JP2003292548A - Emulsion composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emulsion composition that has water resistance enough to inhibit the coating film from being scrubbed off or disappearing, even when physical force is loaded as the coating film is kept in water or the like and gives the coating film retaining adhesion to the substrate, even when the film is permitted to stand under high temperature and high humidity conditions for a long time. <P>SOLUTION: The emulsion composition is produced by emulsion polymerization of (C) an ethylenically unsaturated compound in an aqueous medium in the presence of a polyester formed by polycondensation between (A) the carboxylic acid components including (A1) a dicarboxylic acid bearing a sulfonic acid metal salt group and (A2) a dicarboxylic acid bearing a reactive double bond and (B) the diol components and bears 1-5 meq/g of reactive double bonds in the molecular chain. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has water resistance such that a coating film is not scraped or disappears even if physical force is applied to the formed coating film in contact with water or the like. or,
The present invention relates to an emulsion composition which gives a coating film that retains its adhesiveness to a substrate even when the coating film is left under high temperature and high humidity conditions for a long period of time.

[0002]

2. Description of the Related Art An emulsion composition obtained by emulsion-polymerizing a compound having a polymerizable double bond in the presence of a high molecular compound has a characteristic of being an environmentally friendly water-based composition and has good adhesiveness to a substrate, a coating agent, a binder, Widely used in paints, etc. In particular, a composition using a polyester containing a metal sulfonate as a polymer compound has good adhesiveness to a polyester film, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET), and thus PET in-line coating It is known to be useful as a coating agent for PET and PET films. For example, Japanese Patent No. 3241408 discloses an aqueous medium containing a sulfonate group and a polyester resin having at least one unsaturated double bond per molecule, and an aromatic compound having a polymerizable unsaturated double bond. There is disclosed an aqueous resin composition obtained by polymerizing in water.

[0003]

However, when the present inventor examined the above disclosed technique, in the technique, a polyester resin having a relatively low molecular weight was used, and the reactivity in the polyester resin was found from the description of Examples. When the amount of double bonds was calculated, the content was as low as about 0.8 meq / g, and acrylic acid was added to the polyester diol in the manufacturing method thereof, and the polyester having unsaturated double bonds only at the terminals was used. Since it is a resin, a coating film obtained from an aqueous resin composition obtained by emulsion-polymerizing an ethylenically unsaturated compound in the presence of such a polyester resin has the following problems. In other words, there is still room for improvement in order to exert extremely high water resistance that does not scrape or lose the coating film when wiping the stains on the coating film with a cloth soaked in water. Furthermore, in the above-mentioned technique, even if it is immersed in warm water of about 40 ° C. for 24 hours, it shows good adhesiveness to the base material, but the coating film has a high temperature at the time of storage or use after forming the coating film depending on its application. It was also found that the coating film may be left for a long period of time under high humidity conditions, and under such conditions, the adhesive force of the above coating film decreases with time.

[0004]

The inventors of the present invention have made extensive studies and found that a dicarboxylic acid component containing a dicarboxylic acid (A1) having a metal sulfonate group and a dicarboxylic acid compound (A2) having a reactive double bond. One reactive double bond is present in the molecule formed by polycondensing (A) and the diol component (B).
It was found that an emulsion composition obtained by emulsion-polymerizing an ethylenically unsaturated compound (C) in an aqueous medium in the presence of a polyester having 5 to 5 meq / g solves such a problem, and completed the present invention. .

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.
The polyester used in the present invention contains a metal sulfonate group and has a reactive double bond in the molecule of 1 to 5 me.
The polyester is characterized by having q / g, preferably 1 to 3 meq / g. When the amount of reactive double bonds contained in the polyester is less than 1 meq / g, the water resistance of the coating film obtained from the emulsion composition and the adhesion of the coating film to the substrate under high temperature and high humidity conditions are reduced. Happened 5m
When it exceeds eq / g, when the emulsion composition is coated, a partial gel structure is likely to be formed and the film-forming property itself is poor, and the object of the present invention cannot be achieved.

