JP2003253102A - Aqueous dispersion of polyester resin and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a polyester resin that is made up of a low acid value polyester, and forms a resin film excellent in storage stability, adherence to a substrate, water resistance, and solvent resistance, and a process for manufacturing the dispersion. <P>SOLUTION: The aqueous dispersion of the polyester resin comprises a polyester resin with an acid value of ≤8 mgKOH/g (A), a basic compound (B), and a compound having the activity of a surface active agent or of a protective colloid (C). The mass ratio of (C) to (A) is (C)/(A)=0.1/100-20/100. In manufacturing the dispersion with phase reversal emulsification, the phase reversal emulsification is conducted at a temperature of ≤40°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin aqueous dispersion which is excellent in storage stability and can be applied to various substrates to form a resin film having excellent adhesion, hot water resistance and solvent resistance. is there.

[0002]

2. Description of the Related Art Polyester resin is used as a film-forming resin because it is excellent in processability of the film, resistance to organic solvents (solvent resistance), weather resistance, and adhesion to various substrates. It is used in large quantities as a binder component in the fields of adhesives, coating agents and the like. Particularly in recent years, the use of organic solvents has tended to be restricted from the standpoints of environmental protection, resource conservation, regulation of dangerous substances by the Fire Service Act, and improvement of the work environment. A polyester resin aqueous dispersion finely dispersed in an aqueous medium has been actively developed.

For example, Patent Documents 1 to 3 propose a polyester resin aqueous dispersion in which a high molecular weight polyester resin having a small acid value is dispersed in an aqueous medium. When such an aqueous dispersion is used, processability is improved. It is described that a film having excellent performance such as water resistance and solvent resistance can be formed. However, any of the polyester resin water dispersions described in these documents are dispersed in an aqueous medium by neutralizing the terminal carboxyl groups of the polyester resin with a basic compound, so-called self-emulsifying polyester resin water. Since it is a dispersion, in order to stably disperse the polyester resin in an aqueous medium, it is necessary to have a carboxyl group corresponding to an acid value of 8 mgKOH / g or more, and as a result, the molecular weight of the polyester resin is It was limited.

Further, Patent Documents 4 and 5 propose a method for producing an aqueous dispersion of a polyester resin using a basic compound and a nonionic surfactant. However, the polyester resin water dispersions described in these documents all have a large content of the surfactant with respect to the polyester resin, and when a resin film is formed using such a polyester resin water dispersion, However, a large amount of the surfactant remains in the resin coating, which causes a problem that the water resistance of the resin coating deteriorates. Further, Patent Document 5 is a substantially W / O type emulsion, and depending on the type of material to be coated (base material), there is a problem that it is damaged by the organic solvent contained in the polyester resin aqueous dispersion. .

[0005]

[Patent Document 1] JP-A-9-296100

[Patent Document 2] Japanese Patent Laid-Open No. 2000-26709

[Patent Document 3] Japanese Patent Laid-Open No. 2000-313793

[Patent Document 4] Japanese Patent Publication No. 51-24375

[Patent Document 5] Japanese Patent Publication No. 53-14101

[0006]

Under these circumstances, the object of the present invention is to provide a resin film having a low acid value, which is excellent in storage stability and can form a resin film excellent in adhesion to a substrate, water resistance and solvent resistance. Another object of the present invention is to provide a polyester resin aqueous dispersion using the above polyester resin and a method for producing the same.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the content of a surfactant can be reduced by controlling the temperature during phase inversion emulsification. Also found that a polyester resin having a low acid value can be stably dispersed in an aqueous medium, and that the resin coating formed from the aqueous dispersion thus obtained has good coating performance, and completes the present invention. Came to.

That is, the gist of the present invention is, firstly, a polyester resin (A) having an acid value of less than 8 mgKOH / g.
And a basic compound (B) and a compound (C) having a surfactant or a protective colloid action, and the mass ratio of (A) to (C) is (C) / (A) = 0.1. / 100 ~
It is a polyester resin aqueous dispersion characterized by being 20/100. Secondly, an organic solvent solution of polyester resin (A) is dispersed in water together with a basic compound (B) and a compound having a surfactant or a protective colloid action (C), and an aqueous dispersion is produced by phase inversion emulsification. The method for producing a polyester resin aqueous dispersion, wherein the phase inversion emulsification is performed at 40 ° C. or lower. Thirdly, there is provided a method for producing a polyester resin aqueous dispersion, which comprises removing the organic solvent after phase inversion emulsification.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polyester resin aqueous dispersion (hereinafter, referred to as an aqueous dispersion) of the present invention comprises (A) a polyester resin having an acid value of less than 8 mgKOH / g, (B) a basic compound, and (C) a surfactant or An aqueous dispersion obtained by dispersing a compound having a protective colloid action in an aqueous medium,
The mass ratio of (A) and (C) is (C) / (A) = 0.1 /
The polyester resin aqueous dispersion is 100 to 20/100. The aqueous medium is a medium containing water as a main component, and preferably contains 50% by mass or more of water.

First, the polyester resin (A) will be described. In the present invention, the acid value of the polyester resin is less than 8 mgKOH / g, more preferably 2 to 6 mgKOH / g, and further preferably 2 to 5 mgKOH / g. A polyester having an acid value of less than 8 mgKOH / g has a relatively high molecular weight, so that the adhesiveness and water resistance when formed into a film are improved. Also, the acid value is 2 mgKO
If it is less than H / g, it tends to be difficult to make it aqueous,
Further, even if it is possible, the volume average particle size becomes large and the storage stability deteriorates, which is not preferable.

The number average molecular weight of the polyester resin is preferably 4,000 or more, more preferably 8,000 or more, further preferably 12,000 or more, and more preferably 15,000 or more. Is most preferred. When the number average molecular weight is less than 4,000, the workability of the resin coating tends to be insufficient. Further, the polyester resin may contain a hydroxyl group within a range that does not impair the water resistance of the resin coating, preferably 30 mgKOH / g or less, and more preferably 20 mgKOH / g or less.

The dispersity of the molecular weight distribution of the polyester resin is not particularly limited, but is preferably 8 or less, more preferably 5 or less. Here, the dispersity of the molecular weight distribution is
It is a value obtained by dividing the weight average molecular weight by the number average molecular weight.

The glass transition temperature (hereinafter referred to as Tg) of the polyester resin is also not particularly limited, but it is -50.
-120 degreeC is preferable and 0-80 degreeC is more preferable.

As the acid component constituting the polyester resin, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acid such as biphenyldicarboxylic acid, oxalic acid, succinic acid, adipic acid,
Saturated aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, hydrogenated dimer acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, unsaturated aliphatic dicarboxylic acids such as dimer acid, 1 , 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5
Examples thereof include norbornene dicarboxylic acid and alicyclic dicarboxylic acid of tetrahydrophthalic acid. These may be anhydrous.

