JPH08295791A - Aqueous polyester resin dispersion - Google Patents

Abstract

PURPOSE: To obtain an aq. polyester resin dispersion having a good shelf stability and forming a coating film excellent in water resistance, solvent resistance, hardness or strength, and heat resistance. CONSTITUTION: This dispersion comprises (A) a polyester resin having a softening point of 40 to 200 deg.C and a no.-average mol.wt. of 5,000 to 30,000 and (B) a polyester resin having a no.-average mol.wt. of 3,000 to 10,000 and obtd. from a polycarboxylic acid component contg. 5-20mol% metal sulfonate group- contg. arom. dicarboxylic acid and a polyol component, and is dispersed in an aq. medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of polyester resin, and more specifically, it has good storage stability, water resistance, solvent resistance, hardness or strength,
And a polyester resin aqueous dispersion which forms a film excellent in heat resistance.

[0002]

As a polyester resin aqueous dispersion,
(1) A mixture of an organic solvent and water contains 0.5 to 10 mol% of a metal sulfonate-containing aromatic dicarboxylic acid as a water-dispersible polycarboxylic acid component, and a molecular weight of 2,500 to
A polyester resin aqueous dispersion (Japanese Patent Publication No. 61-58092) obtained by dissolving or dispersing a polyester resin having a softening point of 30,000 and a softening point of 40 to 200 ° C. is known.

Further, (2) a polyester resin obtained by using 1 to 5 mol% of an ester-forming sulfonic acid metal salt monomer with respect to a carboxylic acid component and a diol component and containing an organic solvent once. Substantially solvent-free polyester resin aqueous dispersion obtained by producing an aqueous resin dispersion and distilling off the organic solvent from the aqueous dispersion under normal pressure or reduced pressure (JP-B-64).
-10547) is known.

(3) A method for producing a water-dispersible polyester resin, wherein the water-dispersible polyester resin has both a metal sulfonate-containing aromatic dicarboxylic acid and a polyethylene glycol segment (Japanese Patent Publication No. 47-4).
No. 0873) is also known.

Further, as a polyester resin aqueous dispersion comprising a plurality of different polyester resins, (4) any of the aqueous dispersions containing crystalline and amorphous polyester resins capable of forming an aqueous dispersion (Japanese Patent Publication No. 60- 1334
Gazette) and (5) a carboxyl group-containing molecular weight of 1,
000-10,000 polyester resin and molecular weight 10,
An aqueous dispersion of a polyester resin partially reacted with 000 to 100,000 hydrophobic polyester resins (Japanese Patent Publication No. 6-99662) is known.

[0006]

However, among polyester resin aqueous dispersions obtained by using an organic solvent or the like, water-dispersible polyester resins such as those disclosed in Japanese Patent Publication No. 61-58092 are organic. Those that are simply dispersed in an aqueous medium containing a solvent, the stability as a dispersion depends on the presence of an organic solvent, and unstable when the composition of the medium changes due to evaporation of the aqueous medium or dilution with water. In some cases, it may become a very high viscosity, coalesce the dispersion particles, etc., to form a sediment, or to form agglomerates.

It is obtained by dissolving or dispersing a water-dispersible polyester resin in an aqueous medium containing an organic solvent such as THF as disclosed in Japanese Patent Publication No. 64-10547 and then distilling off the organic solvent. Polyester resin aqueous dispersion, the finally obtained aqueous dispersion is substantially only water as a medium, the water-dispersible polyester resin has a sufficient affinity for organic solvents, In addition, it is necessary to have an appropriate affinity for an aqueous medium containing an organic solvent and water, and water resistance and solvent resistance tend to be insufficient.

A water-dispersible polyester resin having both a metal sulfonate-containing aromatic dicarboxylic acid and a polyethylene glycol segment as disclosed in JP-B-47-40873 can be easily dissolved or dispersed in water. However, such a water-dispersible polyester resin tends to have poor water resistance. Further, the inclusion of a polyethylene glycol segment in the polymer skeleton has the drawbacks that it is difficult to obtain a water-dispersible polyester having a high glass transition point, the formed film is easily sticky, and the strength is low.

An aqueous dispersion containing a crystalline or non-crystalline polyester resin as disclosed in JP-B-60-1334 requires a large amount of hydrophilic component to disperse the crystalline polyester. The water resistance tends to be poor, and the stability of the dispersion particles tends to be poor due to the crystalline component.

Further, a partially reacted polyester resin having a carboxyl group and a hydrophobic high molecular weight polyester resin as disclosed in Japanese Patent Publication No. 6-99662 are two types of polyesters during the production thereof. Not only the resin binding reaction, but also the high molecular weight polyester resin is decomposed by hydrolysis or transesterification reaction, so that sufficient water resistance or film strength cannot be obtained without using a crosslinking agent.

An object of the present invention is to provide a polyester resin aqueous dispersion that solves the above problems.