The present invention is also characterized in that a reactive double bond is introduced into the molecular chain of the polyester. For that purpose, the reactive double bond must be introduced during the polycondensation of the polyester polyol. Therefore, it is impossible to increase the amount of the reactive double bond by the method of introducing the reactive double bond after once preparing the polyester polyol containing no reactive double bond.

As described above, the polyester used in the present invention is obtained by polycondensing the dicarboxylic acid component (A) and the diol component (B). The dicarboxylic acid (A1) having a metal sulfonate group in the dicarboxylic acid component (A) is 5
-Sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-
Examples thereof include sodium, potassium and lithium salts of sulfophthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and 5 (4-sulfophenoxy) isophthalic acid.

In the dicarboxylic acid component (A), the dicarboxylic acid compound (A2) having a reactive double bond, which is used in combination with the dicarboxylic acid (A1) having a metal sulfonate group, is
An essential component for introducing a reactive double bond into the molecular chain of polyester, maleic acid, maleic anhydride,
Unsaturated dicarboxylic acids such as fumaric acid, fumaric anhydride, itaconic acid, and citraconic acid are mentioned, and fumaric acid is particularly preferable from the viewpoint of easy availability and stability of raw materials.

It is also preferable to use other dicarboxylic acid (A3) in combination during the production of polyester from the viewpoint of improving the strength of the emulsion coating film. Examples of such dicarboxylic acid (A3) include terephthalic acid, isophthalic acid, phthalic acid and hexahydrophthalic anhydride. Aromatic dicarboxylic acids such as acids, phthalic anhydride, norbornane dicarboxylic acid, naphthalene dicarboxylic acid, 4,4-oxybenzoic acid and their lower alkyl esters, malonic acid, glutaric acid, succinic acid, adipic acid, pimelic acid, suberin Examples thereof include acids, sebacic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids, and lower alkyl esters thereof.

As the diol component (B), ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
9-nonanediol, 1,10-dodecanediol,
2,4-Dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-
Pentanediol, 2,2,4-trimethyl-1,6-
Hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4′- Thiodiphenol, 4,4'-methylenediphenol, 4,
4 '-(2-norbornylidene) diphenol, 4,
4'-dihydroxybiphenol, dihydroxybenzene, 4,4'-isopropylidenephenol, 4,4 '
-Isopropylidene bis (2,6-dichlorophenol), 2,5-naphthalene diol, p-xylene diol and the like can be mentioned.

In the above, (A1) / in the component (A)
The molar ratio of (A2) is preferably 3/97 to 40/60, more preferably 8/92 to 30/70. Such molar ratio is 3 /
When it is less than 97, the solubility in an aqueous medium may decrease when emulsion polymerization is performed using the obtained polyester, while when it exceeds 40/60, the strength and water resistance of the emulsion coating film may decrease.

When (A3) is used in combination, (A3)
The compounding ratio of is 40 with respect to the total of (A1) and (A2).
˜220 mol% is preferred. If the blending ratio is less than 40 mol%, the effect of improving the coating film strength is not expected, while 2
If it exceeds 20 mol%, the solubility of the polyester obtained during emulsion polymerization in an aqueous medium may be poor, which is not preferable.

After the esterification reaction, the reaction ratio of the component (A) and the component (B) during the production of the polyester is usually 1.1 to 2.0 times the molar amount of the component (B) with respect to the component (A). , Polycondensation reaction may be performed.

The reaction is carried out by adding the components (A) and (B) to the reactor.
Then, the esterification reaction is carried out with stirring. Examples of the catalyst include titanium-based catalysts such as tetraisopropyl titanate and tetra-n-butyl titanate, antimony-based catalysts such as antimony trioxide, germanium-based catalysts such as germanium oxide, zinc acetate, manganese acetate, and dibutyltin oxide catalysts. Yes, preferably tetra-
n-Butyl titanate is used. Further, two or more kinds of these catalysts may be used in combination. The addition amount of the catalyst is preferably 10 to 1000 ppm with respect to the component (A), and 10
If it is less than ppm, the reaction may not proceed sufficiently, while if it exceeds 1000 ppm, there is no advantage in shortening the reaction time.

