JP2006182950A - Polyester resin aqueous dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin aqueous dispersion which is excellent in storage stability and can form a resin coating film excellent in coating film performance such as adhesiveness to a base material, water resistance and solvent resistance (particularly, solvent resistance to halogenated organic solvents and aromatic organic solvents). <P>SOLUTION: The polyester resin aqueous dispersion is prepared by dispersing in an aqueous medium a polyester resin comprising a polyhydric alcohol component containing 15-60 mol% of a diol compound represented by general formula (1) and a polybasic acid component containing 50 mol% or more of an aromatic polybasic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous polyester resin dispersion that can be applied to various substrates to form a resin film having excellent film performance.

  Polyester resin is a film-forming resin that is excellent in film processability, resistance to organic solvents (solvent resistance), weather resistance, adhesion to various substrates, etc., so it can be used in paints, inks, adhesives, and coating agents. It is used in large quantities as a binder component in such fields.

  In recent years, the use of organic solvents has been tending to be restricted from the standpoints of environmental protection, resource conservation, dangerous goods regulations by the Fire Service Act, and workplace environment improvement. Development of an aqueous polyester resin dispersion in which is finely dispersed in an aqueous medium has been actively conducted.

For example, Patent Documents 1 to 4 propose a polyester resin aqueous dispersion in which a polyester resin having a low acid value and a high molecular weight is dispersed in an aqueous medium. When such an aqueous dispersion is used, processability, water resistance, It describes that a film excellent in performance such as solvent resistance can be formed. However, the resin film formed from the aqueous polyester resin dispersion described in these documents has excellent solvent resistance to alcohol-based organic solvents, but has resistance to halogen-based organic solvents and aromatic organic solvents. There was a problem that it was not enough.
JP-A-9-296100 JP 2000-26709 A JP 2000-313793 A JP 2002-173582 A

  Under such circumstances, the subject of the present invention is excellent in storage stability, adhesion to a substrate, water resistance and solvent resistance (particularly solvent resistance to halogenated organic solvents and aromatic organic solvents), etc. Another object of the present invention is to provide an aqueous polyester resin dispersion capable of forming a resin film having excellent film performance.

  As a result of diligent research to solve the above problems, the present inventors have found that a resin film obtained from an aqueous dispersion of a polyester resin containing a specific polyhydric alcohol component and having a controlled polybasic acid component. The present inventors have found that the solvent resistance to halogen-based organic solvents and aromatic organic solvents is excellent, and have completed the present invention.

That is, the present invention provides a diol compound represented by the general formula (1) in which a polyester resin comprising at least a polyhydric alcohol component and a polybasic acid component is dispersed in an aqueous medium. Polyester resin aqueous dispersion characterized by containing 15 to 60 mol% of polyhydric alcohol component and 50 mol% or more of aromatic polybasic acid as polybasic acid component based on the total amount of polybasic acid component body;

The aqueous polyester resin dispersion of the present invention can form a resin film excellent in film performance such as adhesion to a substrate, water resistance and solvent resistance. Therefore, the polyester resin aqueous dispersion of the present invention may be used alone, for example, as a paint, a coating agent or an adhesive in applications requiring such coating performance, or may be mixed with other components to form a binder. It may be used as an ingredient. Specifically, the polyester resin aqueous dispersion of the present invention is an anchor coating agent and an adhesion-imparting agent (easy adhesion) for various films such as PET films, polyolefin films, and vapor-deposited films; various types such as aluminum plates, steel plates, and plated steel plates. Anchor coating agent and adhesion-imparting agent (easy adhesion) for metal plates; pre-coated metal paints, paper coating agents or fiber treatment agents; adhesives for bonding substrates such as paper, metal plates and resin sheets; and inks These binders can be used for the purpose of improving their performance.
Further, since the aqueous polyester resin dispersion of the present invention has excellent solvent resistance to halogenated organic solvents and aromatic organic solvents, in dry cleaning using such organic solvents, the image receiving part of a printing part such as clothing is received. It can be suitably used as a layer or as a binder component of ink or toner.
Examples of the printing method include a melt transfer method, an ink jet method, and an electrophotographic method.

  The aqueous polyester resin dispersion of the present invention (hereinafter sometimes simply referred to as “aqueous dispersion”) is a liquid material containing a polyester resin dispersed in an aqueous medium. Here, the aqueous medium is a medium composed of a liquid containing water, and may contain a basic compound or an organic solvent described later. Further, “dispersed and contained” means that the polyester resin is suspended as particles in an aqueous medium, and a part thereof may be dissolved in the aqueous medium.

  In the present invention, the polyester resin dispersed in the aqueous medium is obtained by polycondensation of at least a specific polyhydric alcohol component and a specific polybasic acid component.

で表されるジオール化合物（以下、ジオール化合物（１）という）を、多価アルコール成分全量に対して１５〜６０モル％含み、好ましくは２０〜６０モル％、より好ましくは２５〜５０モル％、最も好ましくは３０〜４０モル％で含む。ポリエステル樹脂が構成成分としてジオール化合物（１）を上記範囲内で含有することにより、水性分散体の貯蔵安定性および樹脂皮膜の基材への密着性および耐水性が向上するだけでなく、樹脂被膜の耐溶剤性、特にハロゲン系有機溶剤や芳香族系有機溶剤への耐溶剤性が向上する。ポリエステル樹脂を構成する多価アルコール成分に占めるジオール化合物（１）の割合が少なすぎる場合には、有機溶剤、ハロゲン系溶剤や芳香族系有機溶剤への耐溶剤性が劣る場合がある。一方で、多すぎる場合には、重合性が悪くなり高分子量のポリエステル樹脂を得ることが困難になる。 The polyhydric alcohol component constituting the polyester resin is represented by the general formula (1);

Is contained in an amount of 15 to 60 mol%, preferably 20 to 60 mol%, more preferably 25 to 50 mol%, based on the total amount of the polyhydric alcohol component. Most preferably, it is contained at 30 to 40 mol%. When the polyester resin contains the diol compound (1) as a constituent component within the above range, not only the storage stability of the aqueous dispersion, the adhesion of the resin film to the substrate and the water resistance are improved, but also the resin film. Solvent resistance, especially resistance to halogenated organic solvents and aromatic organic solvents is improved. When the proportion of the diol compound (1) in the polyhydric alcohol component constituting the polyester resin is too small, the solvent resistance to an organic solvent, a halogen-based solvent or an aromatic organic solvent may be inferior. On the other hand, if the amount is too large, the polymerizability becomes poor and it is difficult to obtain a high molecular weight polyester resin.

