JP2003292549A - 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 an ethylenically unsaturated compound in an aqueous medium in the presence of a polyester prepared by polycondensation between (A1) a dicarboxylic acid component bearing a reactive double bond and (B) the diol component followed by addition reaction of (C) a polycarboxylic anhydride to the resultant polyester. <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 a water resistance such that the coating film is not scraped off or disappears even if physical force is applied to the formed coating film in contact with water or the like. Then
The present invention also 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 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 is characterized by being an environmentally friendly water-based composition and has good adhesiveness to a substrate, a coating agent and a binder. Widely used in paints, etc. In particular, a composition using a polyester containing a carboxyl group as a polymer compound has good adhesiveness to a polyester film, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET), and therefore PET in-line coating or P
It is known to be useful as a coating agent for ET films. For example, JP-A-5-112623 discloses a resin having at least one polar group and at least one unsaturated double bond per molecule, and an aromatic compound having a polymerizable unsaturated double bond. An aqueous resin composition obtained by polymerizing and in a water medium is disclosed, and a carboxyl group is also exemplified as the polar group.

[0003]

However, when the present inventor examined the above disclosed technique, in the polyester polyol having a carboxyl group used herein, the carboxyl group was not produced during production of the polyester polyol, such as polycarboxylic acid or oxycarboxylic acid. Since it is introduced as a carboxylic acid, it is present in the molecular chain, and a coating film obtained from an emulsion composition using such a polyester polyol is a base material even when immersed in warm water of about 40 ° C. for about 24 hours. However, depending on the application, the coating film may be left for a long period of time under high temperature and high humidity conditions during storage or use after the coating film is formed. It was also found that the coating film had a decrease in adhesive strength over time. Further, in the above-mentioned disclosed technique, there is not much disclosure about a method of introducing an unsaturated double bond into a polyester polyol, and acrylic acid is added to the examples, although it is the case of polyester diols having a metal sulfonate group. Only an example is shown, and in this case, since it is a polyester polyol having an unsaturated double bond only at the terminal of the molecular chain, an emulsion composition obtained by emulsion polymerization of an ethylenically unsaturated compound in the presence of the polyester polyol. When the coating film obtained from the above is soiled, even if you wipe the stain with a cloth soaked in water, etc., the coating film will not be scraped off or disappear, and to exhibit extremely high water resistance There was still room for improvement. It has been confirmed by the study of the present applicant that a similar tendency is observed when a carboxyl group is introduced instead of the metal sulfonate base.

[0004]

Therefore, as a result of investigation by the present inventors, a dicarboxylic acid component (A) containing a dicarboxylic acid compound (A1) having a reactive double bond was reacted with a diol component (B). In the presence of a polyester obtained by adding a polycarboxylic acid anhydride (C) to a polyester polyol, that is, a polyester having a polymerizable double bond in the molecular chain and a carboxyl group at the molecular end, in an aqueous medium. It was found that an emulsion composition obtained by emulsion-polymerizing an ethylenically unsaturated compound 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 is a polyester polyol obtained by reacting a dicarboxylic acid component (A) containing a dicarboxylic acid compound (A1) having at least a reactive double bond and a diol component (B) with a polycarboxylic acid anhydride (C). ) Is added to the polyester, and the dicarboxylic acid component (A) is a dicarboxylic acid compound (A1) having a reactive double bond, preferably a dicarboxylic acid compound (A1) having a reactive double bond and other components. Dicarboxylic acid (A2), which is used for introducing a reactive double bond into the molecular chain of polyester, maleic acid,
Unsaturated dicarboxylic acids such as maleic anhydride, fumaric acid, fumaric anhydride, itaconic acid and citraconic acid may be mentioned.

Examples of (A2) include terephthalic acid, isophthalic acid, phthalic acid, hexahydrophthalic anhydride, phthalic anhydride, norbonanedicarboxylic acid, naphthalenedicarboxylic acid, and aromatic dicarboxylic acids such as 4,4-oxybenzoic acid. Its lower alkyl esters, malonic acid, glutaric acid, succinic acid, adipic acid, pimelic acid, suberic acid,
Sebacic acid, adipic acid, azelaic acid, sebacic acid,
Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid and their lower alkyl esters are mentioned.

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.