The esterification reaction is not particularly limited in temperature and time and may be carried out within a known range.
Usually, it is carried out at about 160 to 240 ° C. for about 1 to 10 hours while distilling water or alcohol. The polycondensation reaction to be carried out next is not particularly limited in temperature or time, and may be carried out in a known range, but usually 160 to
The reaction system is gradually depressurized at 260 ° C. for about 0.1 to 10 hours and the reaction is continued at 10 to 500 Pa for about 0.1 to 3 hours.

The polyester used in the present invention preferably contains 2 to 20 mol% of a metal sulfonate base,
Further, 4 to 15 mol% is preferable. If the content is less than 2 mol%, the solubility in an aqueous medium may be poor at the time of emulsion polymerization, while if it exceeds 20 mol%, the coating film obtained from the emulsion composition may have poor water resistance. Absent.

Further, the number average molecular weight of the polyester is 3
When it is 000 to 40,000, the effect of the present invention can be remarkably exhibited, and further preferably 7,000 to 40,000, particularly 8,000 to 30,000. When the number average molecular weight is less than 3,000, the strength of the coating film obtained from the emulsion composition may decrease, and when it exceeds 40,000, the water solubility may decrease, and the polyester may be contained in an aqueous medium during emulsion polymerization. It may become difficult to dissolve, which is not preferable. Further, the glass transition temperature (Tg) of the polyester is preferably −30 to 170 ° C. Tg is -3
If it is less than 0 ° C, blocking of the coating film may become a problem, and if it exceeds 170 ° C, the film-forming temperature may become too high, which is not preferable.

Using the polyester thus obtained,
The ethylenically unsaturated compound (C) is emulsion polymerized in the presence of the polyester in an aqueous medium to obtain an emulsion composition. As the ethylenically unsaturated compound (C), ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid ester, alkyl vinyl ether, silyl group-containing ethylenically unsaturated compound, and styrene are useful.

Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid, maleic acid and itaconic acid.

As the ethylenically unsaturated carboxylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-
Butyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2
-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, diallyl malate, itaconic acid Examples include diallyl and the like.

Examples of the alkyl vinyl ether include propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, tetradodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether and the like.

Examples of the silyl group-containing ethylenically unsaturated compound include γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ -(Meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth)
Acryloxypropyldimethylchlorosilane, γ- (meth) acryloxypropyltripropoxysilane, γ
-(Meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxypropyltributoxysilane, γ- (meth) acryloxybutyltrimethoxysilane, γ- (meth) acryloxypentyltrimethoxysilane, γ -(Meth) acryloxyhexyltrimethoxysilane, γ- (meth) acryloxyhexyltriethoxysilane, γ- (meth) acryloxyoctyltrimethoxysilane, γ- (meth) acryloxydecyltrimethoxysilane, γ- ( Examples thereof include (meth) acryloxydodecyltrimethoxysilane, γ- (meth) acryloxyoctadecyltrimethoxysilane, and γ- (meth) acryloxyoctadecyltrimethoxysilane.

In addition, acrylamide, N-methylol acrylamide, diacetone acrylamide, vinyl acetate, vinyl t-decanoate, allyl alcohol, acrylic chloride, vinyl chloride, vinylidene chloride, vinyl pyridine,
Vinylpyrrolidone, methyl vinyl ketone, acrylamide, acetoacetylated (meth) acrylate, vinyltoluene, (meth) acrylonitrile and the like are also used.

Specific examples of the polymerization initiator used during emulsion polymerization include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, alkyl peroxides, t-butyl hydroperoxide, cumene hydroperoxide, and p. -Methane hydroperoxide, isobutyl peroxide, laurolyl peroxide,
3,5,5-trimethylhexanoyl peroxide,
Octanoyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t
-Butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
Organic peroxides such as 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate and t-butylperoxyisobutyrate, azo Bisisobutyronitrile, dimethylazodiisobutyrate, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-
Azobis (2-methylbutyronitrile), 4,4'-azobis-4-cyanovaleric, 2,2-azobis (2
-Methylbutanamide oxime) dihydrochloride acid and the like. The polymerization initiator is 0.1 to 8.0 with respect to the total of the polyester and the ethylenically unsaturated compound (C).
It is about% by weight. In the polymerization, an organic solvent such as isopropyl alcohol and acetone, a dispersion stabilizer, a rheology modifier, and a pH buffering agent such as phosphate may be used in combination within the range where the effects of the present invention are not lost.