[0012]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent studies in order to solve various drawbacks of the conventional techniques as described above. As a result, two specific polyester resins are dispersed in an aqueous medium. The inventors have found that a polyester resin aqueous dispersion having good storage stability, and forming a film excellent in water resistance, solvent resistance, hardness or strength, and heat resistance can be obtained, and completed the present invention. .

That is, the present invention has a softening point of 40 to 200.
A polyester resin (A) having a number average molecular weight of 5,000 to 30,000, a polycarboxylic acid component containing 5 to 20 mol% of a metal sulfonate-containing aromatic dicarboxylic acid and a polyol component having a molecular weight of 3,000. ~ 10,000
The polyester resin (B) is dispersed in an aqueous medium (C) to provide a polyester resin aqueous dispersion.

The polyester resin aqueous dispersion of the present invention comprises
It forms a film having good storage stability and excellent water resistance, solvent resistance, hardness or strength, and heat resistance.

The polyester resin (A) contained in the aqueous polyester resin dispersion of the present invention has a softening point of 40 to 200.
It is necessary to have a temperature of 5,000 and a number average molecular weight of 5,000 to 30,000. Because the polyester resin (A)
Among the constituent components of the polyester resin aqueous dispersion of the present invention, it is a component that mainly exhibits water resistance, solvent resistance, hardness or strength, and heat resistance performance, and is present in the aqueous dispersion as the core of the dispersion particles. are doing. When the softening point is lower than 40 ° C or when the number average molecular weight is less than 5,000,
This is because a film having sufficient physical properties described above is not formed. When the softening point is higher than 200 ° C. or the number average molecular weight is higher than 30,000, it is difficult to obtain an aqueous dispersion having good storage stability, and a film may not be formed.

The polyester resin (B) contained in the polyester resin aqueous dispersion of the present invention comprises a polycarboxylic acid component containing 5 to 20 mol% of a metal sulfonate-containing aromatic dicarboxylic acid and a number average of a polyol component. It must have a molecular weight of 3,000 to 10,000. This is because the polyester resin (B) is a component that mainly exhibits storage stability in the constituent components of the polyester resin aqueous dispersion of the present invention, and a part thereof wraps the polyester resin (A), or ( It exists in the form of adhering to the periphery of A), and a part thereof exists in a state of being dissolved or dispersed in an aqueous medium. When the amount of the sulfonic acid metal group-containing aromatic dicarboxylic acid is less than 5 mol%, the storage stability may be poor, or the aqueous dispersion itself may not be obtained. When the sulfonic acid metal group-containing aromatic dicarboxylic acid is more than 20 mol%, the viscosity of the obtained aqueous dispersion may be very high, or the formed film may have poor water resistance. is there. Further, when the number average molecular weight is less than 3,000, the water resistance of the film formed by the aqueous dispersion becomes poor, and the physical properties exhibited by the polyester (A) are also deteriorated. Become. Number average molecular weight is 10,
If it is 000 or more, the storage stability of the aqueous dispersion may be inferior.

As long as the polyester resins (A) and (B) of the present invention satisfy the requirements of (A) or (B) disclosed in the present invention, two or more kinds of polyester resins having different components are used. It may be composed of a group consisting of That is, the polyester resin (A) has a softening point of 40 to 200 ° C. and a number average molecular weight of 5,000 to 30,000.
The polyester resin (B) may be composed of one type or two or more types of the polyester resin of
Is an aromatic dicarboxylic acid containing a metal sulfonate group of 5 to
It may be composed of one type or two or more types of a polyester resin having a number average molecular weight of 3,000 to 10,000 and comprising a polycarboxylic acid component and a polyol component contained in an amount of 20 mol%.

The polyester resin (A) has a softening point of 40 to
It is not particularly limited as long as it is a polyester resin having a number average molecular weight of 5,000 to 30,000 at 200 ° C., but does not contain a metal sulfonate-containing aromatic dicarboxylic acid or contains 4 mol% or less. It is preferable that the polyester resin is composed of a polycarboxylic acid component and a polyol component. In this case, the aqueous medium (C) further has a number average molecular weight of 32 to 300 and an sp value of 8.5.
It is preferable that the main component is water containing the organic compound of 15 at a concentration of 50% by weight or less. When this requirement is satisfied, an aqueous dispersion of polyester resin having good storage stability, a formed film having excellent solvent resistance, high strength, and particularly good water resistance can be obtained.

The polyester resin aqueous dispersion of the present invention comprises
Further, the ratio of the polyester resins (A) and (B) to the aqueous medium (C) is (B) / {(A) + (B)} = 5 to 50% by weight {(A) + (B)} / {(A) + (B) + (C)} = 5
It is preferable to satisfy the formula of ˜50 wt%.

When the value represented by the above formula (B) / {(A) + (B)} is less than 5% by weight, the resulting aqueous dispersion has poor storage stability, or, more significantly, the aqueous dispersion. You may not get your body. On the other hand, when it is more than 50% by weight, the viscosity of the obtained aqueous dispersion may be very high, or the formed film may have poor water resistance.

