran, converted to polystyrene). The relative viscosity was determined by dissolving the polyester resin in an equal weight mixture of phenol / 1,1,2,2-tetrachloroethane at a concentration of 1% by weight and measuring the viscosity at 20 ° C. using an Ubbelohde viscosity tube. The relative viscosity was measured only for a resin that was not dissolved in tetrahydrofuran and could not be analyzed by GPC. (4) Glass transition temperature of polyester resin 10 mg of polyester resin was used as a sample, and a DSC (differential scanning calorimetry) device (DS manufactured by Perkin Elmer)
Using C7), the temperature was measured at a heating rate of 10 ° C./min, and the intermediate value of the temperatures at the two bending points derived from the glass transition in the obtained heating curve was determined. And

(5) Solid Content Concentration of Aqueous Dispersion of Polyester Resin An appropriate amount of an aqueous dispersion of polyester resin was weighed,
The mixture was heated at 80 ° C. until the weight of the residue (solid content) reached a constant weight, and the solid content was determined. (6) Light Transmittance of Aqueous Dispersion of Polyester Resin The aqueous dispersion of polyester resin was placed in a quartz cell having a cell length of 0.2 cm, and the light transmittance at a temperature of 25 ° C. to light having a wavelength of 750 nm was measured. Note that distilled water was used as a blank. (7) Viscosity of aqueous dispersion of polyester resin Cone-plate type viscometer [Rheology Co., Ltd.
Shear rate 10 sec using MR-3 Solid Liquid Meter]
The viscosity at c-1 and a temperature of 25 ° C. was measured. However, in consideration of the thixotropy of the aqueous dispersion, the viscosity at the time when the rotation was started and reached a steady state was determined. (8) Storage Stability of Aqueous Dispersion of Polyester Resin 100 ml of an aqueous dispersion of polyester resin was sealed in a glass container, and left for 30 days in a laboratory room temperature kept at 20 to 25 ° C. At this time, the change in appearance was visually observed, and the storage stability was evaluated by measuring the viscosity by the method (7).

(9) Water resistance and alcohol resistance of the film-formed product The film-formed product obtained under the predetermined conditions was treated with distilled water at room temperature.
Alternatively, it was partially immersed in ethanol, gently pulled up after 10 minutes, and air-dried, and the change in appearance was evaluated according to the following criteria. ：: No change in appearance was observed. Δ: The interface of the liquid when immersed in distilled water or ethanol is observed in the coating even after drying. X: The part which had been immersed was clearly damaged such as whitening or partial dissolution. (10) Thermal Weight Reduction Rate of Film Formed Product After measuring the total weight including the PET film of the film formed product formed on the PET film under predetermined conditions, hot air circulating drying previously set to 110 ° C. Heated by throwing into the machine and holding for 30 minutes,
It was taken out and the total weight was measured. The total weight before and after this heat treatment was compared to determine the thermal weight loss rate of the film-formed product excluding the PET film. The weight of the PET film was measured before forming the film-forming product, and
It was previously confirmed that the T film did not change in weight due to the heat treatment.

Examples 1 to 12 and Comparative Examples 1 to 6 [Production of polyester resin-1] 1578 g of terephthalic acid and 83 g of isophthalic acid as acid components constituting the polyester resin, 374 g of ethylene glycol and neopentyl as alcohol components Glycol 730 g was prepared, and these mixtures were placed in an autoclave at 260 ° C.
For 2.5 hours to carry out an esterification reaction. Next, 0.262 g of germanium dioxide was added as a catalyst,
The temperature of the system was raised to 280 ° C. in 30 minutes, and the pressure of the system was gradually reduced to 0.1 Torr after one hour. The polycondensation reaction was further continued under these conditions, and after 1.5 hours, the system was brought to normal pressure with nitrogen gas, and the temperature of the system was lowered. When the temperature reached 260 ° C., 50 g of isophthalic acid and 38 g of trimellitic anhydride were further added as acid components. Was added and the mixture was stirred at 255 ° C. for 30 minutes and discharged in a sheet form. Then, after sufficiently cooling this to room temperature, it is pulverized with a crusher, and a sieve is used for opening 1 to 4.
A 6 mm fraction was collected, and granular polyester resin A-1 was collected.
As obtained. In a similar manner, polyester resins A-2 to A-7 were obtained such that the constitution of the acid component and the alcohol component was under the conditions shown in Table 1 below. In addition, the above 28
Polyester resin A-8 was obtained by extending the polycondensation reaction performed at 0 ° C. and 0.1 Torr to 2 hours.