The emulsion polymerization method for obtaining the emulsion composition of the present invention is not particularly limited, but practically, the polyester is dissolved in water to form a solution having a solid content of 10 to 60% by weight, and 100% by weight of the polyester is added to the solution. 5 to 300 parts by weight, preferably 10 to 50 parts by weight, of the ethylenically unsaturated compound (C) and a polymerization initiator are added to carry out polymerization. The reaction temperature during polymerization is usually 5 to 90 ° C.
Then, the reaction is completed in about 1 to 24 hours. After completion of the reaction, residual monomers may be removed under reduced pressure depending on the case.

Thus, an emulsion composition having a polymer in which a reactive double bond in the molecular chain of a polyester having a carboxyl group at the terminal and a double bond of an ethylenically unsaturated compound are reacted as a dispersoid is obtained. The average particle size of the polymer component in the composition is 10 to 300 nm, preferably 10 to 100 nm, more preferably 10 to 50 nm, and the coating film obtained from the composition is characterized by excellent dryness.

In the emulsion composition of the present invention, if necessary, a film-forming aid such as a hindered phenol-based antioxidant, a flame retardant, an ultraviolet absorber, a catalyst deactivator or solvent, and a plasticizer, Various defoaming agents, thickeners such as modified cellulose, pigment dispersants and leveling agents, coloring pigments such as titanium white, phthalocyanine blue, carbon black, iron oxide, calcium carbonate, magnesium carbonate, barium sulfate, various silicas, talc. , Extenders such as mica and clay, and fillers such as glass fibers can be added. It is also possible to blend various resins such as an aqueous acrylic resin, an aqueous epoxy resin, an aqueous melamine resin, and an aqueous blocked isocyanate with the emulsion composition.

The emulsion composition of the present invention is used for coating agents, paints, adhesives, sealing agents and various binders. In particular, it is useful as a coating agent for various plastics by taking advantage of the good adhesiveness of the emulsion coating film to the substrate under high temperature and high humidity conditions. Above all, P
Since it has good adhesiveness to polyester such as ET, it is useful as an in-line coating of PET or a functional coating agent for imparting functionality such as easy printing, antistatic and heat resistance imparting to a PET film.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, "%" and "part" mean
Unless otherwise specified, it is based on weight. Example 1 In a reactor equipped with a stirrer, a thermometer, a nitrogen gas blowing port and a distillation port, under a nitrogen gas atmosphere, 0.08 mol of 5-sodium sulfoisophthalic acid (A1) and fumaric acid (A2)
0.4 mol, 0.2 mol of terephthalic acid (A3), 0.32 mol of isophthalic acid (A3) and 1.5 mol of ethylene glycol (B) were charged all at once to prepare tetra-n-butyl titanate (catalyst). 100 ppm was added to the dicarboxylic acid component (A), an esterification reaction was carried out at 160 to 200 ° C., and 98% of the theoretical amount of water was distilled. Next, the reaction temperature is raised to 240 to 260 ° C. and 10 to 20 Pa.
Polycondensation was carried out for 2 hours under reduced pressure, containing 4.6 mol% of sodium sulfonate base and having a reactive double bond amount of 2.2 m.
Polyester having eq / g, number average molecular weight of 11,000 and Tg of 35 ° C. was obtained. Next, 100 parts of the above polyester and 400 parts of ion-exchanged water were charged into a reactor equipped with a stirrer, a thermometer, and a nitrogen gas blowing port, and the temperature was raised to 80 to 90 ° C. to dissolve it into an aqueous solution. A mixture of 0.5 parts of ammonium sulfate and 30 parts of styrene (C) was added dropwise over 5 minutes, and emulsion polymerization was carried out at the same temperature for 3 hours. The average particle size of the polymer component of the obtained emulsion composition was 30 nm.
A biaxially stretched P having a thickness of 50 μm
Coat on ET film by air knife method and apply at 80 ℃ for 1
A test film having a thickness of 10 μm was prepared by drying for 0 minutes, and the physical properties of the emulsion composition were evaluated as follows.