  The chemical name of the diol compound (1) is bis [4- (hydroxyethoxy) phenyl] sulfone, and this compound is SE-2 from Meisei Chemical Co., Ltd., and SEO-2 from Nikka Chemical Co., Ltd. Available as BS-EO from Konishi Chemical Co., Ltd.

  The polyhydric alcohol component other than the diol compound (1) constituting the polyester resin is not particularly limited as long as it is a compound having two or more hydroxyl groups per molecule, for example, an aliphatic glycol having 2 to 10 carbon atoms, C6-C12 alicyclic glycol, ether bond containing glycol, etc. are mentioned.

  Specific examples of the aliphatic glycol having 2 to 10 carbon atoms include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 2-methyl-1,3-propane. Diol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, etc. It is done.

Specific examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol.
Specific examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polytetramethylene glycol, polyethylene glycol, and polypropylene glycol. In addition, since the water resistance of a polyester resin, solvent resistance, a weather resistance, etc. may fall when an ether bond increases, the ratio of the ether bond containing glycol containing glycol to the polyhydric alcohol component of a polyester resin is 10 mol%. Or less, more preferably 5 mol% or less.

  Further, bisphenols (such as bisphenol A) such as 2,2-bis (4-hydroxyethoxyphenyl) propane and ethylene oxide or propylene oxide adducts thereof can also be used as the polyhydric alcohol component.

  Furthermore, as a polyhydric alcohol component, a trifunctional or higher functional alcohol component such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like may be contained, but in order to suppress gelation at the time of polyester resin production The ratio of the trifunctional or higher polyhydric alcohol in the polyhydric alcohol component of the polyester resin is preferably 10 mol% or less, and more preferably 5 mol% or less.

  As the polyhydric alcohol component other than the diol compound (1), ethylene glycol and neopentyl glycol are preferable because they are industrially produced in large quantities and are inexpensive, and these are preferably used alone or in combination.

  In the present invention, the polybasic acid component constituting the polyester resin is an aromatic polybasic acid in an amount of 50 mol% or more, preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%, based on the total amount of the polybasic acid component. More preferably 80 to 100 mol%, still more preferably 90 to 100 mol%, most preferably 100 mol%. In the present invention, when the polybasic acid component contains the aromatic polybasic acid in a proportion within the above range, the processability, solvent resistance, water resistance, workability, hardness, and the like of the resulting resin film are improved. Furthermore, since the ratio of the aromatic polybasic acid is increased within the above range, the ratio of the aromatic ester bond that is harder to hydrolyze than the aliphatic or alicyclic ester bond to the resin skeleton increases. An aqueous dispersion using a polyester resin can suppress a decrease in molecular weight even when stored for a long period of time, and the storage stability is further improved. When the ratio of the aromatic polybasic acid in the polybasic acid component of the polyester resin is too small, the solvent resistance to halogenated solvents and aromatic organic solvents may be poor.

  Examples of the aromatic polybasic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid. And trifunctional or higher aromatic carboxylic acids such as trimellitic anhydride, pyromellitic anhydride, benzophenone anhydride tetracarboxylic acid, trimesic acid and the like. In order to suppress gelation during the production of the polyester resin, the proportion of the trifunctional or higher aromatic carboxylic acid in the polybasic acid component of the polyester resin is preferably 10 mol% or less, and preferably 5 mol% or less. Is more preferable.

  Two or more kinds of aromatic polybasic acids may be included in combination, and in that case, the total ratio thereof may be within the above range.

  Among the above-mentioned aromatic polybasic acids, terephthalic acid and isophthalic acid are preferable because they are industrially produced in large quantities and are inexpensive, and it is preferable to use them alone or in combination. The total proportion of terephthalic acid and isophthalic acid in the polybasic acid component of the polyester resin is preferably 50 mol% or more, more preferably 60 to 100 mol%, further preferably 70 to 100 mol%, more preferably 80 to 100 mol. % Is particularly preferable, 90 to 100 mol% is more particularly preferable, and 100 mol% is most preferable.

  Moreover, as a ratio of the terephthalic acid which occupies for the polybasic acid component of a polyester resin, it is preferable that it is 30 mol% or more, It is more preferable that it is 40-100 mol%, It is further that it is 50-100 mol% 60 to 100 mol% is particularly preferable, and 70 to 100 mol% is most preferable. By increasing the proportion of terephthalic acid in the polybasic acid component of the polyester resin, the film performance such as hardness, solvent resistance, and processability of the resin coating is improved more effectively, and further, the resulting aqueous dispersion is stored. The stability tends to be further improved.

Examples of the polybasic acid component other than the aromatic polybasic acid constituting the polyester resin include aliphatic polybasic acids and alicyclic polybasic acids.
Among aliphatic polybasic acids, aliphatic dicarboxylic acids include succinic acid, succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, hydrogenated dimer acid, etc. Examples thereof include dicarboxylic acids and unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and dimer acid.

  Among the alicyclic polybasic acids, the alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornene dicarboxylic acid and anhydride Products, tetrahydrophthalic acid and anhydrides thereof.

  In addition, tribasic or higher polybasic acids other than aromatic polybasic acids such as ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), 1,2,3,4-butanetetracarboxylic Although the acid etc. may be contained, in order to suppress gelation at the time of polyester resin manufacture, the ratio of the polybasic acid more than trifunctional in the polybasic acid component of a polyester resin is 10 mol% or less Preferably, it is 5 mol% or less.

  In addition, as long as the object of the present invention can be achieved, a polybasic acid component having a carboxyl group such as 5-sodium sulfoisophthalic acid or a hydrophilic group other than a hydroxyl group can be used as the polybasic acid component. Since the water resistance of the resin coating formed from the body tends to deteriorate, it is preferable not to use such a polybasic acid component.