Among the above-mentioned polybasic acid components, aromatic dicarboxylic acids are preferable, terephthalic acid and isophthalic acid are particularly preferable, and terephthalic acid is particularly preferable. The proportion of the aromatic dicarboxylic acid in the acid component of the polyester resin is preferably 50 mol% or more, more preferably 70 mol% or more. Increasing the proportion of aromatic dicarboxylic acid increases the number of aromatic ester bonds that are difficult to hydrolyze, improving the hardness, hot water resistance, and solvent resistance of the film formed from the aqueous dispersion (hereinafter referred to as the resin film). In addition, the storage stability of the aqueous dispersion is improved.

Further, trifunctional or higher functional acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, trimesic acid and ethylene glycol bis. (Anhydrotrimellitate), glycerol tris (anhydrotrimellitate), 1,
2,3,4-butanetetracarboxylic acid and the like may be contained. At this time, from the viewpoint of maintaining good processability of the resin coating, the proportion of trifunctional or higher functional acid in the acid component of the polyester resin is preferably limited to 5 mol% or less.

As the polyhydric alcohol component constituting the polyester resin, an aliphatic glycol having 2 to 10 carbon atoms,
An alicyclic glycol having 6 to 12 carbon atoms, an ether bond-containing glycol, or the like is preferable. Specifically, ethylene glycol, 1,2-propanediol, 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, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol and the like can be mentioned.

Further, ethylene oxide or propylene oxide adducts of bisphenols such as 2,2-bis (4-hydroxyethoxyphenyl) propane, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can also be used.

Among the above polyhydric alcohol components, ethylene glycol or neopentyl glycol is preferable, and the total proportion of ethylene glycol and neopentyl glycol in the polyhydric alcohol component of the polyester resin is preferably 50 mol% or more, 60 mol% or more is more preferable, and 70 mol% or more is particularly preferable. Since ethylene glycol and neopentyl glycol are industrially produced in large quantities, they are inexpensive, and the various performances of the resin coating are balanced. Ethylene glycol improves the chemical resistance of the resin coating, and neopentyl glycol is In particular, since it has the advantage of improving the weather resistance of the resin coating, it is preferable as the polyhydric alcohol component of the polyester resin.

Further, a polyfunctional alcohol having a functionality of 3 or more, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like may be contained. At this time, from the viewpoint of maintaining good processability of the resin coating, it is preferable that the proportion of the trifunctional or higher polyhydric alcohol in the alcohol component of the polyester resin be within the range of 5 mol% or less.

Further, the polyester resin may be copolymerized with a monocarboxylic acid, a monoalcohol or a hydroxycarboxylic acid, and examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid. Acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid, 4-hydroxyphenylstearic acid, stearyl alcohol, 2-phenoxyethanol, ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxybenzoic acid, etc. You can

The polyester resin can be produced by polycondensing one or more of the above polybasic acid components and one or more of the polyhydric alcohol components by a known method. For example, all monomer components and / or The low polymer is reacted in an inert atmosphere at 180 to 250 ° C. for about 2.5 to 10 hours to carry out an esterification reaction, and subsequently in the presence of a transesterification reaction catalyst under a reduced pressure of 130 Pa or less 220 to 280. A method of obtaining a polyester resin by advancing the polycondensation reaction at a temperature of ° C until the desired molecular weight is reached can be mentioned.

When a desired acid value or hydroxyl value is imparted to the polyester resin, a polybasic acid component or a polyhydric alcohol component is further added following the above polycondensation reaction, and the polybasic acid component and the polyhydric alcohol component are dissolved under an inert atmosphere. Examples thereof include a method of polymerizing.

The content of the polyester resin in the aqueous dispersion of the present invention is preferably 5 to 50% by mass,
It is more preferably 10 to 40% by mass. When the content of the polyester resin exceeds 50% by mass, the viscosity of the aqueous dispersion becomes very high, which may make it difficult to form the resin coating, and when the content is less than 5% by mass, Not practical.

Next, the basic compound (B) will be described. The aqueous dispersion of the present invention needs to contain a basic compound. The basic compound neutralizes the carboxyl group of the polyester resin to generate a carboxyl anion, and the electric repulsive force between the anions causes the polyester resin fine particles to disperse stably without aggregation. Without this action of electric repulsion, it is difficult to obtain a good aqueous dispersion, but on the other hand, because of the low acid value of the polyester resin, a sufficiently stable aqueous dispersion cannot be obtained only by the action of the carboxyl anion. It is necessary to use an emulsifier and a compound having a protective colloid action described later together.

As the basic compound, an organic amine having a boiling point of 250 ° C. or lower, preferably 160 ° C. or lower, or ammonia is preferable because it easily volatilizes during the formation of the resin film. Specific examples of organic amines preferably used include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine. ,
Ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-
Butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-
Examples include ethylmorpholine, among which ammonia,
It is preferable to use triethylamine or N, N-dimethylethanolamine.

Next, the compound (C) having a surfactant or protective colloid action will be described. In order to produce the aqueous dispersion of the present invention, it is necessary to use water and the above-mentioned polyester resin and basic compound together with a surfactant or a compound having a protective colloid action. As described above, it is possible to supplement the storage stability, which was not sufficient only by the electric repulsive force of the carboxyl anion of the polyester resin.

The surfactant includes all known surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Among the surfactants, it is preferable to use a nonionic surfactant because of its excellent mixing stability with the pigment and generation of bubbles.
The hile Lipophile Balance) is preferably 8 to 20, more preferably 10 to 18, and even more preferably 11 to 14.9. Examples of the nonionic surfactant include alkylene oxide adducts of alkylphenols such as nonylphenol and octylphenol and alkylene oxide adducts of higher alcohols. Such nonionic surfactants include Igepal manufactured by Aldrich.
Series, NAROACTY N-1 made by Sanyo Kasei Co., Ltd.
00, Naloacty N-120, Naloacty N-1
40 mag, Naloacty series, Sannonic SS-
120, Sannonic SS-90, Sannonic SS-
70 etc., Sannonic SS series, Sannonic FD
-140, Sannonic FD-100, Sannonic F
D-80, Sannonic FD series, Cedran FF
-220, Cedran FF-210, Cedran FF-200,
Cedran FF-180 etc., Cedran FF series, Cedran SNP-112 etc., Cedran SNP series, New Pole PE-64, New Pole PE-74, New Pole PE 75 etc., New Pole PE series, San Morin 11 and the like.