[Production of polyester resin-2] 1,477 terephthalic acid was used as an acid component constituting the polyester resin.
g, isophthalic acid 185 g, adipic acid 162 g, and ethylene glycol 400 as an alcohol component.
g and neopentyl glycol (868 g) were prepared, and the mixture was heated in an autoclave at 260 ° C. for 2.5 hours to perform an esterification reaction. Then 0.349 g of germanium dioxide was added and the temperature of the system was raised to 2 over 30 minutes.
The temperature was raised to 80 ° C., and then the pressure of the system was gradually reduced to 0.1 Torr after one hour. The polycondensation reaction was further continued under these conditions, and after 1.7 hours, the system was returned to normal pressure with nitrogen gas, and the temperature of the system was lowered. When the temperature reached 250 ° C., 42.7 g of trimellitic anhydride was further added as an acid component. Add,
Continue stirring at 245 ° C. for 10 minutes (first stage depolymerization),
Then, the temperature of the system was lowered to 210 ° C., and 70.3 g of 2,2-bis (4-hydroxyethoxyphenyl) propane was further added as an alcohol component and reacted for 55 minutes (second stage depolymerization). Paid out. Then, after sufficiently cooling this to room temperature, it was pulverized with a crusher, and a fraction having an opening of 1 to 6 mm was collected using a sieve to obtain a granular polyester resin A-9. In a similar manner, a polyester resin A-10 was obtained in such a manner that the constitution of the acid component and the alcohol component met the conditions shown in Table 1 below.

[Production of polyester resin-3] 1 kg of the polyester resin A-7 obtained above and a bifunctional epoxy compound as a chain extender (Nagase Kasei Kogyo Co., Ltd.)
And "Denacol" EX-711) (11.3 g) and triphenylphosphine (0.5 g) were prepared and dry-blended. A twin-screw extruder (PCM-45, manufactured by Ikeigai Iron Works Co., Ltd.) ) To make the vent hole 35T
Melt kneading was carried out at an extrusion rate of 300 g / min while maintaining a reduced pressure of not more than orr to obtain a sheet-like resin. Then, after sufficiently cooling this to room temperature, pulverize with a crusher,
A fraction having an opening of 1 to 6 mm was collected using a sieve to obtain a polyester resin A-11.

The components and properties of the polyester resin obtained above are shown in Table 1 below. Among these polyester resins, A-6, A-7 and A-10 did not satisfy the requirements as the polyester resin in the present invention.

[0045]

[Table 1]

Next, the polyester resin obtained above was subjected to aqueous treatment by any of the following aqueous treatments (a) to (c) to obtain an aqueous polyester resin dispersion B-1. ~ B-19. [Aqueous treatment (a) method] A single-shaft type homodisper equipped with a jacketed 2L glass container which is sealed when mounted [Tokiki Kagaku Kogyo Co., Ltd .; K. Using ROBOMIX], distilled water, polyester resin and other raw materials were collectively charged into a glass container and stirred at a stirring speed of 6,000 rpm, and no precipitation of resin particles was observed at the bottom of the container. It was confirmed that it was completely suspended. Then, while maintaining this state, the heated water was passed through the jacket after 10 minutes. When the temperature in the system reached 60 ° C. or the higher of the glass transition temperatures of the polyester resin, the stirring speed was increased to 7,
000 rpm, the system temperature was 73 to 75 ° C., and the mixture was further stirred for 30 minutes under these conditions to obtain a milky white uniform liquid.
Then, pass cold water through the jacket and stir at a speed of 3,500.
By cooling to room temperature while stirring at rpm, a polyester resin aqueous dispersion was obtained.