The above expression {(A) + (B)} / {(A) +
The value represented by (B) + (C)} may be 5% by weight or less for convenience in use, but the polyester resin aqueous dispersion of the present invention has a solid content of about 5% by weight. The viscosity cannot be so high that it cannot be handled normally, and too low a solid content concentration not only wastes transportation and storage costs, but also increases the drying process when the aqueous dispersion is put to use. It is not preferable because it consumes extra energy and time. On the other hand, if it is more than 50% by weight, the viscosity of the aqueous dispersion may be very high.

The aqueous medium (C) contained in the polyester resin aqueous dispersion of the present invention is a liquid medium containing water as a main component. The composition of this aqueous medium depends on the characteristics of the polyester resins (A) and (B), mainly on the content of the sulfonic acid metal group-containing dicarboxylic acid, and the characteristics of the resulting aqueous dispersion, particularly the average particle size of the dispersion. It may be adjusted so that the viscosity becomes a desired value.

In the present invention, the number average molecular weight of the polyester resin means the number average molecular weight measured by gel permeation chromatography using dimethylformamide containing LiBr at a concentration of 10 mmol / l (mmol / l) as a mobile phase. Say.

In the present invention, the softening point of the polyester resin means the softening point measured according to the method specified in ASTM (E28-58T). The polyester resins (A) and (B) of the present invention can be synthesized by a conventionally known method.

The above preferred polyester resin (A)
Can be synthesized, for example, by the method shown below,
It is not limited to those shown in this example. The water-dispersible polyester resin having a group represented by the general formula —SO ₃ M can be obtained by reacting the following polycarboxylic acid component and the following polyol component by a known method in a known manner.
That is, in the presence or absence of a catalyst in an inert gas atmosphere, each of the above-mentioned polycarboxylic acid component and polyol component is preferably heated to 180 to 300 ° C. for esterification or transesterification reaction, and then reduced pressure The target polyester resin (A) is prepared by polycondensing underneath.

Instead of polycondensing under reduced pressure, this step is eliminated or the organic compound consisting of an aliphatic hydrocarbon and / or an aromatic hydrocarbon or a mixture thereof is refluxed and then the organic compound is added. The target polyester resin (A) is also prepared by distilling it out of the system.

First of all, a typical example of a dicarboxylic acid containing a metal sulfonate as a polycarboxylic acid component will be described.
4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and metal salts thereof, and the condensable dicarboxylic acid derivatives thereof can also be used. it can. As the metal salt, Li, Na, K, Mg, Ca,
Examples include salts such as Cu and Fe. Particularly preferred is 5-sodium sulfoisophthalic acid or dimethyl 5-sodium sulfoisophthalate.

As the polycarboxylic acid component other than the above,
For example, terephthalic acid, isophthalic acid, o-phthalic acid,
Aromatic dicarboxylic acids other than sulfonic acid metal group-containing dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid,
Aliphatic dicarboxylic acids such as 2,2-dimethylglutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid and itaconic acid, 1,3-cyclopentanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydro-o-phthalic acid, hexahydro-
Alicyclic dicarboxylic acids such as o-phthalic acid, tetrachloro-o-phthalic acid, het acid, and hymic acid (“Himimic acid” is a product of Hitachi Chemical Co., Ltd., a registered trademark of the same), and condensation of these is possible. Derivatives can be used. These polycarboxylic acids can be used alone or as a mixture of two or more.

In addition, a total of 1 in all polycarboxylic acid components
If it is 0 mm% or less, fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid and eleostearic acid, p-hydroxybenzoic acid , Hydroxybenzoic acids such as p- (2-hydroxyethoxy) benzoic acid and salicylic acid, trifunctional or higher functional polycarboxylic acids such as trimellitic acid and pyromellitic acid, and condensable derivatives thereof can be used.

On the other hand, examples of the polyol component include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol and 1,6-hexane. Glycol, 2,7-dimethyl-4,7-octanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2
Aliphatic diol such as 4-trimethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol, 1,3-cyclohexanedimethanol, 1,4- Alicyclic diols such as cyclohexanedimethanol, 1,4-dihydroxyethoxybenzene, aromatic diols such as ethylene oxide or propylene oxide adducts of bisphenol A, and the like are used, and these are used as one kind or a mixture of two or more kinds. be able to.

It is more preferable to use the aliphatic glycol having a carbon number of 4 or less in an amount of 10 mol% or more in the total polyol component of the polyester resin. Further, various polyols having three or more functional groups such as glycerin, trimethylolpropane and pentaerythritol can be used as long as they are 10 mol% or less of the polyol component in the polyester resin.

Typical examples of the above catalysts include antimony oxide, barium oxide,
Zinc acetate, manganese acetate, cobalt acetate, zinc succinate,
Examples thereof include zinc borate, cadmium formate, lead monoxide, calcium silicate, dibutyltin oxide, butylhydroxytin oxide, tetraisopropyl titanate, tetrabutyl titanate, magnesium methoxide and sodium methoxide. Further, the above polycondensation is preferably carried out under a reduced pressure condition of 0.1 to 10 mm (mmHg) of mercury.