Further, instead of the surfactant, a compound having a protective colloid action may be used. The protective colloid action is to adsorb on the surface of resin fine particles in an aqueous medium, and shows a so-called "mixing effect", "osmotic pressure effect", or "stabilizing effect" called "volume limiting effect" to prevent adsorption between resin fine particles. Refers to the preventive action. As the compound having a protective colloid action, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinylpyrrolidone, polyacrylic acid, a polymer of a vinyl monomer having acrylic acid and / or methacrylic acid as one component, Examples thereof include polyitaconic acid, gelatin, gum arabic, casein, and swelling mica. The surfactant or the compound having a protective colloid action may be used alone or in combination of two or more. In the present specification, the term “surfactant or compound having protective colloid action” will be simply referred to as “surfactant or the like” hereinafter.

In the aqueous dispersion of the present invention, the polyester resin (A) and the surfactant (C) have a mass ratio (C) / (A) of 0.1 / 100 to 20/100. It must be in the range, preferably 0.5 / 100 to
15/100 range, more preferably 1.0 / 100
The range is from 10 to 100.

When the value of (C) / (A) exceeds 20/100, in the desolvation step to be described later, not only the aqueous dispersion becomes foamy but the production becomes problematic, but also the surface active agent and the like form a resin film. A large amount remains inside and the water resistance of the resin coating deteriorates, which is not preferable. Also, (C) /
If the value of (A) is less than 0.1 / 100, the storage stability of the aqueous dispersion tends to deteriorate.

Next, the volume average particle diameter of the aqueous dispersion will be described. In the present invention, the volume average particle diameter of the aqueous dispersion is preferably 500 nm or less, more preferably 300 nm or less, further preferably 200 nm or less, and particularly preferably 150 nm or less. When the volume average particle size exceeds 500 nm, the polyester in the obtained aqueous dispersion is likely to settle,
Storage stability tends to be impaired. To make the volume average particle diameter of the aqueous dispersion 500 nm or less, for example, the production method described below may be used.

Next, the method for producing the aqueous dispersion of the present invention will be described in detail. The production of the aqueous dispersion of the present invention consists essentially of two steps, a dissolution step and a dispersion step,
Further, a solvent removing step is added if necessary.
The dissolving step is a step of dissolving the polyester resin in an organic solvent, and the dispersing step is a step of dispersing the polyester resin solution dissolved in the organic solvent in water together with the basic compound, the surfactant and the like. The solvent removing step is a step of removing a part or all of the organic solvent used in the dissolving step of the polyester resin from the obtained aqueous dispersion to the outside of the system.

Each step will be described below. First, in the dissolving step, the polyester resin is dissolved in an organic solvent. At this time, it is preferable that the concentration of the polyester resin in the obtained solution is in the range of 10 to 70% by mass.
The range of 0 to 60 mass% is more preferable, and the range of 30 to 50 mass% is particularly preferable. When the concentration of the polyester resin in the solution exceeds 70% by mass, the viscosity increases greatly when mixed with water in the next dispersion step, and the aqueous dispersion obtained from such a state has a volume average The particle size tends to be large, which is not preferable in terms of storage stability. When the concentration of the polyester resin is less than 10% by mass, the concentration of the polyester resin is further lowered by the next dispersion step and a large amount of the organic solvent is removed during the solvent removal step, which is uneconomical. is there. The device for dissolving the polyester resin in the organic solvent is not particularly limited as long as it has a tank into which a liquid can be charged and can be appropriately stirred. If the polyester resin is difficult to dissolve, heating may be performed.

As the organic solvent, known ones can be used, for example, a ketone organic solvent, an aromatic hydrocarbon organic solvent, an ether organic solvent, a halogen-containing organic solvent, an alcohol organic solvent, an ester. Examples of the organic solvent include glycol organic solvents. Methyl ethyl ketone (2-butanone) (hereinafter M
EK), acetone, diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone)
(Hereinafter referred to as MIBK), 2-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone,
4-heptanone, cyclopentanone, cyclohexanone, etc. can be illustrated. Aromatic hydrocarbon organic solvents include toluene, xylene, benzene, etc., ether organic solvents include dioxane, tetrahydrofuran, halogen-containing organic solvents include carbon tetrachloride, trichloromethane, dichloromethane, etc., alcoholic solvents. As the organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, se
c-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, etc. As the ester organic solvent, ethyl acetate, acetic acid-n-propyl acetate, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-sec-
Butyl, acetic acid-3-methoxybutyl, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, etc., as glycol-based organic solvents, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether. , Ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ester It can be exemplified ether acetate. Further, further, 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide,
Examples thereof include organic solvents such as diacetone alcohol and ethyl acetoacetate.

As these organic solvents, the above-mentioned ones can be used alone or in combination of two or more kinds. In order to obtain the aqueous dispersion of the present invention, 10% by mass or more of the polyester resin is dissolved. It is necessary to select an organic solvent so that
More preferably, the organic solvent capable of dissolving is 3
An organic solvent capable of dissolving 0 mass% or more is even more preferable. As such an organic solvent, acetone, MEK, MIBK, dioxane, tetrahydrofuran, cyclohexanone alone, acetone / ethylene glycol monobutyl ether mixed solution, MEK / ethylene glycol monobutyl ether mixed solution, MIBK / ethylene glycol monobutyl ether mixed solution, dioxane / Ethylene glycol monobutyl ether mixed solution, tetrahydrofuran / ethylene glycol monobutyl ether mixed solution, cyclohexanone / ethylene glycol monobutyl ether mixed solution, acetone / isopropanol mixed solution, MEK / isopropanol mixed solution, MIBK / isopropanol mixed solution, dioxane / isopropanol mixed solution, Tetrahydrofuran / isopropanol mixed solution, cyclohex Non / isopropanol mixture solution or the like can be suitably used. When using a mixed solution, prepare a mixed solution with an arbitrary mixing ratio and dissolve the polyester resin in the mixed solution,
Alternatively, the polyester may be previously dissolved with an organic solvent having a higher dissolving power for the polyester, and a prescribed amount of another organic solvent may be added before the dispersion step described later.

Next, the dispersion step will be described. In the dispersion step, the polyester resin solution obtained in the dissolution step,
Phase inversion emulsification is performed by mixing with water, a basic compound, a surfactant and the like. In the present invention, it is preferable that a basic compound, a surfactant and the like are added to a solution containing a polyester resin, and water is gradually added to disperse the solution, and by using such a method. The particle size of the obtained aqueous dispersion can be 500 nm or less, and the storage stability becomes good.

In the present invention, "inversion emulsification" means
It means that the system is changed from the organic solvent phase to the aqueous phase by adding an amount of water exceeding the amount of the organic solvent contained in the solution of the polyester resin to the organic solvent.