[Aqueous Treatment (b) Method] The polyester resin aqueous dispersion obtained by the above method (a) is directly connected to a step of jetting a fluid to an impingement plate at a high pressure and a cooling step (5 times with a double pipe). Once under a condition of pressure 700 kg / cm ² using a jet pulverizing treatment apparatus (“Homogenizer” 15MR-8TA manufactured by APV GAULIN Co., Ltd.) equipped with a mechanism capable of applying cold water at a temperature of not more than 0 ° C. Was performed to obtain a finer-grained polyester resin aqueous dispersion. In the above-mentioned jet pulverization treatment, it was confirmed that the treatment liquid was immediately cooled to room temperature or lower by passing through the cooling step.

[Aqueous treatment (c) method] 5 with jacket
L type glass stirrer, which is hermetically sealed when attached [Tokiki Kagaku Kogyo Co., Ltd .; K.
Using Combimix 3M-5], distilled water, polyester resin and other raw materials are collectively charged into a glass container, and the stirring speed of a high-speed shearing stirring blade (homodisper) is 6,000 rpm. When the stirring was carried out at a stirring speed of 15 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was completely suspended. Therefore, while maintaining this state,
After 0 minute, the jacket was heated by passing hot water through it. When the temperature in the system reaches 60 ° C. or the higher one of the glass transition temperatures of the polyester resin, the stirring speed of the homodisper is increased to 6,500 rpm, and the temperature in the system is reduced to 7
The temperature was adjusted to 0 to 73 ° C., and the mixture was stirred under these conditions for 30 minutes to obtain a milky white uniform liquid. And let cold water pass through the jacket,
The homodisper stirring speed was reduced to 3,000 rpm, and the mixture was cooled to room temperature with stirring to obtain a polyester resin aqueous dispersion.

Table 2 below shows the composition of each component in the aqueous polyester resin dispersions of Examples 1 to 12 and Comparative Examples 1 to 6 and the method of making the aqueous dispersion aqueous.

[0050]

[Table 2]

The aqueous polyester resin dispersion obtained by any of the above methods was filtered under pressure (air pressure: 2 kg / cm ² ) through a 300-mesh stainless steel filter (wire diameter: 0.035 mm, plain weave). The filtrate was subjected to the evaluation of the characteristics of the aqueous dispersion of the polyester resin and the preparation of a film-formed product. In each of the aqueous dispersions, almost no resin remained on the filter after filtration. Moreover, the film formation product was produced by the following formation method-I.

[Method for Forming Film Forming Product-I] A polyester resin aqueous dispersion was applied to a desktop coating apparatus [Film Applicator No. No. manufactured by Yasuda Seiki Co., Ltd.] 542-AB
Using a mold and a bar coater], and coat the smooth surface of a commercially available aluminum stay so that the dry film thickness is 1.0 μm.
Keep this horizontal and set the drying temperature to 100 ° C or 80 ° C.
The coating was dried for 1 minute in an oven adjusted to ° C. to obtain a uniform coating (coated product).

The results of evaluating the properties of the aqueous dispersion of polyester resin and the film-formed product are shown in Table 3 below. In Comparative Example 1, the surface of the obtained film-formed product was rough, probably because the resin particles in the aqueous dispersion were somewhat large.
There was almost no gloss. Further, for Comparative Example 6,
Cracks occurred in the film-formed product produced at a drying temperature of 100 ° C., and the characteristics could not be evaluated.

[0054]

[Table 3]

Comparative Example 7 An aqueous polyester dispersion was prepared in the same manner as in Example 1 except that the amounts of the organic solvent and distilled water were changed.

Comparative Example 8 An aqueous dispersion of a polyester resin was prepared in exactly the same manner as in Comparative Example 1, except that the aqueous solution was changed to the method (a).

In Comparative Examples 7 and 8 described above, resin granules large enough to be easily discriminated by touch remain in the obtained aqueous dispersion, and the above-mentioned filtration under pressure was attempted. However, filter clogging occurred. Tables 2 and 3 also show the composition of each component in the aqueous dispersion of polyester resin and the method of making the aqueous dispersion aqueous for Comparative Examples 7 and 8.