(Water resistance) Using a gauze soaked with ion-exchanged water, the coated surface of the test film was rubbed at a pressure of 3 kg / cm ² , and the number of reciprocations until the gauze reached the surface of the underlying PET film was measured. . The evaluation criteria are as follows. ○ ・ ・ ・ 100 times or more △ ・ ・ ・ 60 to 99 times × ・ ・ ・ 59 times or less

(Adhesiveness) (1) After leaving the above-mentioned test film for 1 month in an atmosphere of 60 ° C. and 90% RH, a cross-cut having a side of 1 mm was made on the film with a cutter, and cellophane adhesive was applied from above. The operation of pressing the tape [manufactured by Nichiban Co., Ltd. (17 mm width)] and then forcibly peeling off the coating film was repeated 3 times, and the number of remaining pieces per 100 grids was measured. The evaluation criteria are as follows. ○: 100 pieces △: 90 to 99 pieces × ... 89 pieces or less

(2) The test film was allowed to stand in warm water at 60 ° C. for 24 hours, and then the film was treated in the same manner as in (1) above and evaluated in the same manner.

Example 2 In Example 1, the charging composition at the time of polyester production was
5-sodium sulfoisophthalic acid (A1) 0.15 mol, fumaric acid (A2) 0.4 mol, terephthalic acid (A
3) The reaction was carried out in the same manner except that the amounts of 0.2 mol, 0.25 mol of isophthalic acid (A3) and 1.5 mol of ethylene glycol (B) were changed, and the metal sulfonate base was adjusted to 7.5.
A polyester having a mol% of 12,000, a number average molecular weight of 12,000, a reactive double bond amount of 2.2 meq / g, and a Tg of 50 ° C. is obtained, and emulsion polymerization is performed in the same manner to obtain a polymer component having an average particle diameter of 35.
nm emulsion compositions were prepared and evaluated in the same manner as above.

Example 3 In Example 1, the charging composition at the time of polyester production was 5
-Sodium sulfoisophthalic acid (A1) 0.08 mol, fumaric acid (A2) 0.24 mol, terephthalic acid (A
3) The same reaction was carried out except that 0.4 mol, 0.28 mol of isophthalic acid (A3) and 1.5 mol of ethylene glycol (B) were used, and the metal sulfonate contained 4.0 mol%. A polyester having a number average molecular weight of 15,000, a reactive double bond amount of 1.3 meq / g and a Tg of 63 ° C. was obtained, and emulsion polymerization was carried out in the same manner to produce an emulsion composition having an average particle diameter of the polymer component of 35 nm. It evaluated similarly.

Example 4 The procedure of Example 1 was repeated except that 29 parts of methyl methacrylate (C) was used instead of styrene (C) during the emulsion polymerization, to obtain an emulsion composition having an average particle diameter of 34 nm as the polymer component. The product was manufactured and evaluated in the same manner as above.

Example 5 The procedure of Example 1 was repeated except that 25 parts of propyl vinyl ether (C) was used instead of styrene (C) at the time of emulsion polymerization to obtain an emulsion composition having an average particle diameter of 40 m as a polymer component. The product was manufactured and evaluated in the same manner as above.

COMPARATIVE EXAMPLE 1 In Example 1, the composition used in the polyester production was 0.6 mol of terephthalic acid (A3) and isophthalic acid (A3).
0.28 mol, 5-sodium sulfoisophthalic acid (A
1) The same reaction was carried out except that 0.08 mol, fumaric acid (A2) 0.04 mol, and ethylene glycol (B) 1.5 mol were added, and the sulfonic acid metal base was contained in 3.2 mol%, A polyester having a reactive double bond amount of 0.2 meq / g, a number average molecular weight of 23,000, and Tg of 67 ° C. was obtained, and emulsion polymerization was performed in the same manner to produce an emulsion composition having an average particle diameter of the polymer component of 30 nm. It evaluated similarly.