The dispersion step is preferably performed at 40 ° C. or lower, more preferably 30 ° C. or lower, further preferably 20 ° C. or lower, particularly preferably 15 ° C. or lower. By carrying out the dispersion step at 40 ° C. or lower, the particle diameter of the obtained aqueous dispersion can be 500 nm or less even if the content of the surfactant and the like is small, and the storage stability becomes good. The temperature of the above-mentioned dispersion step is preferably maintained at 40 ° C. or lower throughout this step, but the temperature of the system may be difficult to maintain because the liquid temperature easily rises due to shearing heat insulation by stirring. Even in such a case, it is preferable to control the temperature to 40 ° C. or lower (not to exceed 40 ° C.) until the addition of 0.8 times the amount of water contained in the polyester resin solution is completed, and more preferably The above temperature is controlled until the addition of 1-fold amount of water is completed, and more preferably, the addition of 1.1-fold amount of water is completed.

The amount of the basic compound used in the production method of the present invention is defined by the equivalent ratio to the total molar amount of the carboxyl groups of the polyester resin (A). When the acid value of the polyester resin (A) is CmgKOH / g and the equivalent ratio of the basic compound (B) to be used to the total molar amount of carboxyl groups of the polyester resin is D, it is used within the range of the following formula (1). Is more preferable, the range of the following formula (2) is more preferable, and the range of the following formula (3) is still more preferable.

[0041]   −1.375 × C + 11.5 ≦ D ≦ −5 × C + 50 (1)   -1.75 × C + 15 ≦ D ≦ −4.25 × C + 42 (2)   -2 x C + 18 ≤ D ≤ -3.5 x C + 34 (3)

FIG. 1 shows the relationship between the acid value of the polyester resin in the dispersion step represented by the above formulas (1) to (3) and the equivalent ratio of the necessary basic compound to the total molar amount of the carboxyl groups of the polyester resin. Is illustrated. From FIG. 1, it can be seen that the basic compound used for dispersing the low acid value polyester resin requires a much larger amount than the amount at which the carboxyl groups of the polyester resin are just neutralized (1 equivalent). Recognize. In particular, when the acid value of the polyester resin is reduced to about 2 mgKOH / g, the tendency is remarkably increased. On the other hand, when the acid value is about 8 mgKOH / g, the tendency becomes smaller and half the equivalent of the carboxyl group of the polyester is neutralized (0.5 times equivalent).
As described above, it is possible to disperse with a basic compound amount of preferably twice the equivalent or more.

When D is smaller than (-1.375 × C + 11.5), the effect of electric repulsion between the carboxyl anions produced by neutralizing the carboxyl groups of the polyester in the dispersing step becomes insufficient, This causes problems such as polyester agglomeration and precipitation. Further, even if an aqueous polyester dispersion is produced, the particle size becomes large and the storage stability becomes poor, which is not preferable. On the other hand, D is (-5 x
When it exceeds C + 50), a large amount of basic compound remains in the obtained aqueous dispersion, which is not preferable.
Further, when the solvent removal treatment as described below is performed, the polyester resin is aggregated and the solvent removal becomes difficult, which is not preferable. When the solvent removal step is performed after the dispersion step, the final basic compound content in the aqueous dispersion may be less than 1% by mass.

An apparatus for carrying out the dispersion step is not particularly limited as long as it has a tank into which a liquid can be put and can carry out appropriate stirring. Examples of such a device include devices that are widely known to those skilled in the art as a solid / liquid stirring device and an emulsifier (for example, a homomixer). When using an emulsifier having a large shear such as a homomixer, the liquid temperature may increase due to the shear heat insulation, and therefore it is preferable to use it while cooling. The dispersing step may be carried out under any conditions of normal pressure, reduced pressure and increased pressure.

The content of the organic solvent in the aqueous dispersion of the present invention is not particularly limited, but is preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 5% by mass or less, 1 A mass% or less is particularly preferable, and a mass% or less is most preferable. When the content of the organic solvent exceeds 30% by mass, the material to be coated may be damaged by the organic solvent contained in the aqueous dispersion depending on the type of the material to be coated, which is not preferable.

Next, a solvent removing step may be provided. The solvent removal step is a step of distilling an organic solvent contained in the aqueous dispersion to remove a part or all of the organic solvent from the aqueous dispersion. This step can be performed under reduced pressure or normal pressure. When the solvent is removed under normal pressure, agglomerates may be easily generated, but in such a case, it is performed under reduced pressure and the internal temperature is adjusted to 70
℃ or less, preferably 60 ℃ or less, more preferably 50
It is advisable to adjust the temperature so that it is below ℃. An apparatus for performing the solvent removal step may be any apparatus that is equipped with a tank into which a liquid can be charged and can perform appropriate stirring.

If a foaming phenomenon occurs during solvent removal, an antifoaming agent may be added for the purpose of suppressing this. The antifoaming agent includes known water-based antifoaming agents such as silicone type, silica, silicone compound type and polyamide type.
The amount of the defoaming agent is 1-1000 ppm, preferably 5-100 pp, relative to the mass of the aqueous dispersion to be desolvated.
Add m. Examples of such antifoaming agents include SN deformer 381, SN deformer 470, SN deformer 777, SN deformer 5013, SN deformer JK manufactured by San Nopco Ltd.

According to the above-mentioned production method, the polyester resin aqueous dispersion of the present invention has a volume average particle diameter of the polyester resin dispersed to 500 nm or less, and the appearance thereof causes precipitation, phase separation or skinning in an aqueous medium. It is obtained in a uniform state in which a portion where the solid content concentration locally differs from the other portion is not found.

In the production of the aqueous dispersion, a filtration step may be provided during the step for the purpose of removing foreign matters and the like. In such a case, for example, a stainless steel filter of about 300 mesh (wire diameter 0.035 mm, plain weave) may be installed and pressure filtration (air pressure 0.2 MPa) may be performed.

Next, a method of using the aqueous dispersion of the present invention will be described. Since the aqueous dispersion of the present invention is excellent in film forming ability, it is uniformly coated on the surface of various substrates by known film forming methods such as dipping method, brush coating method, spray coating method and curtain flow coating method. Then
If necessary, after setting at around room temperature, it is subjected to a heat treatment for drying and baking, whereby a uniform resin film can be formed in close contact with various substrate surfaces. As a heating device at this time, an ordinary hot air circulation type oven, an infrared heater or the like may be used. The heating temperature and heating time are appropriately selected depending on the type of the substrate to be coated,
Considering economy, the heating temperature is 60 to 25
0 degreeC is preferable, 70-230 degreeC is more preferable, 80
To 200 ° C. is particularly preferable, and the heating time is from 1 second to
30 minutes is preferable, 5 seconds to 20 minutes is more preferable, 1
0 second to 10 minutes is particularly preferable.