The above preferred polyester resin (B)
Can be synthesized, for example, by the method shown below,
It is not limited to those shown in this example. The above-mentioned polycarboxylic acid component and polyol component can be made known and reacted by a conventional method to obtain a water-dispersible polyester resin having a group represented by the general formula —SO ₃ M. That is, in the presence or absence of a catalyst in an inert gas atmosphere, each of the above-mentioned polycarboxylic acid component and polyol component is preferably heated to 180 to 300 ° C. for esterification or transesterification reaction, and then, The target polyester resin (B) is prepared by polycondensation under reduced pressure.

Instead of polycondensing under reduced pressure, this step is eliminated or the organic compound consisting of an aliphatic hydrocarbon and / or an aromatic hydrocarbon or a mixture thereof is refluxed and then the organic compound is added. The target polyester resin (B) is also prepared by distilling it out of the system.

As the polycarboxylic acid component of the polyester resin (B), a dicarboxylic acid containing a metal sulfonate group similar to that shown in the example of the polyester resin (A),
Alternatively, a condensable dicarboxylic acid derivative thereof, and an aromatic dicarboxylic acid other than the sulfonic acid metal group-containing aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a condensable derivative thereof can be used. Fatty acids, hydroxybenzoic acids, or polycarboxylic acids having three or more functional groups and their condensable derivatives can be used as long as they are 40 mol% or less in total in all polycarboxylic acid components.

Examples of the polyol component include the same aliphatic diols, alicyclic diols, and aromatic ring diols as shown in the examples of the polyester resin (A). As long as it is 40 mol% or less of the polyol component, various tri- or higher functional polyols such as glycerin, trimethylolpropane and pentaerythritol can be used.

The polyester resin aqueous dispersion of the present invention comprises
The polyester resin (A) and (B) obtained as described above is made into fine particles and (B) wraps (A), or (B) is attached to the periphery of (A) in an aqueous medium. It was prepared to be present in.

Such an aqueous polyester resin dispersion can be prepared, for example, by the following method.
It is not limited to those shown in these examples. The polyester resin (A) or (B), which has been previously melt-mixed at a temperature equal to or higher than the softening point of the higher softening point, is 60 to 140 in the aqueous medium (C).
The polyester resin aqueous dispersion is obtained by heating to ° C.

Polyester resin (A) and (B)
And 5 to 40% by weight of the aqueous medium (C) based on the total weight of (A) and (B) are mixed in advance and further diluted with the aqueous medium (C) to obtain a polyester resin aqueous dispersion. .

Polyester resins (A) and (B) each crushed are treated with 60 in an aqueous medium (C).
Heat to ~ 140 ° C to obtain an aqueous polyester resin dispersion. The polyester resin (B) is mixed in advance with the aqueous medium (C), and the polyester resin (A) is added to the mixture and heated to 60 to 140 ° C. to obtain a polyester resin aqueous dispersion.

Water was added to a mixture of the polyester resins (A) and (B) with an organic compound having a number average molecular weight of 32 to 300 and an sp value of 8.5 to 15 in advance to obtain a polyester resin aqueous dispersion. .

Various mixing devices of a polyester resin (A) premixed with an organic compound having a number average molecular weight of 32 to 300 and an sp value of 8.5 to 15 and a polyester resin (B) premixed with water. Then, an aqueous dispersion of polyester resin is obtained by using an emulsifying and dispersing device. Further, if necessary, the organic compound is distilled off from the aqueous dispersion under normal pressure or reduced pressure.

For example, the polyester resin aqueous dispersion obtained as in the above example is further subjected to the above organic dispersion by distilling off the organic compound from the aqueous dispersion under normal pressure or reduced pressure, if necessary. The content of the compound may be reduced, or the organic compound may not be substantially contained.

Typical examples of the above-mentioned organic compounds having a number average molecular weight of 32 to 300 and an sp value of 8.5 to 15 include, for example, methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, and normal butyl alcohol. Secondary alcohols such as butyl alcohol, amyl alcohol, cyclohexanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, esters such as ethyl acetate, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, etc. In addition to organic compounds of glycol ethers, dimethylformamide, tetrahydrofuran,
Examples thereof include N-methyl-2-pyrrolidone and dioxane. These organic compounds may be used alone or in combination of two or more. When two or more types are mixed and used, the aqueous medium (C) preferably contains water as a main component, the total content of which is 50% by weight or less.

The polyester resin aqueous dispersion of the present invention comprises
It may be prepared by a method other than the method shown in the above example. However, the finally obtained polyester resin aqueous dispersion is the polyester resin (A) as described above.
The ratio of the polyester resin (B) and the aqueous medium (C) is (B) / {(A) + (B)} = 5 to 50% by weight {(A) + (B)} / {(A) + (B) + (C)} = 5
It is preferable to satisfy the two formulas of ˜50% by weight.