The polyester resin may be copolymerized with monocarboxylic acid, monoalcohol, hydroxycarboxylic acid, such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, stearyl alcohol, 2-phenoxyethanol, ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxybenzoic acid and the like can be used.
These compounds are preferably 4 mol% or less, particularly preferably 2 mol% or less, based on all monomer components constituting the polyester resin.

  In the present invention, the acid value of the polyester resin is preferably 2 to 40 mgKOH / g, more preferably 3 to 30 mgKOH / g, still more preferably 4 to 25 mgKOH / g, and 5 to 20 mgKOH / g. It is particularly preferred that When the acid value exceeds 40 mgKOH / g, the molecular weight of the polyester resin tends to be small, the processability of the resin film tends to deteriorate, and the water resistance may be insufficient. Moreover, when the acid value is less than 2 mgKOH / g, it tends to be difficult to obtain a stable aqueous dispersion.

  Further, the polyester resin may contain a hydroxyl group as long as the water resistance of the resin film is not impaired, and the hydroxyl value is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, More preferably, it is 10 mgKOH / g or less.

  The number average molecular weight of the polyester resin is preferably 2,000 to 50,000, more preferably 3,000 to 40,000, still more preferably 4,000 to 30,000, It is especially preferable that it is 000-20,000. If the number average molecular weight is less than 2,000, the processability of the resin film tends to be insufficient. When the number average molecular weight exceeds 50,000, it tends to be difficult to obtain an aqueous dispersion.

  The degree of dispersion of the molecular weight distribution of the polyester resin is not particularly limited. However, since the storage stability of the aqueous dispersion tends to be excellent, the degree of dispersion of the molecular weight distribution is preferably 8 or less, more preferably 6 or less, and 4 or less. More preferred is 3 or less. Here, the degree of dispersion of the molecular weight distribution is a value obtained by dividing the weight average molecular weight by the number average molecular weight.

  The glass transition temperature of the polyester resin (hereinafter sometimes simply referred to as “Tg”) is also not particularly limited, but is preferably 0 to 120 ° C. because the storage stability of the aqueous dispersion tends to be excellent. -110 degreeC is more preferable, 40-100 degreeC is more preferable, and 60-90 degreeC is especially preferable.

  In the present invention, the polyester resin can be produced by polycondensing at least the polybasic acid component and the polyhydric alcohol component by a known method. For example, all the monomer components and / or low polymers thereof are reacted at 180 to 260 ° C. for about 2.5 to 10 hours under an inert atmosphere to carry out an esterification reaction, followed by 130 Pa in the presence of a transesterification catalyst. Examples thereof include a method of obtaining a polyester resin by proceeding a polycondensation reaction under the following reduced pressure at a temperature of 220 to 280 ° C. until a desired molecular weight is reached.

In the case of imparting a desired acid value or hydroxyl value to the polyester resin, a method in which a polybasic acid component or a polyhydric alcohol component is further added following the polycondensation reaction, and depolymerization is performed in an inert atmosphere. Can be mentioned.
Examples of a method for imparting a desired acid value to the polyester resin include a method in which a polybasic acid anhydride is further added following the polycondensation reaction, and an addition reaction is performed with a hydroxyl group of the polyester resin in an inert atmosphere.

  When the depolymerization and / or addition reaction is performed using a polybasic acid component or a polyhydric alcohol component, the content ratio of the polyester resin constituent components such as the diol compound (1) and the aromatic polybasic acid is determined by depolymerization and / or Or the ratio regarding the total polybasic acid component or polyhydric alcohol component containing the polybasic acid component and polyhydric alcohol component used for addition reaction should just be in the said range, respectively. For example, when depolymerization is performed using a polybasic acid component, the proportion of aromatic polybasic acid, the total proportion of terephthalic acid and isophthalic acid, and the proportion of terephthalic acid are the polybasic acid components used for depolymerization. The ratio with respect to all the polybasic acid components containing each should just be in the said range, respectively. Further, for example, when depolymerization is performed using a polyhydric alcohol component, the ratio of the diol compound (1) is within the above range with respect to the total polyhydric alcohol components including the polyhydric alcohol component used for depolymerization. I just need it.

The polyester resin of the present invention is preferably a polyester resin having a carboxyl group introduced by the above depolymerization and / or addition reaction using a polybasic acid. By introducing a carboxyl group by depolymerization and / or addition reaction, the molecular weight and acid value of the polyester resin can be easily controlled.
Examples of the polybasic acid used in the depolymerization and / or addition reaction include the polybasic acid components described in the constituent components of the polyester resin. Among them, aromatic polybasic acids are preferable, and among the aromatic polybasic acids. The aromatic dicarboxylic acid terephthalic acid, isophthalic acid, phthalic anhydride, and trifunctional polybasic acid trimellitic acid and trimellitic anhydride are preferable.

Next, the aqueous dispersion of the present invention will be described.
The aqueous dispersion of the present invention is a liquid material containing the above-described polyester resin dispersed in an aqueous medium.
The content of the polyester resin dispersed in the aqueous medium is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and 10 to 40% by mass with respect to the total amount of the aqueous dispersion. More preferably, it is more preferably 15 to 35% by mass. If the content of the polyester resin is less than 1% by mass, it is not practical. If it exceeds 60% by mass, the viscosity of the aqueous dispersion becomes very high, and it may be difficult to form a resin film substantially.

The aqueous medium is a medium made of a liquid containing water, and may contain an organic solvent or a basic compound.
The content of the organic solvent contained in the aqueous dispersion may be damaged by the organic solvent in the aqueous dispersion depending on the working environment and the type of the coating material. It is preferably small, specifically, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and more preferably 5% by mass with respect to the total amount of the aqueous dispersion. % Or less is particularly preferable, and 1% by mass or less is most preferable.

As the organic solvent, known ones can be used, for example, ketone organic solvents, aromatic hydrocarbon organic solvents, ether organic solvents, halogen-containing organic solvents, alcohol organic solvents, ester organics. A solvent, a glycol type organic solvent, etc. are mentioned.
Examples of the ketone organic solvent include methyl ethyl ketone (2-butanone) (hereinafter referred to as MEK), 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 and the like.