The thickness of the resin film formed using the aqueous dispersion of the present invention is appropriately selected depending on the purpose and application, but is preferably 0.01 to 40 μm, and 0.1 to 40 μm. 30 μm is more preferable, 0.5 to 20 μm
m is particularly preferred.

In the aqueous dispersion of the present invention, if necessary, a curing agent, various additives, pigments such as titanium oxide, zinc white, carbon black, etc., dyes, other aqueous polyester resins, aqueous urethane resins, aqueous solutions. An aqueous resin such as an olefin resin or an aqueous acrylic resin can be blended.

The curing agent is not particularly limited as long as it is a curing agent reactive with a functional group of the polyester resin, for example, a carboxyl group or its anhydride or hydroxyl group, and examples thereof include urea resin, melamine resin and benzoguanamine. Amino resin such as resin, polyfunctional epoxy compound,
Examples thereof include polyfunctional isocyanate compounds and various blocked isocyanate compounds thereof, polyfunctional aziridine compounds, carbodiimide group-containing compounds, oxazoline group-containing polymers, and phenol resins. Even if one of these is used, two or more types are used in combination. You may.

Examples of the additives include anti-repellent agents, leveling agents, defoamers, anti-armpit agents, rheology control agents, pigment dispersants, UV absorbers, lubricants and the like. Incidentally, the above-mentioned curing agent, various additives, pigments, dyes,
The aqueous resin or the like may be added in advance when the polyester resin is dissolved or dispersed.

[0055]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

(1) Constitution of polyester resin Obtained from 1 H-NMR analysis (300 MHz, manufactured by Varian). In addition, for resins containing constituent monomers for which no identifiable / quantifiable peaks are observed on the 1 H-NMR spectrum, methanol decomposition was performed in a sealed tube at 230 ° C. for 3 hours and then subjected to gas chromatogram analysis for quantitative analysis. went. (2) Acid value of polyester resin 0.5 g of polyester resin is dissolved in 50 ml of water / dioxane = 1/9 (volume ratio), titrated with KOH using cresol red as an indicator, and KOH consumed for neutralization
The value obtained by converting the number of mg per 1 g of polyester resin was determined as the acid value.

(3) Hydroxyl Value of Polyester Resin 3 g of polyester resin is precisely weighed, 0.6 ml of acetic anhydride and 50 ml of pyridine are added, and the mixture is stirred at room temperature for 48 hours for reaction, followed by addition of 5 ml of distilled water. And then 6
By continuing stirring at room temperature for a period of time, acetic anhydride was also converted to acetic anhydride for the portion not used in the above reaction. 50 ml of dioxane was added to this solution, and cresol red
Titration with KOH using thymol blue as an indicator, and when the amount of KOH consumed for neutralization (W1) and the amount of acetic anhydride initially charged did not react with the polyester resin and became all acetic acid, it was neutralized. From the amount of KOH required (calculated value: W0), the difference (W0-W1) was determined by the mg number of KOH, and the value obtained by dividing this by the g number of the polyester resin was taken as the hydroxyl value. (4) Number average molecular weight of polyester resin The number average molecular weight is determined by GPC analysis (Shimadzu Corporation liquid delivery unit LC-10ADvp type and ultraviolet-visible spectrophotometer S.
PD-6AV type is used, detection wavelength: 254 nm, solvent:
It was calculated by using tetrahydrofuran and polystyrene.

(5) Glass transition temperature of polyester resin Using 10 mg of polyester resin as a sample, DSC (differential scanning calorimetry) apparatus (DSC manufactured by Perkin Elmer Co., Ltd.)
7) is used and the temperature is raised at a rate of 10 ° C./min.
The intermediate value of the two bending point temperatures derived from the glass transition in the obtained temperature rising curve was determined, and this was determined as the glass transition temperature (Tg).
And (6) Solid Content Concentration of Aqueous Dispersion An appropriate amount of the aqueous dispersion is weighed and heated at 105 ° C. until the mass of the residue (solid content) reaches a constant weight.
The solid content concentration of the aqueous dispersion was determined. The solid content concentration is a total value of the surfactant and the polyester resin.

(7) Content of Organic Solvent in Aqueous Dispersion Gas Chromatograph GC-8A [FI, manufactured by Shimadzu Corporation
D detector used, carrier gas: nitrogen, column packing material (manufactured by GL Sciences): PEG-HT (5%)-
UNIPORT HP (60/80 mesh), column size: diameter 3 mm × 3 m, sample injection temperature (injection temperature): 150 ° C., column temperature: 60 ° C., internal standard substance: n-butanol], and the aqueous dispersion is made into water. What was diluted with was put directly into the apparatus, and the content rate of the organic solvent was obtained. The detection limit was 0.01% by mass. (8) Storage stability of aqueous dispersion 30 ml of the aqueous dispersion was placed in a 50 ml glass sample bottle.
The appearance was visually observed after being placed in a container and stored at 25 ° C. for 60 days.

(9) Volume average particle size of the aqueous dispersion A 0.1% aqueous dilution of MICROTRACUPA (model 9340-UP, manufactured by Nikkiso Co., Ltd.) was used.
The volume average particle size was measured in A). (10) Thickness of resin coating Thickness gauge (MICROFINE manufactured by Union Tool Co., Ltd.
Σ) is used to measure the thickness of the substrate in advance, a resin coating is formed on the substrate using the aqueous dispersion, and then the thickness of the substrate having this resin coating is measured by the same method. The difference was defined as the thickness of the resin coating.

(11) Adhesion of Resin Coating A base type coating device (manufactured by Yasuda Seiki Co., Ltd., film applicator No. 542-AB type, equipped with a bar coater) was used to coat an aqueous water dispersion on a substrate, ℃
By heating for 1 minute in the oven set to
A resin coating with a thickness of approximately 1 μm is formed on the base material, and then the adhesive tape (width 18 mm) specified in JIS Z1522 is attached to the resin coating leaving the end, and an eraser is rubbed over it. After the adhesive tape was adhered to the film, the end of the adhesive tape was formed at a right angle to the film and then peeled off instantaneously. The surface of the peeled adhesive tape was measured by a surface infrared spectroscope (SYSTEM 200 manufactured by Perkin Elmer Co., Ltd.).
0, using a 60 ° Ge × 50 × 20 × 2 mm prism) to examine whether or not the resin coating adheres to the adhesive tape surface, and evaluated the adhesion of the resin coating to the substrate according to the following criteria. . In addition, as the base material, a biaxially stretched PET film (manufactured by Unitika Ltd., thickness 12 μ
m) was used. ◯: No peak derived from the resin coating is observed on the adhesive tape surface. X: A peak derived from the resin coating is recognized on the adhesive tape surface. (12) The above biaxially-stretched PE is prepared by using a water resistant tabletop coating device for resin coating.
Aqueous dispersion is coated on T film, 130 ℃
By heating for 1 minute in the oven set to
After forming a resin film having a thickness of about 1 μm, the PET film having the resin film formed thereon is partially immersed in water at 25 ° C., gently pulled up after 2 hours, and air-dried.
The appearance of the resin film was visually observed and evaluated according to the following criteria. ◯: No change in appearance is observed. X: Whitening or dissolution is partially observed.