The polyester resin aqueous dispersion of the present invention comprises
It may contain a neutralizing agent and / or an emulsifying agent. Typical examples of the neutralizing agent include ammonia, organic amines such as triethylamine, diethanolamine, triethanolamine, dimethylethanolamine, N-methylmorpholine, NaO, and the like.
Examples thereof include hydroxides of alkali metals or alkaline earth metals such as H, KOH, and Ca (OH) ₂ .

Representative examples of emulsifiers include alkylbenzene sulfonic acid, alkyl sulfuric acid,
Examples include various anionic emulsifiers such as potassium or sodium salts of alkylallyl polyether sulfate, ammonium salts, and various nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene alkylallyl ethers. .

The amount of the neutralizing agent used is preferably an amount sufficient to neutralize the acidic functional groups of the polyester resins (A) and (B). It is desirable to appropriately adjust the amount used so that the value becomes about 7. When an emulsifier is used, the water resistance of the film may be reduced, so the amount used is preferably 5% by weight or less based on the total weight of the polyester resins (A) and (B).

The polyester resin aqueous dispersion of the present invention can be used in the fields of fiber processing, paper processing, film processing, printing, painting, etc. as a main constituent of adhesives, paints, inks, binders and various treating agents. .

The polyester resin of the present invention can be used alone or, if necessary, in combination with other resins and in combination with a crosslinking agent. That is, it can be expected that the hardness, heat resistance, water resistance, and durability of the obtained film or the like will be further improved by combining with such other resin or crosslinking agent.

Typical examples of the other resins mentioned above include acrylic emulsion, synthetic rubber latex, water-based acrylic resin, water-based urethane resin, water-based phenol resin, water-based polyester resin other than the polyester resin water-based dispersion of the present invention, and the like. One or two or more of these may be appropriately selected depending on the purpose of use and the processing method.

Typical examples of the above-mentioned cross-linking agent include aminoplasts, epoxy compounds, polyisocyanate compounds, polyisocyanate compounds in which isocyanate groups are primarily protected, and ethyleneimine compounds. Of these, Depending on the purpose of use and processing method,
You may select as appropriate.

If necessary, it can be used in a form to which an inorganic filler or the like is added.

[0054]

The present invention will be described in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, all parts and% are based on weight unless otherwise specified.

Various test items or measurement items were performed by the following methods. (1) Number average molecular weight It was measured by gel permeation chromatography using dimethylformamide containing LiBr at a concentration of 10 mmol / l as a mobile phase.

(2) Softening point The softening point was measured by the ring and ball method according to the method specified by ASTM (E28-58T).

(3) Particle size of water dispersion The average particle size (equivalent hydrodynamic diameter) analyzed by the cumulant method was used for measurement by the dynamic light scattering method.

(4) Storage Stability of Aqueous Dispersion The aqueous dispersion of polyester resin was stored at 40 ° C. for 1 week and visually evaluated for appearance change, sedimentation and the like.

Evaluation 5: No change in appearance and no sedimentation. 4: The appearance is changed (color change, etc.), but there is no sedimentation. 3: A small amount of sediment formed. 2: A change in appearance and a precipitate were generated at the same time. 1: A large amount of sediment or aggregate was formed.

(5) Water resistance of coating film A polyester resin aqueous dispersion is applied to a polyethylene terephthalate film having a thickness of 125 micrometers (μm) so that the film thickness after drying is 10 μm, and dried at a temperature of 90 ° C. for 2 minutes. After that, it was further heated at 140 ° C. for 1 minute.

The coated film thus obtained is
It was immersed in ion-exchanged water at 25 ° C. for 24 hours, and the degree of whitening and the state of coating film adhesion were observed. Evaluation 5: Whitening did not occur, and the coating film remained completely on the film.

4: Very pale white. The coating film is completely left. 3: Thin or partially whitened. The coating film is completely left. 2: The entire coating film is white, or there is partial floating or elution. 1: The entire coating film turns white and peels off easily with a finger. Alternatively, more than half of the coating film is floating or is eluted and lost.

(6) Solvent resistance of coating film The coated film obtained as described above was treated with gauze impregnated with xylene to obtain 4.9 × 10 ⁴ Pascal (Pa).
The following reciprocating friction was performed by applying the following contact load, and the number of reciprocating motions until the polyethylene terephthalate film as the base material was exposed due to dissolution of the film or breakage of the film was measured.

Evaluation 5: 100 times or more 4: 60 times or more 3: 40 times or more 2: 20 times or more 1: less than 20 times (7) Pencil scratch value of coating film The coated film obtained as described above is applied on a steel plate. The film was fixed on the surface of the film and the pencil scratching value was measured by scratching and breaking of the film by a hand scratching method specified in JIS K 5400 to evaluate the hardness and strength of the film.

Evaluation 5: No scratches or tears at 2H. 4: H does not scratch or tear. 3: HB does not scratch or break. 2: B does not scratch or break. 1: B is scratched or broken.