Examples of the aromatic hydrocarbon organic solvent include toluene, xylene, benzene and the like.
Examples of the ether organic solvent include dioxane and tetrahydrofuran.
Examples of the halogen-containing organic solvent include carbon tetrachloride, trichloromethane, dichloromethane and the like.
Examples of the alcohol organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl. Examples include alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol.

Examples of the ester organic solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate. Examples thereof include diethyl carbonate and dimethyl carbonate.
Examples of the glycol organic solvent include 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. And diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate and the like.

In addition to the above organic solvents, other organic solvents can be used, for example, organic compounds such as 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, and ethyl acetoacetate. A solvent is mentioned.
These organic solvents described above can be used alone or in combination of two or more.

  Among these organic solvents, those having a solubility in water at 20 ° C. of 5 g / L or more are preferably used, and more preferably 10 g / L or more. When the solubility of the organic solvent in water is less than 5 g / L, the aqueous dispersion may cause phase separation, which is not preferable.

  Moreover, as a boiling point of an organic solvent, 250 degrees C or less is preferable, 150 degrees C or less is more preferable, and 100 degrees C or less is further more preferable. When the boiling point exceeds 250 ° C., it tends to be difficult to volatilize the organic solvent by drying from the resin film.

  Further, from the viewpoint of easy removal of the organic solvent from the aqueous dispersion, it is preferable to use an organic solvent having a boiling point of 100 ° C. or lower or an organic solvent azeotropic with water. N-propanol, isopropanol, n-butanol, MEK, MIBK, tetrahydrofuran, dioxane, cyclohexanone, ethylene glycol monobutyl ether and the like can be suitably used.

  The water contained in the aqueous dispersion is not particularly limited, and distilled water, ion exchange water, city water, industrial water, and the like can be used, but it is preferable to use distilled water or ion exchange water.

  The volume average particle size of the aqueous dispersion of the present invention, that is, the volume average particle size of the polyester resin dispersed and contained in the aqueous medium is preferably 400 nm or less, more preferably 300 nm or less. Further, it is more preferably 200 nm or less, particularly preferably 150 nm or less, and most preferably 100 nm or less. When the volume average particle diameter exceeds 400 nm, the polyester resin in the obtained aqueous dispersion tends to settle, which is not preferable.

The aqueous dispersion of the present invention preferably contains a basic compound. By the basic compound, the carboxyl group of the polyester resin is neutralized to generate a carboxyl anion, and the polyester resin is stably dispersed without agglomeration due to the electric repulsive force between the anions.
As the basic compound, inorganic bases such as sodium hydroxide and potassium hydroxide can also be used. However, an organic amine having a boiling point of 250 ° C. or lower, preferably 160 ° C. or lower from the viewpoint of being easily volatilized at the time of resin film formation, Or ammonia is preferable. 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, Examples include diethanolamine, triethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine. Among them, ammonia, triethylamine, N, N It is preferred to use dimethyl ethanolamine.
A basic compound can be used individually or in combination of 2 or more types.

  The content of the basic compound in the aqueous dispersion is not particularly limited as long as it is an amount that can partially neutralize the carboxyl group of the polyester resin, but the content of the basic compound is the total moles of carboxyl groups of the polyester resin. It is preferably 0.5 to 20 times equivalent to the amount, more preferably 0.8 to 10 times equivalent, still more preferably 0.9 to 5 times equivalent, and 1 to 2 times equivalent. It is particularly preferred that When the content of the basic compound is less than 0.5 times equivalent, the polyester resin may settle during storage of the aqueous dispersion, and when it exceeds 20 times equivalent, the viscosity of the aqueous dispersion is remarkably high. As a result, the workability may deteriorate.

Next, the manufacturing method of the aqueous dispersion of this invention is demonstrated.
The production method of the aqueous dispersion of the present invention includes 1) a method in which a polyester resin is dissolved in an organic solvent, and water is added to the polyester resin solution to obtain an aqueous dispersion. 2) a polyester resin, a basic compound, and an organic material. Examples include a method in which an aqueous dispersion is obtained by charging a solvent and water all at once into a container and heating the system while stirring.

First, the manufacturing method 1) will be described.
The production method 1) substantially comprises two steps, a dissolution step and a phase inversion emulsification step, and a solvent removal step is added as necessary. The dissolution step is a step of dissolving the polyester resin in an organic solvent, and the phase inversion emulsification step is a step of dispersing the polyester resin solution dissolved in the organic solvent in water together with the basic compound. The solvent removal step is a step of removing a part or all of the organic solvent used in the polyester resin dissolving step out of the system from the obtained aqueous dispersion.

  In the dissolving step, the polyester resin is dissolved in an organic solvent. At this time, it is preferable to make the density | concentration of the polyester resin in the solution obtained into the range of 10-70 mass% with respect to the solution whole quantity, the range of 20-60 mass% is more preferable, and the range of 30-50 mass% is more preferable. Particularly preferred. When the concentration of the polyester resin in the solution exceeds 70% by mass, in the next phase inversion emulsification step, the viscosity increases greatly when mixed with water, and the aqueous dispersion obtained from such a state is The volume average particle size tends to increase, which is not preferable in terms of storage stability. In addition, 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 phase inversion emulsification step, or a large amount of organic solvent is removed during the solvent removal step. It is an economy. An apparatus for dissolving the polyester resin in the organic solvent is not particularly limited as long as it includes a tank into which a liquid can be charged and can be appropriately stirred. Moreover, when the polyester resin is difficult to dissolve, it may be heated. In addition, the polyester resin used at a melt | dissolution process may be individual, or may mix and use 2 or more types.

  As the organic solvent, those described above can be used singly or in combination of two or more, but in order to obtain the aqueous dispersion of the present invention, the polyester resin can be dissolved by 10% by mass or more. It is preferable to select an organic solvent. Examples of such organic solvents include 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, cyclohexane Non / isopropanol mixture solution or the like can be suitably used.