Comparative Example 2 In Example 1, the charging composition at the time of polyester production was 5
-Sodium sulfoisophthalic acid (A1) 0.06 mol, fumaric acid (A2) 0.89 mol, succinic anhydride (A
3) 0.05 mol and ethylene glycol (B) 1.5
The reaction was carried out in the same manner except that the amount of the sulfonic acid metal base was 3.0 mol% and the amount of the reactive double bond was 6.0 me.
A polyester having q / g, a number average molecular weight of 12,000 and a Tg of 45 ° C. was obtained. Similarly, emulsion polymerization was carried out to produce an emulsion composition having a polymer component having an average particle diameter of 36 nm, and the same evaluation as above was carried out.

Comparative Example 3 0.014 mol of 5-sodium sulfoisophthalic acid (A1) and dimethyl terephthalate (A) were placed under a nitrogen gas atmosphere in a reactor equipped with a stirrer, a thermometer and a nitrogen gas inlet.
3) 0.28 mol, dimethyl isophthalate (A3) 0.
28 mol, 0.54 mol of neopentyl glycol (B) and 0.72 mol of ethylene glycol (B) were charged all at once, and 100 ppm of tetra-n-butyl titanate (catalyst) was added to the total amount of the dicarboxylic acid component. 230
The esterification reaction was carried out at ° C for 2 hours. Next, adipic acid (A
3) Add 0.2 mol to bring the reaction temperature to 220-230 ° C.
The reaction system was heated to 250 ° C. in 30 minutes, the system pressure was gradually reduced, and the reaction was continued at 1300 Pa for 1 hour to obtain a polyester diol having a molecular weight of 2500. Next, 100 parts of the polyester diol, 100 parts of toluene, 5.8 parts of acrylic acid, and p were placed in a reactor equipped with another stirrer, a thermometer, a nitrogen gas blowing port, and a distillation port.
-Toluenesulfonic acid 0.5 part, phenothiazine 0.0
02 parts was added and the reaction was carried out under toluene reflux. When the theoretical amount of water (1.45 parts) was distilled off, the reaction was terminated, the metal sulfonate contained 0.7 mol%, the amount of reactive double bonds was 0.8 meq / g, and the number average molecular weight was 2600. , Tg65
A polyester having a double bond at the molecular end at ℃ was obtained.
Emulsion polymerization was carried out in the same manner as in Example 1 to produce an emulsion composition having a polymer component with an average particle diameter of 50 nm, and the same evaluation as above was carried out. Table 1 shows the evaluation results of the above Examples and Comparative Examples.

[0040]

[0041]

The emulsion composition of the present invention comprises a dicarboxylic acid component (A) containing a dicarboxylic acid (A1) having a metal sulfonate group and a dicarboxylic acid compound (A2) having a reactive double bond, and a diol component (A). It is obtained by emulsion polymerization of an ethylenically unsaturated compound (C) in an aqueous medium in the presence of a polyester having a reactive double bond in the molecular chain obtained by polycondensing B) in the amount of 1 to 5 meq / g. Therefore, the coating film obtained from the emulsion composition has water resistance such that the coating film is not scraped off or disappears even if physical force is applied in a state of being in contact with water or the like, and Even if the coating film is left under high temperature and high humidity conditions for a long period of time, it exhibits an excellent effect of maintaining the adhesiveness to the substrate.

Continued front page    F-term (reference) 4J011 KA06 KB19 KB29                 4J027 AB02 AB05 AB06 AB07 AB08                       AB15 AB16 AB17 AB18 AB23                       AB24 AB25 AJ04 BA03 BA04                       BA05 BA06 BA07 BA08 BA10                       BA14 BA15 CB02 CB03 CD08                 4J038 DD181 DD191 GA13 GA15                       MA08 MA10 MA14 NA04 NA12                       NA14

Claims (2)

[Claims] 1. A dicarboxylic acid component (A) containing a dicarboxylic acid (A1) having a metal sulfonate group and a dicarboxylic acid compound (A2) having a reactive double bond, and a diol component (B) are polycondensed. 1 reactive double bond in the molecular chain
An emulsion composition obtained by emulsion-polymerizing an ethylenically unsaturated compound (C) in an aqueous medium in the presence of a polyester having 5 to 5 meq / g. 2. A polyester having a number average molecular weight of 3,000.
The emulsion composition according to claim 1, wherein the emulsion composition is -40,000.