(8) Heat resistance of adhesive layer The film thickness after drying the polyester resin aqueous dispersion is 20 μm.
The coated film obtained in the same manner as described above except that the coating is carried out so that it is laminated with a polyethylene terephthalate film having a thickness of 50 μm, and pressure-bonded at a temperature of 140 ° C. and a pressure of 1.96 × 10 ⁵ Pa for 5 minutes Then, it was cut into a width of 25 mm (mm) to prepare a test piece.

The test piece thus obtained was allowed to stand for 30 minutes in an atmosphere at a temperature of 40 ° C., and then a weight of 200 was applied.
Using a weight of gram (g), a load was applied in the manner of 180 ° peeling, and at 50 ° C., the time until the peeling progressed 60 mm, or how many mm peeled in 240 minutes was measured.

Evaluation 5: Delamination of 30 mm or less in 240 minutes. 4: Delamination of 60 mm or less in 240 minutes. 3: 60 mm peeling in 120 minutes or less. 2: 60 mm peeling in 60 minutes or less. 1: 60 mm peeling in 30 minutes or less.

(9) Synthetic Example of Water-Dispersible Polyester Resin Synthetic Example 1 558 parts of ethylene glycol, 468 parts of neopentyl glycol, 896 parts of terephthalic acid, 598 parts of isophthalic acid and 0.5 part of butylhydroxytin oxide were placed in a reaction vessel. Charge into the reaction vessel and raise the temperature from 180 ° C to 240 ° C over 240 minutes, then continue the reaction at 240 ° C for about 290
Part of the distillate was trapped. Subsequently, 0.5 parts of tetraisopropyl titanate was charged, and at 220 to 280 ° C,
The polycondensation reaction was performed under a reduced pressure of 10 to 0.5 mm of mercury column. Thus, the molecular weight is 16,400 and the softening point is 158.
A polyester resin having a temperature of ℃ was obtained. Hereinafter, this will be referred to as a polyester resin (A1). Or just A1
Sometimes abbreviated.

Synthesis Example 2 A reaction vessel was charged with 558 parts of ethylene glycol, 468 parts of neopentyl glycol, 896 parts of terephthalic acid, 553 parts of isophthalic acid, and 0.5 parts of butylhydroxytin oxide. The temperature is raised over a period of 2 minutes and the reaction is continued at 240 ° C. for about 280
Part of the distillate was trapped. Subsequently, 80 parts of dimethyl 5-sodiumsulfoisophthalate and 0.5 part of tetraisopropyl titanate were charged and the distillate was removed at 240 ° C. until the reaction product became transparent. The polycondensation reaction was carried out under a reduced pressure of 0.5 mm. A polyester resin (A2) having a molecular weight of 14,700 and a softening point of 176 ° C. was obtained.

Synthetic Examples 3 to 6 Polyester resins (A3) to (A6) were obtained by the same method as in Synthetic Example 1 or 2 with the composition of Table 1. The molecular weights and softening points of these polyester resins are summarized in Table 1.

Synthesis Example 7 558 parts of ethylene glycol, 477 parts of diethylene glycol, 896 parts of terephthalic acid, 448 parts of isophthalic acid and 0.5 part of butylhydroxytin oxide were charged into a reaction container and the mixture was heated from 180 ° C. to 240 ° C. for 240 minutes. Then, the temperature was raised, and then the reaction was continued at 240 ° C. to trap about 260 parts of distillate. Subsequently, 266 parts of dimethyl 5-sodium sulfoisophthalate and 0.5 part of tetraisopropyl titanate were charged and the distillate was removed at 240 ° C. until the reaction product became transparent. The polycondensation reaction was carried out under a reduced pressure of 0.5 mm. A polyester resin (B1) having a molecular weight of 14700 and a softening point of 176 ° C. was obtained.

Synthetic Examples 8 and 9 A polyester resin (B) was prepared in the same manner as in Synthetic Example 7 except that the ratio of raw materials used was changed as shown in Table 2.
2) and (B3) were obtained.

Table 2 shows the compositions, molecular weights and softening points of the polyester resins (B1) to (B3) together.

[0075]

[Table 1] << Footnotes in Table 1 >> All the numbers indicating "composition" in the table mean "mol%".

“EG” ………………………… Abbreviation of “ethylene glycol” “NPG” …………………… Abbreviation of “neopentyl glycol” “DEG” ……………… Abbreviation of “diethylene glycol” “TPA” …………………… Abbreviation of “terephthalic acid” “IPA” …………………… Abbreviation of “isophthalic acid” “AA” …………………… Abbreviation of "adipic acid" Abbreviation of "SSI" ............... "5-sodium sulfoisophthalic acid" Composition analysis was performed by measurement of nuclear magnetic resonance.

Since the numerical values indicating "molecular weight" in the table are all one-hundredths of the measured values, they are actually multiplied by 100 (× 100). The unit of the numerical value showing the "softening point" in the table is "° C".

[0078]

[Table 2] << Footnotes in Table 2 >> The symbols and numerical units in the table are the same as in Table 1.