  In the phase inversion emulsification step, the polyester resin solution obtained in the dissolution step is mixed with the water and the basic compound to perform phase inversion emulsification. In the present invention, it is preferable to carry out phase inversion emulsification by adding a basic compound to the polyester resin solution and gradually adding water thereto. Also, when the rate of water addition is high, a mass of polyester resin is formed, which tends to no longer disperse in the aqueous medium, resulting in a poor yield of the resulting aqueous dispersion, Not economical. In the present invention, “phase inversion emulsification” means that an amount (mass) of water exceeding the amount (mass) of organic solvent contained in this solution is added to an organic solvent solution of the polyester resin, so that more water is contained than the organic solvent. It means that the polyester resin is dispersed in the liquid phase.

  The phase inversion emulsification step is preferably performed at 40 ° C. or less, more preferably at 30 ° C. or less, further preferably at 20 ° C. or less, and particularly preferably at 15 ° C. or less. By performing the phase inversion emulsification step at 40 ° C. or less, the volume average particle size of the obtained aqueous dispersion becomes small, and an aqueous dispersion excellent in storage stability can be obtained. In addition, in the solvent removal step to be described later, it is possible to suppress the formation of a polyester resin precipitate caused by the aggregation of the aqueous dispersion, and as a result, the yield is improved and it is economical. The apparatus for performing the phase inversion emulsification step is not particularly limited as long as it includes a tank into which a liquid can be charged and can be appropriately stirred. Examples of such an apparatus include apparatuses widely known to those skilled in the art as a solid / liquid stirring apparatus and an emulsifier (for example, a homomixer). When using a high shearing emulsifier such as a homomixer, the liquid temperature may rise due to shear heat, so it is preferable to use it while cooling. The phase inversion emulsification step may be performed under normal pressure, reduced pressure, or increased pressure.

Next, the production method 2) will be described.
An apparatus is provided that is equipped with a tank into which a liquid can be charged and that can appropriately stir a mixture of an aqueous medium and a polyester resin powder or granular material charged into the tank. As such a device, a device widely known to those skilled in the art as a solid / liquid stirring device or an emulsifier can be used. Usually, a simple lid is provided and used under normal pressure or slight pressure. However, if necessary, an apparatus capable of pressurization of 0.1 MPa or more can be used.

  An aqueous medium composed of water, a basic compound and an organic solvent, and a granular or powdered polyester resin are put into the tank of this apparatus, and are preferably coarsely dispersed by stirring and mixing at a temperature of 40 ° C. or lower. At this time, when the shape of the polyester resin is a sheet or a large lump that is difficult to coarsely disperse, the following heating process may be performed. Next, the temperature in the tank is preferably 45 ° C or higher, more preferably (Tg-20) ° C or higher of the polyester resin, and further preferably (Tg-10) ° C or higher of the polyester resin, preferably 15 to 120. The aqueous dispersion of the present invention can be obtained by making the polyester resin sufficiently aqueous by continuing stirring for a minute and then cooling to 40 ° C. or lower, preferably with stirring.

  The content of the organic solvent and the content of the basic compound in the aqueous medium used are particularly within the ranges in which the organic solvent content and the basic compound content in the aqueous dispersion are achieved, respectively. Not limited. In particular, the content of the organic solvent in the aqueous medium is such that the organic solvent content in the aqueous dispersion is achieved without desolvation, considering that the organic solvent can be removed in the solvent removal step described below. It may be larger than this value. The organic solvent content in the aqueous medium used in the production method 2) is usually 10 to 50% by mass, preferably 15 to 40% by mass, and more preferably 20 to 30% by mass with respect to the total amount of the aqueous medium. It is. Moreover, the basic compound content in the said aqueous medium is 0.5-2 mass% normally with respect to the aqueous medium whole quantity, Preferably it is 0.8-1.5 mass%.

As a heating method in the tank, heating from the outside of the tank is preferable. For example, external heating is performed using an oil bath or a water bath, or a tank is provided with a jacket, and the oil or water heated in the jacket is provided. A method of externally heating the inside of the tank can be exemplified by flowing the water.
Examples of the cooling method in the tank include a method of naturally cooling at room temperature and a method of cooling using 0 to 40 ° C. oil or water in the above heating method. The cooling is preferably performed while stirring the aqueous dispersion. When the aqueous dispersion is cooled without stirring, a polyester resin film may be formed on the liquid surface of the aqueous dispersion (surface in contact with air), which is not preferable.

  The aqueous dispersion thus obtained is added with a solvent removal step as necessary. The solvent removal step is a step of removing a part or all of the organic solvent used in the polyester resin dissolving step and the organic solvent contained in the aqueous medium from the obtained aqueous dispersion.

Specifically, the solvent removal step is a step of removing a part or all of the organic solvent contained in the aqueous dispersion obtained by the production methods 1) and 2) from the aqueous dispersion by distillation. This step can be performed under reduced pressure or normal pressure. When solvent is removed under normal pressure, agglomerates are likely to be generated. In such a case, it is carried out under reduced pressure so that the internal temperature is 70 ° C. or lower, preferably 60 ° C. or lower, more preferably 50 ° C. or lower. It is good to adjust to. As an apparatus for performing the solvent removal step, any apparatus may be used as long as it has a tank into which a liquid can be introduced and can be appropriately stirred. In addition, by performing a solvent removal process, a part or all of the basic compound which is contained in the aqueous dispersion and does not contribute to neutralization of the polyester resin can be removed.
By such a production method, the aqueous dispersion of the present invention is in a uniform state in which a solid content concentration such as precipitation and phase separation is not found locally in the aqueous medium and locally different from other parts. can get.

  As the production method of the present invention, the production method of 2) is preferable because the amount of the organic solvent to be used can be reduced.

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

Next, a method for 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 can be uniformly coated on the surface of various substrates by known film forming methods such as dipping method, brush coating method, spray coating method, curtain flow coating method and the like. Then, after setting it at around room temperature as necessary, it is subjected to heat treatment for drying and baking, whereby a uniform resin film can be formed in close contact with the surfaces of various substrates. As a heating device at this time, a normal hot air circulation type oven, an infrared heater, or the like may be used. In addition, the heating temperature and the heating time are appropriately selected depending on the type of the substrate to be coated, etc., but considering the economy, the heating temperature is preferably 60 to 250 ° C., 70 -230 degreeC is more preferable, and 80-200 degreeC is especially preferable. The heating time is preferably 1 second to 30 minutes, more preferably 5 seconds to 20 minutes, and particularly preferably 10 seconds to 10 minutes.