As the polycarboxylic acid anhydride (C) used for introducing a carboxyl group to the molecular end of polyester, 1,2,4,5-benzenetetracarboxylic acid dianhydride (pyromellitic anhydride), 1, 2, 3,
4-butanetetracarboxylic dianhydride, 1,2,3,4
-Pentanetetracarboxylic dianhydride, 3,3 ', 4,
4'-benzophenone tetracarboxylic acid dianhydride, 5-
(2,5-Dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 5- (2,5-dioxotetrahydrofurfuryl)
-3-cyclohexene-1,2-dicarboxylic acid anhydride,
Cyclopentanetetracarboxylic dianhydride, 2,3
6,7-naphthalenetetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride, ethylene glycol bistrimellitate dianhydride, 2,
2 ', 3,3'-diphenyl tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, etc. are mentioned.

In the above, the component (A
The compounding ratio of 1) is preferably 0.01 to 40 mol%, more preferably 1 to 30 mol%. The blending ratio is 0.01
If it is less than mol%, the water resistance of the coating film obtained from the emulsion composition may decrease, and the adhesiveness of the base material of the coating film under high temperature and high humidity conditions may decrease with time. On the other hand, if it exceeds 40 mol%, the strength and water resistance of the coating film may deteriorate.

When the polyester polyol is produced, the reaction ratio of the component (A) and the component (B) is usually 1.01 to 2.0 times mol of the component (B) with respect to the component (A), and the esterification reaction is carried out. Good. The component (C) is preferably 0.5 to 1.0 times the difference between the number of moles of the component (B) and the number of moles of the component (A), and if it is less than 0.5 times the high temperature and high humidity conditions. The adhesiveness of the emulsion coating below to the substrate may decrease, and if it exceeds 1.0 mole, the number average molecular weight of the polyester may not increase, such being undesirable.

To obtain the above polyester polyol,
Charge the components (A) and (B) and the catalyst, raise the temperature,
The esterification reaction may be carried out while stirring, and 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, and zinc acetate. , Manganese acetate, dibutyltin oxide, and the like, and tetra-n-butyl titanate is preferably used. Further, two or more kinds of these catalysts may be used in combination. The amount of catalyst added is the dicarboxylic acid component (A)
10 to 1000 ppm is preferable, and 10 ppm
If it is less than 10, the reaction may not proceed sufficiently, while 10
Even if it exceeds 00 ppm, there is no advantage such as shortening of reaction time.

The esterification reaction is not particularly limited in temperature and time, and may be carried out within a known range.
It is usually carried out at 160 to 240 ° C. for about 1 to 10 hours while distilling water or alcohol. Then, the reaction system is gradually depressurized at about 200 to 260 ° C. to 0.0
The reaction is continued at 1 to 0.5 MPa for about 0.1 to 3 hours.

Next, the polycarboxylic acid anhydride (C) is added to the obtained polyester polyol. Such a reaction may be carried out at 160 to 200 ° C. for about 1 to 10 hours, and as a result, it is the object. A polyester is obtained. At this time, the above catalyst may be added to the same extent.

Thus, the polyester used for emulsion polymerization can be obtained. In the present invention, the acid value of the polyester is 25 to 200 mgKOH / g, more preferably 30.
It is preferably about 150 mg KOH / g. When the acid value is less than 25 mgKOH / g, the solubility in an aqueous medium is poor at the time of emulsion polymerization, and the adhesiveness of the emulsion coating film to the base material under high temperature and high humidity conditions is poor.
If it exceeds KOH / g, the water resistance of the coating film obtained from the emulsion composition may deteriorate, which is not preferable.

The amount of the reactive double bond in the polyester is preferably 0.01 to 10 meq / g, more preferably 0.05 to 5 meq / g. When the amount of the reactive double bond is less than 0.01 meq / g, the water resistance of the coating film obtained from the emulsion composition and the adhesion of the emulsion coating film to the substrate under high temperature and high humidity conditions may be reduced. If it exceeds 10 meq / g, a partial gel may be generated in the emulsion to deteriorate the film-forming property, which is not preferable.