(13) Solvent resistance of resin film Using a tabletop type coating device, the above-mentioned biaxially stretched PE is used.
Aqueous dispersion is coated on T film, 130 ℃
By heating for 1 minute in the oven set to
After forming a resin film having a thickness of about 1 μm, the PET film on which the resin film is formed is partially immersed in ethanol at room temperature, gently pulled up after 10 minutes, air-dried, and then the appearance of the resin film Was visually observed and evaluated according to the following criteria. ◯: No change in appearance is observed. X: Whitening or dissolution is partially observed.

The polyester resins used in Examples and Comparative Examples were obtained as follows. [Polyester resin P-1] 2492 g of terephthalic acid, 415 g of isophthalic acid, 1516 g of sebacic acid, 1226 g of ethylene glycol, neopentyl glycol 145
The esterification reaction was carried out by heating a mixture consisting of 8 g in an autoclave at 270 ° C. for 4 hours. Then, after adding 3.3 g of zinc acetate as a catalyst, the temperature of the system was adjusted to 27
The temperature was raised to 0 ° C. and the system pressure was gradually reduced to 13 Pa after 1.5 hours. After continuing the polycondensation reaction for another 4 hours under these conditions, the system was pressurized with nitrogen gas, the resin was discharged into a sheet, and allowed to cool at room temperature to obtain a sheet-shaped polyester resin P-1. It was

[Polyester Resin P-2] Terephthalic Acid 2
A mixture of 907 g, 1246 g of isophthalic acid, 1133 g of ethylene glycol and 1614 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. Next, after adding 3.3 g of zinc acetate as a catalyst, the temperature of the system was raised to 265 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours.
And After continuing the polycondensation reaction for another 4 hours under these conditions, the system was pressurized with nitrogen gas, the resin was discharged in strands, cooled with water, and cut into pellets (diameter about 3 mm, length Polyester resin P-2 (about 3 mm) was obtained.

[Polyester Resin P-3] Terephthalic Acid 4
A mixture of 153 g, 993 g of ethylene glycol and 1849 g of neopentyl glycol was heated in an autoclave at 250 ° C. for 4 hours to carry out an esterification reaction. Then, after adding 3.3 g of zinc acetate as a catalyst, the system temperature was raised to 265 ° C., and the system pressure was gradually reduced to 13 Pa after 1.5 hours. After continuing the polycondensation reaction for another 4 hours under these conditions, the system was pressurized with nitrogen gas, the resin was discharged in strands, cooled with water, and cut into pellets (diameter about 3 mm,
Polyester resin P-3 having a length of about 3 mm was obtained.

[Polyester Resin P-4] Terephthalic Acid 4
A mixture of 153 g, ethylene glycol 388 g and 1,2-propanediol 2565 g was heated in an autoclave at 240 ° C. for 3 hours to carry out an esterification reaction. Then, 3.4 g of tetra-n-butyl titanate was added as a catalyst, and while maintaining 240 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. After continuing the polycondensation reaction for another 4 hours under these conditions, the system was pressurized with nitrogen gas, the resin was discharged in strands, cooled with water, and cut into pellets (diameter about 3 mm, length Polyester resin P-4 (about 3 mm) was obtained.

[Polyester Resin P-5] Terephthalic Acid 2
326 g, isophthalic acid 997 g, ethylene glycol 743 g, neopentyl glycol 831 g, 2,2-
Bis (4-hydroxyethoxyphenyl) propane 189
The mixture consisting of 8 g was heated in an autoclave at 250 ° C. for 4 hours to carry out an esterification reaction. Then, 2.6 g of zinc acetate was added as a catalyst, and the system temperature was adjusted to 26
The temperature was raised to 5 ° C., and the system pressure was gradually reduced to 13 Pa after 1.5 hours. After continuing the polycondensation reaction for another 4 hours under these conditions, the system was pressurized with nitrogen gas, the resin was discharged in strands, cooled with water, and cut into pellets (diameter about 3 mm, length Polyester resin P-5 (about 3 mm) was obtained.

[Polyester Resin P-6] Terephthalic Acid 2
284 g, isophthalic acid 1246 g, adipic acid 548
g, ethylene glycol 1226 g, and neopentyl glycol 1458 g were heated in an autoclave at 250 ° C. for 4 hours to carry out an esterification reaction. Then, after adding 3.3 g of zinc acetate as a catalyst, the system temperature was raised to 265 ° C., and the system pressure was gradually reduced to 13 Pa after 1.5 hours. After continuing the polycondensation reaction for another 4 hours under these conditions, the system was pressurized with nitrogen gas, the resin was discharged in strands, cooled with water, and cut into pellets (diameter about 3 mm,
Polyester resin P-6 having a length of about 3 mm was obtained.

[Polyester Resin P-7] Terephthalic Acid 2
A mixture of 907 g, 1246 g of isophthalic acid, 1133 g of ethylene glycol and 1614 g of neopentyl glycol was heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. Then, after adding 1.8 g of antimony trioxide as a catalyst, the system temperature was adjusted to 28
The temperature was raised to 0 ° C. and the system pressure was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction was further continued, and after 4 hours, the system was brought to normal pressure with nitrogen gas, the temperature of the system was lowered, and when the temperature reached 270 ° C, 26 g of trimellitic acid was added and stirred at 250 ° C for 2 hours. Then, the depolymerization reaction was performed. After that, the resin was discharged in a sheet form while being pressurized with nitrogen gas. Then, after sufficiently cooling this to room temperature, it is crushed with a crusher and opened with a sieve 1 to 1.
A 6 mm fraction was collected, and granular polyester resin P-7
Got as.

Table 1 shows the results of the analysis or evaluation of the properties of the polyester resin obtained as described above.