  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, more preferably 0.1 to 30 μm, 0.5-20 micrometers is especially preferable.

  The aqueous dispersion of the present invention includes a curing agent, various additives, a surfactant, a compound having a protective colloid effect, a water-soluble polymer, water, an organic solvent, titanium oxide, zinc white, carbon black, and the like. Pigments; dyes; other water-based polyester resins, water-based urethane resins, water-based olefin resins, water-based resins such as water-based acrylic resins; and the like.

  The curing agent is not particularly limited as long as it is a functional group possessed by a polyester resin, for example, a curing group having reactivity with a carboxyl group or its anhydride and hydroxyl group, such as urea resin, melamine resin, benzoguanamine resin, etc. Examples thereof include amino resins, polyfunctional epoxy compounds, polyfunctional isocyanate compounds and various block isocyanate compounds thereof, polyfunctional aziridine compounds, carbodiimide group-containing compounds, oxazoline group-containing polymers, and phenol resins. One of these curing agents may be used, or two or more may be used in combination.

  Examples of additives include repellency inhibitors, leveling agents, antifoaming agents, anti-waxing agents, rheology control agents, pigment dispersants, ultraviolet absorbers, and lubricants.

Examples of the surfactant include all surfactants such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
Examples of the nonionic surfactant include alkylene oxide adducts of alkylphenols such as nonylphenol and octylphenol, and alkylene oxide adducts of higher alcohols. Examples of such nonionic surfactants include, for example, the Igepal series manufactured by Aldrich; Narrow Acty series such as Narrow Acty N-100, Narrow Acty N-120 and Narrow Acty N-140 manufactured by Sanyo Chemical Co., Ltd. Sannonic SS series such as Sannonic SS-120, Sannonic SS-90, Sannonic SS-70, Sannonic FD-140, Sannonic FD-100, Sannonic FD series such as Sannonic FD-80, Cedran FF-220, Cedran FF-210, Cedran FF series such as Cedran FF-200, Cedran FF-180, Cedran SNP series such as Cedran SNP-112, New Pole such as New Pole PE-64, New Pole PE-74, New Pole PE75 E-Series, Sanmorin 11, and the like.

  Examples of the compound having a protective colloid effect include vinyl alcohol, polyethylene oxide, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, modified starch, polyvinylpyrrolidone, polyacrylic acid, acrylic acid and / or methacrylic acid as a component. Examples thereof include polymerized monomers, polyitaconic acid, gelatin, gum arabic, casein, and swellable mica.

  Examples of the organic solvent include the organic solvents described above. By adding an organic solvent to the aqueous dispersion of the present invention, the content of the organic solvent contained in the aqueous dispersion can be increased to 98% by mass with respect to the total amount of the aqueous dispersion.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
(1) Composition of polyester resin
^It calculated | required from < ¹ > H-NMR analysis (The product made by Varian, 300MHz). In addition, with respect to a resin containing a constituent monomer that does not have an assignable / quantifiable peak on the ¹ H-NMR spectrum, it was subjected to methanol decomposition at 230 ° C. for 3 hours in a sealed tube, and then subjected to gas chromatogram analysis for quantitative analysis. Went.
(2) Acid value of polyester resin 0.5 g of polyester resin was dissolved in 50 ml of water / dioxane = 1/9 (volume ratio), titrated with KOH using cresol red as an indicator, and the amount of KOH consumed for neutralization. A value obtained by converting the number of mg per 1 g of the polyester resin was determined as an acid value.

(3) Hydroxyl value of the polyester resin 3 g of the polyester resin is precisely weighed, added with 0.6 ml of acetic anhydride and 50 ml of pyridine, stirred at room temperature for 48 hours, and then reacted with 5 ml of distilled water. By further stirring for 6 hours at room temperature, all acetic anhydride that was not used in the above reaction was changed to acetic acid. Add 50 ml of dioxane to this solution, titrate with KOH using cresol red / thymol blue as an indicator, and the amount of KOH consumed for neutralization (W ₁ ) and the amount of acetic anhydride initially charged with the polyester resin. From the amount of KOH required for neutralization (calculated value: W ₀ ) when acetic acid is completely used without reaction, the difference (W ₀ -W ₁ ) is obtained in mg of KOH, and this is calculated. The value divided by the number of grams of the polyester resin was taken as the hydroxyl value.

(4) Number average molecular weight and weight average molecular weight of the polyester resin The number average molecular weight is determined by GPC analysis (liquid feeding unit LC-10ADvp type and UV-visible spectrophotometer SPD-6AV type manufactured by Shimadzu Corporation), detection wavelength: 254 nm , Solvent: tetrahydrofuran, converted to polystyrene). In addition, the dispersion degree of molecular weight distribution can be calculated | required as a value which remove | divided the weight average molecular weight by the number average molecular weight.
(5) Glass transition temperature of the polyester resin 10 mg of the polyester resin is used as a sample, and measured using a DSC (Differential Scanning Calorimetry) device (DSC7 manufactured by PerkinElmer Co., Ltd.) at a temperature rising rate of 10 ° C./min. An intermediate value of two bending point temperatures derived from the glass transition in the temperature rising curve was determined, and this was taken as the glass transition temperature (Tg).

(6) Solid Content Concentration of Aqueous Dispersion About 1 g of the aqueous dispersion was weighed (Xg), and the mass of the residue (solid content) after drying at 150 ° C. for 2 hours was weighed (Yg) ), And the solid content concentration was determined by the following formula.
Solid content concentration (% by mass) = Y × 100 / X
(7) Content of organic solvent in aqueous dispersion For the aqueous dispersion E-9 obtained in Example 6, the content of the organic solvent in the aqueous dispersion was determined as follows.
Gas chromatograph GC-8A manufactured by Shimadzu Corporation [using FID detector, 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], an aqueous dispersion diluted with water was directly charged into the apparatus. The organic solvent content was determined. The detection limit was 0.01% by mass.
In addition, about the aqueous dispersion E-1 to E-5 and E-6 to E-8, the content rate of the organic solvent was computed from the preparation composition at the time of aqueous dispersion manufacture.