Example 1 60 parts of polyester resin (A1) and 40 parts of polyester resin (B2) were added to 90 parts.
Part dissolved in N-methyl-2-pyrrolidone,
60-80 using container with heating and stirring device
While maintaining the temperature at 0 ° C, 210 parts of water was added little by little over 60 minutes to obtain a milky white polyester resin aqueous dispersion.

The particle size of the obtained aqueous dispersion is 210 nm.
And the aqueous dispersion was stored at 40 ° C. for 1 week,
There was no change in appearance. The film on the polyethylene terephthalate film was slightly clouded, but the water resistance, solvent resistance, and pencil scratch value were all good, and the heat resistance of the adhesive layer was also good.

Comparative Example 1 A pulverized product of 100 parts of polyester resin (A2) passing through a 10 mm screen was prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the pulverized product of A2 was charged, and 1
When stirring was continued for 20 minutes at a temperature of 100 ° C., a milky white polyester resin aqueous dispersion was obtained, but insoluble matter corresponding to 60 parts of the charged A2 remained in the container.

The obtained aqueous dispersion had a solid content concentration of 12% by weight and a particle diameter of 320 nm.
When stored for 1 week at room temperature, a large amount of white precipitate was formed. The water resistance and pencil scratch value of the film on the polyethylene terephthalate film were good, and the heat resistance of the adhesive layer was also good.

Example 2 80 parts of polyester resin (A2) and 20 parts of polyester resin (B1)
In each case, pulverized products each passing a 10 mm screen were prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged and the stirring was continued at a temperature of 100 ° C. for 120 minutes. ,
A milky white polyester resin aqueous dispersion was obtained.

The particle diameter of the obtained aqueous dispersion is 180 nm.
And the aqueous dispersion was stored at 40 ° C. for 1 week,
There was no change in appearance. The film on the polyethylene terephthalate film had good water resistance, solvent resistance, and pencil scratch resistance, and the adhesive layer also had good heat resistance.

Example 3 Of 60 parts of polyester resin (A2) and 40 parts of polyester resin (B1),
In each case, a pulverized product that passed through a 10 mm screen was prepared in advance. While stirring and mixing 90 parts of isopropyl alcohol and 310 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged, and stirring was continued at a temperature of 80 ° C. for 120 minutes. A translucent polyester resin aqueous dispersion having a milky white color was obtained.
From the obtained aqueous dispersion, isopropyl alcohol and water were distilled off under reduced pressure of 10 to 20 mmHg to obtain 400 parts of a milky white polyester resin aqueous dispersion substantially containing water as a medium.

The particle diameter of the obtained aqueous dispersion is 160 nm.
And the aqueous dispersion was stored at 40 ° C. for 1 week,
There was no change in appearance. The film on the polyethylene terephthalate film had good water resistance, solvent resistance, and pencil scratch resistance, and the adhesive layer also had good heat resistance.

Example 4 40 parts of polyester resin (A2) and 60 parts of polyester resin (B1)
In each case, pulverized products each passing a 10 mm screen were prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged and the stirring was continued at a temperature of 100 ° C. for 120 minutes. ,
A milky white polyester resin aqueous dispersion was obtained.

The particle diameter of the obtained aqueous dispersion was 86 nm, and when the aqueous dispersion was stored at 40 ° C. for 1 week, there was no change in appearance. The solvent resistance of the film on the polyethylene terephthalate film was good, and the heat resistance of the adhesive layer was also good.

Example 5 60 parts of polyester resin (A3) and 40 parts of polyester resin (B1)
In each case, pulverized products each passing a 10 mm screen were prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged and the stirring was continued at a temperature of 100 ° C. for 120 minutes. ,
A translucent polyester resin aqueous dispersion was obtained.

The particle diameter of the obtained aqueous dispersion was 60 nm, and when the aqueous dispersion was stored at 40 ° C. for 1 week, there was no change in appearance. The solvent resistance of the film on the polyethylene terephthalate film was good.

Example 6 60 parts of polyester resin (A4) and 40 parts of polyester resin (B1)
In each case, pulverized products each passing a 10 mm screen were prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged and the stirring was continued at a temperature of 100 ° C. for 120 minutes. ,
A translucent polyester resin aqueous dispersion was obtained.

The particle diameter of the obtained aqueous dispersion is 160 nm.
And the aqueous dispersion was stored at 40 ° C. for 1 week,
There was no change in appearance. The physical properties of the film on the polyethylene terephthalate film were good.

Comparative Example 2 60 parts of polyester resin (A6) and 40 parts of polyester resin (B1)
In each case, pulverized products each passing a 10 mm screen were prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged and the stirring was continued at a temperature of 100 ° C. for 120 minutes. ,
A milky white polyester resin aqueous dispersion was obtained.

The particle diameter of the obtained aqueous dispersion is 120 nm.
And the aqueous dispersion was stored at 40 ° C. for 1 week,
There was no change in appearance. The water resistance, solvent resistance, pencil scratch value, and heat resistance of the adhesive layer of the film on the polyethylene terephthalate film were all lowered.