[0071]

[Table 1]

Example 1 A 3 L polyethylene container was charged with 500 g of polyester resin P-1 and 500 g of MEK, and the container was heated with warm water of about 60 ° C. while stirring with a stirrer (M manufactured by Tokyo Rika Co., Ltd., M
The polyester resin was completely dissolved in MEK by stirring using AZELA 1000) to obtain a polyester resin solution having a solid content concentration of 50% by mass. Next, 400 g of the above polyester resin solution was charged into a glass container with a jacket (content: 2 L), cold water was passed through the jacket to keep the system temperature at 13 ° C., and the mixture was stirred with a stirrer (Tokyo Rika Co., Ltd., MAZELA 1000) (rotation speed.
600 rpm). Then, with stirring, 13.5 g of triethylamine as a basic compound and a surfactant (made by Aldrich, Ige) previously dissolved in water.
100 g of a 10 mass% aqueous solution of palCO720, HLB = 14.2) was added, and subsequently 286.5 g of distilled water at 13 ° C. was added at a rate of 100 g / min. The temperature in the system was always 15 ° C. or lower during the entire addition of distilled water. After the addition of distilled water was completed, the mixture was stirred for 30 minutes to obtain an aqueous dispersion having a solid content concentration of 26 mass%.

Example 2 400 g of polyester resin P-1 and 600 g of MEK were put into a 3 L polyethylene container, and agitator (manufactured by Tokyo Rika Co., Ltd., M
The polyester resin was completely dissolved in MEK by stirring using AZELA 1000) to obtain a polyester resin solution having a solid content concentration of 40% by mass. Next, 500 g of the above polyester resin solution was charged into a glass container with a jacket (content of 2 L), cold water was passed through the jacket to keep the system temperature at 13 ° C., and the mixture was stirred with a stirrer (Tokyo Rika Co., Ltd., MAZELA 1000) (rotation speed.
600 rpm). Then, with stirring, 13.5 g of triethylamine as a basic compound and a surfactant (made by Aldrich, Ige) previously dissolved in water.
100 g of a 10 mass% aqueous solution of palCO720, HLB = 14.2) was added, and subsequently, 386.5 g of distilled water at 13 ° C. was added at a rate of 100 g / min. The temperature in the system was always 15 ° C. or lower during the entire addition of distilled water. After the addition of distilled water was completed, the mixture was stirred for 30 minutes to obtain an aqueous dispersion having a solid content concentration of 21% by mass. Furthermore, this aqueous dispersion 80
0 g and 52.3 g of distilled water were put in a 2 L flask and about 120
The mixture was heated in an oil bath heated to ℃ and desolvated under normal pressure. The solvent removal was terminated when the amount of the distilled off reached about 360 g, cooled to room temperature, and filtered through a 300 mesh stainless steel filter. Next, after measuring the solid content concentration of this aqueous dispersion, distilled water was added so that the solid content concentration was 30% by mass to obtain an aqueous dispersion.

Example 3 In a 3 L polyethylene container, 500 g of polyester resin P-1 and 500 g of MEK were put, and while stirring the container with warm water of about 60 ° C., a stirrer (Tokyo Rika Co., Ltd., M
The polyester resin was completely dissolved in MEK by stirring using AZELA 1000) to obtain a polyester resin solution having a solid content concentration of 50% by mass. Next, 400 g of the above polyester resin solution was charged into a glass container with a jacket (content: 2 L), cold water was passed through the jacket to keep the system temperature at 13 ° C., and the mixture was stirred with a stirrer (Tokyo Rika Co., Ltd., MAZELA 1000) (rotation speed.
600 rpm). Thereafter, while stirring, 13.5 g of triethylamine as a basic compound and a surfactant (Cedran FF-180, manufactured by Sanyo Kasei Co., Ltd., HLB = 11.1.
15 g of 7) was added, and subsequently 371.5 g of distilled water at 13 ° C. was added at a rate of 100 g / min. The temperature in the system was always 15 ° C. or lower during the entire addition of distilled water. After the addition of distilled water was completed, the mixture was stirred for 30 minutes to obtain an aqueous dispersion having a solid content concentration of 27% by mass.

Example 4 400 g of polyester resin P-1 and 600 g of MEK were placed in a 3 L polyethylene container, and the container was heated with warm water of about 60 ° C. while stirring with a stirrer (Made by Tokyo Rika Co., Ltd., M
The polyester resin was completely dissolved in MEK by stirring using AZELA 1000) to obtain a polyester resin solution having a solid content concentration of 40% by mass. Next, 500 g of the above polyester resin solution was charged into a glass container with a jacket (content of 2 L), cold water was passed through the jacket to keep the system temperature at 13 ° C., and the mixture was stirred with a stirrer (Tokyo Rika Co., Ltd., MAZELA 1000) (rotation speed.
600 rpm). Then, with stirring, 13.5 g of triethylamine as a basic compound and a surfactant (Cedran FF-180, manufactured by Sanyo Kasei Co., Ltd., HLB = 1)
15 g of 1.7) was added, and subsequently 471.5 g of distilled water at 13 ° C. was added at a rate of 100 g / min. The temperature in the system was always 15 ° C. or lower during the entire addition of distilled water.
After adding distilled water, stir for 30 minutes to obtain a solid content of 22
A mass% aqueous dispersion was obtained. Furthermore, this aqueous dispersion 6
00g and 39.5g of distilled water were put in a 1L flask, and about 50
The solvent was removed under reduced pressure by heating in an oil bath heated to ℃. About the solvent removal, the mass of (flask + aqueous dispersion) is about 2
It ends when 70 g of weight is reduced, and after cooling to room temperature, 30
It was filtered with a 0 mesh stainless steel filter. Next, after measuring the solid content concentration of this aqueous dispersion, distilled water was added so that the solid content concentration would be 30% by mass to obtain an aqueous dispersion.

Example 5 Example 4 was repeated except that dimethylaminoethanol was used as the basic compound, the addition amount was 11.9 g, and 473.1 g of distilled water at 13 ° C. was added at a rate of 100 g / min. An aqueous dispersion having a solid content concentration of 30% by mass was obtained by the same method as described in.

Example 6 The organic solvent was changed from MEK to MEK / isopropanol = 9 /
An aqueous dispersion having a solid content concentration of 30 mass% was obtained by the same method as in Example 4 except that the amount was changed to 1 (mass ratio).

Example 7 Surfactant was manufactured by Sanyo Kasei Co., Ltd., Sannonic FD-
An aqueous dispersion having a solid content concentration of 30% by mass was obtained in the same manner as in Example 4 except that the content was changed to 80 (HLB = 11.7).

Example 8 An aqueous dispersion having a solid content concentration of 30% by mass was obtained in the same manner as in Example 4, except that the polyester resin was changed to P-2.

Example 9 The polyester resin was changed to P-3, 11.9 g of triethylamine was added, and the temperature was 100 ° C./min at 13 ° C.
An aqueous dispersion having a solid content concentration of 30% by mass was obtained by the same method as in Example 4 except that 473.1 g of distilled water in Example 2 was added.