(8) Storage Stability of Aqueous Dispersion 30 ml of the aqueous dispersion was placed in a 50 ml glass sample bottle and stored at 38 ° C., and the number of days until the aqueous dispersion lost its fluidity (solidified) was examined. In addition, the thing which does not solidify after 50 days preservation | save was set as (circle). Those that solidified in less than 50 days of storage indicated the number of days of storage when solidified. The longer the number of days that can be stored without solidification is, the better. If it is 30 days or longer, there is no practical problem.
(9) Volume average particle diameter of aqueous dispersion The aqueous dispersion was diluted to 0.1% with water, and the volume average particle diameter was measured using MICROTRAC UPA (model 9340-UPA) manufactured by Nikkiso.
(10) Thickness of resin film After measuring the thickness of the base material in advance using a thickness meter (manufactured by Union Tool, MICROFINE Σ), and forming the resin film on the base material using an aqueous dispersion The thickness of the substrate having this resin film was measured by the same method, and the difference was taken as the thickness of the resin film.

(11) Adhesion of resin coating Using a tabletop coating device (manufactured by Yasuda Seiki, film applicator No. 542-AB, equipped with bar coater), an aqueous dispersion is coated on the substrate and set to 150 ° C. By heating for 3 minutes in an oven, a resin film having a thickness of about 1 μm was formed on the substrate. Next, the adhesive tape (width 18 mm) specified in JIS Z1522 is pasted on the resin coating leaving an end, and then the adhesive tape is rubbed with an eraser and adhered sufficiently, and then the end of the adhesive tape is applied to the film. It was peeled off instantaneously after making a right angle to it. By analyzing the peeled adhesive tape surface with a surface infrared spectrometer (using a Perkin-Elmer SYSTEM2000, Ge60 ° 50 × 20 × 2 mm prism), it is determined whether or not a resin film is attached to the adhesive tape surface. And the adhesion of the resin film to the substrate was evaluated according to the following criteria. As a base material, a metal plate (tin-free steel plate) having a thickness of 0.19 mm was used.
○: No peak derived from the resin film is observed on the adhesive tape surface.
X: A peak derived from the resin film is observed on the adhesive tape surface.

(12) Water resistance of resin coating Using a tabletop coating device, the aqueous dispersion is coated on a 0.19 mm thick metal plate (tin-free steel plate) and heated in an oven set at 150 ° C for 3 minutes. As a result, a resin film having a thickness of about 1 μm was formed. Thereafter, the metal plate on which the resin film is formed is immersed in hot water at 60 ° C., gently lifted after 10 minutes and air-dried, and then the appearance of the resin film is visually observed and evaluated according to the following criteria. did.
○: No change in appearance is observed, and there is no practical problem.
(Triangle | delta): Whitening is seen partially and there exists a problem in practical use.

(13) Solvent resistance of resin film Using a tabletop coating apparatus, an aqueous dispersion is coated on a metal plate (tin-free steel plate) having a thickness of 0.19 mm, and is placed in an oven set at 150 ° C. for 3 minutes. By heating, a resin film having a thickness of about 1 μm was formed. Thereafter, the resin film was rubbed with a cotton swab impregnated with an organic solvent, and one reciprocation was performed once, and the number of times until the resin film dissolved and the metal surface was exposed was examined. As the organic solvent, tetrachloroethylene (halogen organic solvent), isopropyl alcohol, and xylene (aromatic organic solvent) were used.
In addition, when the metal surface was not exposed even after rubbing 50 times, it was described as “> 50”.
Moreover, it was judged that there was no practical problem if the solvent resistance was 10 times or more.

The polyester resins used in Examples and Comparative Examples were obtained as follows.
[Polyester resin P-1]
A mixture consisting of 2367 g of terephthalic acid, 789 g of isophthalic acid, 1168 g of ethylene glycol, 1009 g of neopentyl glycol, and 1929 g of bis [4- (hydroxyethoxy) phenyl] sulfone is heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. It was. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under these conditions, the polycondensation reaction was continued, and after 8 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 250 ° C., 158 g of isophthalic acid was added as a depolymerizing agent, and 2 at 250 ° C. The depolymerization reaction was performed by stirring for a period of time. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-1.

[Polyester resin P-2]
A mixture consisting of 1736 g of terephthalic acid, 1420 g of isophthalic acid, 1168 g of ethylene glycol, 1009 g of neopentyl glycol and 1929 g of bis [4- (hydroxyethoxy) phenyl] sulfone is heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. It was. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under these conditions, the polycondensation reaction was continued, and after 8 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 250 ° C., 158 g of isophthalic acid was added as a depolymerizing agent, and 2 at 250 ° C. The depolymerization reaction was performed by stirring for a period of time. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-2.

[Polyester resin P-3]
A mixture consisting of 1736 g of terephthalic acid, 1420 g of isophthalic acid, 1168 g of ethylene glycol, 1009 g of neopentyl glycol and 1929 g of bis [4- (hydroxyethoxy) phenyl] sulfone is heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. It was. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under these conditions, the polycondensation reaction was continued, and after 8 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when the temperature reached 250 ° C., 120 g of trimellitic acid was added as a depolymerizing agent. The depolymerization reaction was performed by stirring for 2 hours. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-3.

[Polyester resin P-4]
A mixture of 789 g of terephthalic acid, 2367 g of isophthalic acid, 1168 g of ethylene glycol, 1009 g of neopentyl glycol, and 1929 g of bis [4- (hydroxyethoxy) phenyl] sulfone is heated in an autoclave at 260 ° C. for 4 hours for esterification reaction. It was. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under these conditions, the polycondensation reaction was continued, and after 8 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 250 ° C., 158 g of isophthalic acid was added as a depolymerizing agent, and 2 at 250 ° C. The depolymerization reaction was performed by stirring for a period of time. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-4.