Comparative Example 3 60 parts of polyester resin (A2) and 40 parts of polyester resin (B2)
In each case, pulverized products each passing a 10 mm screen were prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged and the stirring was continued at a temperature of 100 ° C. for 120 minutes. As a result, a milky white polyester resin aqueous dispersion was obtained, but an insoluble matter having a weight corresponding to 50 parts of the charged A2 and B2 remained in the container.

The solid content concentration of the obtained aqueous dispersion was 14% by weight, and the particle size could not be measured. Aqueous dispersion at 40 ℃
When stored for 1 week at room temperature, a large amount of white precipitate was formed. The water resistance and pencil scratching value of the film on the polyethylene terephthalate film were good, and the heat resistance of the adhesive layer was also good.

[Comparative Example 4] A crushed product of 60 parts of polyester resin (A2) and 40 parts of polyester resin (B3), each of which passed through a 10 mm screen, was prepared in advance. While stirring and mixing 90 parts of normal butyl cellosolve and 210 parts of water in a container having a heating and stirring device, the above-mentioned two kinds of pulverized products were charged and the stirring was continued at a temperature of 100 ° C. for 120 minutes. A translucent polyester resin aqueous dispersion was obtained.

The particle diameter of the obtained aqueous dispersion was 60 nm, and when the aqueous dispersion was stored at 40 ° C. for 1 week, there was no change in appearance. The water resistance, pencil scratch value, and heat resistance of the film on the polyethylene terephthalate film were inferior.

Example 7 60 parts of polyester resin (A5), 40 parts of polyester resin (B1) crushed in advance through a 10 mm screen, and 25 parts of water were used in an atmosphere pressure type kneader. Then, after kneading at a jacket temperature of 140 ° C. for 40 minutes to form a light brown transparent mixture, 42 parts of water was added little by little over 1 hour while maintaining the temperature of the mixture at 80 to 100 ° C. 233 parts of water was added to obtain a milky white polyester resin aqueous dispersion.

The particle diameter of the obtained aqueous dispersion is 180 nm.
And the aqueous dispersion was stored at 40 ° C. for 1 week,
There was no change in appearance. The film on the polyethylene terephthalate film had good water resistance, solvent resistance, and pencil scratch resistance, and the adhesive layer also had good heat resistance.

The compositions of the polyester resin aqueous dispersions of Examples 1 to 7 and Comparative Examples 1 to 4 are summarized in Tables 3, 4 and 5.

[0102]

[Table 3]

[0103]

[Table 4]

[0104]

[Table 5] << Footnotes in Table 3 >> The numerical values shown in the columns of polyester resins "A1" to "A6" and "B1" to "B3" mean "% by weight" in all polyester resins.

The numerical values shown in the medium column mean "% by weight" based on the total polyester resin. “NMP” …………………… Abbreviation for “N-methyl-2-pyrrolidone” “BCS” ……………… Abbreviation for “normal butyl cellosolve” The solid content is the total of polyester resin and medium "% By weight" of the polyester resin.

The unit of particle diameter is nanometer (nm). However, "-" shown in the column of particle diameter indicates that measurement was impossible.

[0107]

The storage stability is good, and the water resistance is
Since it is a polyester resin aqueous dispersion that forms a film excellent in solvent resistance, hardness or strength, and heat resistance,
Aqueous resins suitable for use as adhesives, paints, resins for inks, or by blending the polyester resin aqueous dispersion of the present invention alone or with a small amount of a cross-linking agent, etc. as a coating agent for film, paper, and fiber processing Provided.

Claims (5)

[Claims] 1. A softening point of 40 to 200 ° C., a number average molecular weight of 5,
000 to 30,000 polyester resin (A) and a polycarboxylic acid component containing 5 to 20 mol% of a sulfonic acid metal group-containing aromatic dicarboxylic acid and a polyol component having a number average molecular weight of 3,000 to 10,000 A polyester resin (B), wherein the polyester resin (B) is dispersed in an aqueous medium (C). 2. The polyester resin aqueous dispersion according to claim 1, which contains a metal sulfonate-containing aromatic dicarboxylic acid as a polycarboxylic acid component of the polyester resin (A). 3. The polycarboxylic acid component of the polyester resin (A) contains 0 to 4 mol% of a sulfonic acid metal group-containing aromatic dicarboxylic acid.
The polyester resin aqueous dispersion described. 4. The aqueous medium (C) has a number average molecular weight of 32 to 3
The polyester resin according to any one of claims 1 to 3, wherein the main component is water containing an organic compound having a sp value of 8.5 and an sp value of 8.5 to 15 at a concentration of 50% by weight or less. Aqueous dispersion. 5. The ratio of polyester resins (A) and (B) to the aqueous medium (C) is (B) / {(A) + (B)} = 5.
˜50% by weight and {(A) + (B)} / {(A) + (B) + (C)} = 5
It is characterized by satisfying the formula of -50% by weight.
The polyester resin aqueous dispersion according to any one of 1.