Example 10 The polyester resin was changed to P-4, 19.5 g of triethylamine was added, and the mixture was heated at 13 ° C. at a rate of 100 g / min.
Example 4 except that 465.5 g of distilled water in Example 4 was added.
An aqueous dispersion having a solid content concentration of 30% by mass was obtained by the same method as described in.

Example 11 An aqueous dispersion was obtained in the same manner as in Example 4, except that the polyester resin was changed to P-5.

Example 12 A dispersion having a solid content concentration of 30% by mass was obtained in the same manner as in Example 4, except that the polyester resin was changed to P-6.

Example 13 The polyester resin was changed to P-7, 17.3 g of triethylamine was added, and 13 ° C. was added at a rate of 100 g / min.
An aqueous dispersion having a solid content concentration of 30% by mass was obtained in the same manner as in Example 4 except that 467.7 g of distilled water in Example 2 was added.

Comparative Example 1 The same operation as in Example 3 was repeated except that the amount of triethylamine added was changed to 6.3 g (equivalent ratio 7 of basic compound).
When 478.7 g of distilled water at 13 ° C. was added at a rate of g / min, the polyester resin was entangled with the stirring blades during the addition of distilled water, and a uniform aqueous dispersion could not be obtained.

Comparative Example 2 The same operation as in Example 3 was carried out without adding Cedran FF-180. When the stirring was stopped, the polyester resin was precipitated and a uniform aqueous dispersion could not be obtained. .

Comparative Example 3 The same operation as in Example 3 was repeated except that triethylamine was not added and Cedran FF-180 (45 g) was added.
When 455 g of distilled water at 3 ° C. was added, the polyester resin was entangled with the stirring blades during the addition of distilled water, and a uniform aqueous dispersion could not be obtained.

Comparative Example 4 The same operation as in Example 4 was repeated except that the amount of triethylamine added was changed to 36.1 g (equivalent ratio of basic compound: 40).
448.9 g of distilled water at 13 ° C at a rate of 00 g / min
When added, the polyester resin was precipitated during the solvent removal step, and a uniform aqueous dispersion could not be obtained.

Comparative Example 5 In Example 4, when distilled water was added to the polyester resin solution, the temperature inside the system was always kept at 48 to 50 ° C., and the polyester resin was precipitated during the solvent removal step.
No uniform aqueous dispersion was obtained.

Comparative Example 6 45 g of Cedran FF-180 was used, and 100 g / mi
An aqueous dispersion having a solid content concentration of 30% by mass was obtained by the same method as in Example 4 except that 455 g of distilled water at 13 ° C. was added at a rate of n.

In Table 2, used in Examples and Comparative Examples,
The ratio of the surfactant to the polyester resin, the equivalent ratio of the basic compound to the total molar amount of the carboxyl groups of the polyester, the values on the left and right sides of the formula (1), the acid value of the polyester resin, the content of the organic solvent, and the obtained value. The results of examination on the volume average particle diameter of the aqueous dispersion, the storage stability of the aqueous dispersion, the adhesion of the resin coating, the water resistance and the solvent resistance are shown. In addition, the content rate of the organic solvent was calculated from the charged amount at the time of dispersion when the solvent was not removed, and the content rate was determined from the measurement result by gas chromatography when the solvent was removed.

[0092]

[Table 2]

From the above examples and comparative examples, the polyester resin aqueous dispersion of the present invention is excellent in storage stability only when a basic compound and a surfactant are allowed to coexist, and a resin film formed from the same is obtained. It can be seen that the adhesiveness to the substrate, water resistance, and solvent resistance are excellent. When the proportion of the surfactant is high, the adhesiveness, water resistance and solvent resistance of the resin coating deteriorate. It is also understood that by controlling the temperature during phase inversion emulsification, an aqueous dispersion having good storage stability can be obtained even if the amount of surfactant used is small.

[0094]

The polyester resin aqueous dispersion of the present invention can form a resin film having excellent adhesion to a substrate, water resistance, and solvent resistance. Therefore, it can be used alone as a paint, coating agent or adhesive. Alternatively, it can be suitably used as a binder component by mixing other components, such as PET film, polyolefin film, vapor deposition film, anchor coating agent for various films and adhesiveness imparting agent (easy adhesion), aluminum plate, steel plate and plated steel plate, Anchor coating agent for various metal plates, adhesiveness imparting agent (easy adhesion), precoat metal paint, paper coating agent, fiber treatment agent, adhesive agent for bonding substrates such as paper, metal plate, resin sheet, ink It can be used for applications such as binders, to improve their performance.

[Brief description of drawings]

FIG. 1 shows the acid value of polyester resin in the dispersion step,
It is a figure which shows the relationship of the equivalent ratio of the required basic compound with respect to the total molar amount of the carboxyl group of polyester resin.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Sachiko Kokuryo             4-1-3 Kutaro-cho, Chuo-ku, Osaka City, Osaka Prefecture             Unitika Corporation Osaka Head Office F-term (reference) 4F070 AA47 AC46 AE14 AE15 CA02                       CB03 CB15                 4J002 AB032 AB042 AB052 AD012                       AD022 BE022 BG012 BJ002                       CF031 CF041 EN026 EN036                       EN106 EU236 FD140 FD310                       FD312 GH01 GJ01

Claims (5)

[Claims] 1. A polyester resin (A) having an acid value of less than 8 mgKOH / g, a basic compound (B) and a compound (C) having a surfactant or a protective colloid action, and (A) and ( The mass ratio with (C) is (C) / (A) = 0.
A polyester resin aqueous dispersion, which is 1/100 to 20/100. 2. The volume average particle diameter of the polyester resin is 500.
2. The polyester resin aqueous dispersion according to claim 1, which has a thickness of not more than nm. 3. A solution of a polyester resin (A) in an organic solvent is dispersed in water together with a basic compound (B) and a surfactant or a compound (C) having a protective colloid action, and an aqueous dispersion is obtained by phase inversion emulsification. The method for producing, wherein the phase inversion emulsification is performed at 40 ° C. or lower, and the method for producing the polyester resin aqueous dispersion according to claim 1 or 2. 4. The method for producing a polyester resin aqueous dispersion according to claim 3, wherein the amount of the basic compound used is in a range satisfying the following formula (1). −1.375 × C + 11.5 ≦ D ≦ −5 × C + 50 (1) [In the formula (1), C is the acid value (mgKOH / g) of the polyester resin (A), and D is the basic compound (B). )of,
The equivalent ratio to the total molar amount of the carboxyl groups of the polyester resin (A) is shown. ] 5. The method for producing a polyester resin aqueous dispersion according to claim 3, further comprising a step of removing the organic solvent after the phase inversion emulsification.