[Polyester resin P-5]
A mixture of 1736 g of terephthalic acid, 1420 g of isophthalic acid, 849 g of ethylene glycol, 1049 g of neopentyl glycol, and 965 g of bis [4- (hydroxyethoxy) phenyl] sulfone was heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. It was. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction was continued, and after 8 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when 250 ° C. was reached, 132 g of isophthalic acid was added as a depolymerizing agent. The depolymerization reaction was performed by stirring for a period of time. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-5.

[Polyester resin P-6]
A mixture of 947 g terephthalic acid, 473 g isophthalic acid, 1309 g 1,4-cyclohexanedicarboxylic acid, 416 g adipic acid, 1168 g ethylene glycol, 1009 g neopentyl glycol, 1929 g bis [4- (hydroxyethoxy) phenyl] sulfone in an autoclave, The esterification reaction was carried out by heating at 260 ° C. for 4 hours. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under these conditions, the polycondensation reaction was continued, and after 8 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 250 ° C., 158 g of isophthalic acid was added as a depolymerizing agent, and 2 at 250 ° C. The depolymerization reaction was performed by stirring for a period of time. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-6.

[Polyester resin P-7]
A mixture of 1736 g of terephthalic acid, 1420 g of isophthalic acid, 849 g of ethylene glycol, 1049 g of neopentyl glycol and 643 g of bis [4- (hydroxyethoxy) phenyl] sulfone is heated in an autoclave at 260 ° C. for 4 hours to carry out an esterification reaction. It was. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under these conditions, the polycondensation reaction was continued. After 8 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when 250 ° C. was reached, 126 g of isophthalic acid was added as a depolymerizing agent. The depolymerization reaction was performed by stirring for a period of time. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-7.

[Polyester resin P-8]
Esterification reaction by heating a mixture of 2367 g of terephthalic acid, 789 g of isophthalic acid, 719 g of ethylene glycol, 871 g of neopentyl glycol and 1803 g of 2,2-bis (4-hydroxyethoxyphenyl) propane at 260 ° C. for 4 hours. Went. Next, 1.5 g of antimony trioxide was added as a catalyst, the temperature of the system was raised to 280 ° C., and the pressure of the system was gradually reduced to 13 Pa after 1.5 hours. Under this condition, the polycondensation reaction was continued, and after 4 hours, the system was brought to atmospheric pressure with nitrogen gas, the temperature of the system was lowered, and when it reached 250 ° C., 158 g of isophthalic acid was added as a depolymerizing agent. The depolymerization reaction was performed by stirring for a period of time. Thereafter, the resin was discharged in a sheet while being pressurized with nitrogen gas. And after fully cooling to room temperature, this was grind | pulverized with the crusher, the fraction of 1-6 mm of openings was extract | collected using the sieve, and it obtained as granular polyester resin P-8.

Table 1 shows the results of analyzing the characteristics of the polyester resin obtained as described above.
In addition, the polyester resin in this invention is P-1 to P-5.

Using the above polyester resin, an aqueous dispersion of the present invention was obtained by the following method.
Example 1
10. 300 g of polyester resin P-1, 140 g of isopropyl alcohol, and 11 g of a stirrer equipped with a jacketed 2 liter glass container that can be sealed (Toki Robotics, manufactured by Tokushu Kika Kogyo Co., Ltd.) When 2 g of triethylamine and 548.8 g of ion-exchanged water were charged into a glass container and stirred at a rotational speed of the stirring blade (homodisper) at 7000 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was completely suspended It was confirmed that it was in a state. Therefore, while maintaining this state, hot water was passed through the jacket after 10 minutes. Then, the system temperature was kept at 70 to 75 ° C. and further stirred for 1 hour. Thereafter, cold water is allowed to flow through the jacket, the rotational speed is lowered to 5000 rpm, the mixture is cooled to room temperature (about 25 ° C.) with stirring, and the undispersed granular polyester resin is removed by filtration through a 250 mesh stainless steel filter. As a result, an aqueous dispersion E-1 was obtained.

(Examples 2-5, Comparative Examples 1-3)
Aqueous dispersions E-2 to E-8 were obtained by carrying out the same operations as in Example 1 with the charge composition shown in Table 2.

(Example 6)
500 g of the aqueous dispersion E-1 obtained in Example 1 and 132 g of ion-exchanged water were placed in a 1 liter glass two-necked flask and mixed well. A Liebig condenser was installed in the flask, and the contents were heated to 90-100 ° C. at normal pressure with stirring in an oil bath to distill off isopropyl alcohol and water. When the amount of distillation reached 148 g, the heating was stopped and the mixture was cooled to room temperature (about 25 ° C.). After cooling, the mixture was filtered with a 250 mesh stainless steel filter to obtain an aqueous dispersion E-9.
In addition, the content rate of the organic solvent (isopropanol) of the aqueous dispersion E-9 was 0.3 mass%.

  Table 3 shows the results of examining the characteristic values and performances of the aqueous dispersions obtained in the examples and comparative examples. The adhesion, water resistance, and solvent resistance of the resin film of the aqueous dispersion E-9 were evaluated using an aqueous dispersion obtained by adding 5 g of ethylene glycol monobutyl ether to 100 g of the aqueous dispersion E-9.

From the above Examples and Comparative Examples, it can be seen that the aqueous polyester resin dispersion of the present invention is excellent in solvent resistance, particularly solvent resistance to halogenated organic solvents and aromatic organic solvents.
Furthermore, it turns out that it is excellent also in storage stability, adhesiveness, and water resistance.

Claims (2)

A polyester resin comprising at least a polyhydric alcohol component and a polybasic acid component is dispersed in an aqueous medium, and the diol compound represented by the general formula (1) is used as the polyhydric alcohol component. An aqueous polyester resin dispersion comprising 15 to 60 mol% of the total amount and containing 50 mol% or more of an aromatic polybasic acid as the polybasic acid component based on the total amount of the polybasic acid component;

The polyester resin aqueous dispersion according to claim 1, wherein the polyester resin contains terephthalic acid as a polybasic acid component in an amount of 30 mol% or more based on the total amount of the polybasic acid component.