Examples 13 to 15, 17 to 19 and Comparative Examples 9 to 12 100 g of the aqueous dispersion of the polyester resin obtained in Examples 3, 5, 9 or Comparative Examples 2, 4, and 6 was treated with the above homodisper. 2,000 rpm, distilled water and / or an organic solvent was gradually added to the mixture so as to have a composition shown in Table 4 below, and stirring was continued for 30 minutes after the addition to obtain an aqueous polyester resin dispersion. Obtained. The obtained aqueous dispersion of polyester resin was subjected to pressure filtration (air pressure: 2 kg / cm ² ) using a 300-mesh stainless steel filter (wire diameter: 0.035 mm, plain weave), and the obtained filtrate was used to produce a film-formed product. . In each of the aqueous dispersions, almost no resin remained on the filter after filtration. Further, a film-formed product was prepared by the following forming method-II. However, at the time of this film formation, foaming was observed in Comparative Example 9 due to insufficient coating performance of the aqueous dispersion. Similarly, in Comparative Example 10, cracks occurred, and the characteristics of the film-formed product could not be evaluated.

[Method of Forming Film Forming Product-II] A commercially available PET film (12 μm thick, without corona treatment, etc.) was prepared by using a gravure coater [manufactured by Hirano Techseed Co., Ltd.] 0.8 dry film thickness
The coating was continuously formed so as to have a thickness of μm, and dried (at a drying temperature of 80 ° C. or 90 ° C. for a drying time of 1 minute) in an attached oven and wound up to obtain a film-formed product.

Example 16 100 g of the aqueous dispersion of the polyester resin obtained in Example 3
Was stirred at 3,000 rpm with the above homodisper, and 50 g of water and a hydrophilic melamine resin [Cymel 303 (manufactured by Mitsui Cytec Co., Ltd., solid concentration: 100%) were added thereto.
%)], And stirring was continued for 30 minutes after the addition to obtain an aqueous polyester resin dispersion containing a melamine resin. This aqueous dispersion was subjected to the above-mentioned pressure filtration, and a film-formed product was prepared by the above-mentioned formation method-II using the obtained filtrate. In addition, also in this example, the resin hardly remained on the filter after the filtration.

The above Examples 13 to 19 and Comparative Examples 9-1
Table 4 shows the compounding conditions in Example 2. Table 5 below shows the results of evaluating the properties of the aqueous dispersion and the film-formed product.

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

The polyester resin aqueous dispersion of the present invention comprises:
It has excellent storage stability, mixing stability with other components, and dilution stability.In addition to the excellent processability, hardness, adhesion to substrates, and weather resistance inherent to polyester resins, water resistance and A film-formed product having excellent chemical resistance can be easily formed and obtained by a low-temperature, short-time drying treatment without using a curing agent. Therefore, the polyester resin aqueous dispersion of the present invention is useful in a wide range of fields and applications as an adhesive, an ink, a fiber treatment agent, a paper coating agent, and various coating agents. Further, the film formed product obtained by the present invention is particularly excellent in water resistance and chemical resistance,
The layer structure is not broken even if various aqueous or organic solvent-based coating agents are further applied on the film-formed product.
Therefore, by taking advantage of this point, it is possible to produce a revolutionary multilayer coating laminate which has not been obtained until now.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Daisuke Shirasawa 23 Uji Kozakura, Uji-city, Kyoto Unitika, Ltd. On-site F-term (reference) 4J002 CF011 CF031 CF051 CF061 CF071 CF081 CF091 CF101 DF006 EN026 EN106 EU076 EU236 FD090 FD140 GH00 GJ01 GK02 GK04 HA06 4J038 DD041 DD051 DD061 DD121 GA06 JA32 JA56 JA57 PC10 MA08 MA08 PC08

Claims (2)

[Claims] 1. An aqueous polyester resin dispersion comprising the following components (A) to (C), wherein fine particles of the polyester resin are uniformly dispersed in an aqueous medium. (A) It is composed of a polybasic acid component and a polyhydric alcohol component, has an acid value of 8 to 40 mgKOH / g, has a glass transition temperature of 40 ° C. or more, or has a number average molecular weight of 9.0.
Polyester resin having a value of 00 or more. (B) Basic compound (C) 0.5 to 50 based on aqueous dispersion of polyester resin
% By weight of an organic solvent having a boiling point of 150 ° C. or lower selected from ketones, alcohols and glycol derivatives. 2. A thermogravimetric reduction rate of 5% or less when obtained from the aqueous polyester resin dispersion according to claim 1 and subjected to a heat treatment in an atmosphere at 110 ° C. for 30 minutes. Film formation.