The polyester used in the present invention can exert the effect of the present invention remarkably when the number average molecular weight is 3,000 to 40,000, and further, 7,000 to 40.
000, particularly preferably 7,000 to 30,000 is preferable. 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 it may be 4,000.
When it exceeds 0, the water solubility is lowered, and the polyester is difficult to dissolve in an aqueous medium during emulsion polymerization, which is not preferable. Further, the glass transition temperature (Tg) of the polyester is preferably −20 to 150 ° C. T
When g is less than -20 ° C, blocking of the coating film of the emulsion composition may occur, and when it exceeds 150 ° C, the film forming temperature of the emulsion composition becomes too high, which is not preferable.

Next, the polyester obtained above is used to emulsion polymerize the ethylenically unsaturated compound in an aqueous medium to obtain an emulsion composition. Such ethylenically unsaturated compounds include ethylenically unsaturated carboxylic acids,
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.

As the silyl group-containing ethylenically unsaturated compound, 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,
You may use vinylpyrrolidone, methyl vinyl ketone, acrylamide, acetoacetylated (meth) acrylate, vinyltoluene, (meth) acrylonitrile, etc.

Specific examples of the polymerization initiator used in 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% by weight with respect to the total of polyester and ethylenically unsaturated compound.
used. In the polymerization, organic solvents such as isopropyl alcohol and acetone, dispersion stabilizers, rheology control agents, and p salts such as phosphates are used as long as the effects of the present invention are not lost.
An H buffer may be used together.

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 obtain a solution having a solid content of 10 to 60% by weight, and 100% by weight of the polyester is added to the solution. Polymerization is carried out by adding 5 to 300 parts by weight, preferably 10 to 50 parts by weight, of an ethylenically unsaturated compound and a polymerization initiator to parts by weight. The reaction temperature during the polymerization is usually 5 to 90 ° C. and 1
The reaction is completed in about 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 dispersoid of a polymer obtained by reacting a reactive double bond in the molecular chain of a polyester having a carboxyl group at the terminal with a double bond of an ethylenically unsaturated compound 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.

The emulsion composition of the present invention contains, if necessary, antioxidants such as hindered phenols, flame retardants, ultraviolet absorbers, catalyst deactivators and solvents, and film-forming aids such as plasticizers. 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.

[0028]

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, fumaric acid (A1) 0.
05 mol, dimethylnaphthalenedicarboxylic acid (A2)
0.95 mol, and neopentyl glycol (B) 0.
8 mol and 0.6 mol of ethylene glycol (B) were charged all at once, and 100 ppm of tetra-n-butyl titanate (catalyst) was added to the dicarboxylic acid component (A) to obtain 1
The esterification reaction is carried out in nitrogen gas at 60 to 200 ° C. for 5 hours to distill off 98% of the theoretical amount of methanol, and further 24
A polyester polyol was obtained by reacting at 0 ° C. and 0.2 MPa under reduced pressure for 30 minutes. Next, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (C) (0.35 mol) was further charged, and the reaction temperature was 160 to 180 ° C. Addition reaction for 3 hours, number average molecular weight 8000, acid value 126mgKOH
/ G, reactive double bond amount 0.12 meq / g, Tg11
A 0 ° C. polyester was obtained. Next, the above polyester 1 was placed in a reactor equipped with a stirrer, a thermometer, and a nitrogen gas inlet.
00 parts, 400 parts of ion-exchanged water, and 0.04 of ammonia
(1.1 times mol of the carboxyl group in the polyester) was added and dissolved at 80 to 90 ° C to obtain an aqueous solution.
Next, a mixture of 0.5 parts of ammonium persulfate and 30 parts of styrene 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 35 nm. The emulsion composition was applied on a biaxially stretched PET film having a thickness of 50 μm by an air knife method and dried at 80 ° C. for 10 hours to prepare a test film having a film thickness of 10 μm. It was evaluated as.

(Water resistance) Using a gauze soaked with ion-exchanged water, the coated surface of the test film was rubbed at a pressure of 1 kg / cm ^{2 and} the number of reciprocations until the gauze reached the underlying PET film surface 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 in an atmosphere of 60 ° C. and 90% RH for one month, 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, then treated in the same manner as in (1) above, and evaluated in the same manner.

Example 2 An ester was prepared in the same manner as in Example 1 except that the amounts of fumaric acid (A1) and dimethylnaphthalene dicarboxylic acid (A2) were changed to 0.2 mol and 0.8 mol, respectively. The number average molecular weight of 80
00, acid value 128 mg KOH / g, reactive double bond amount 0.49 meq / g, Tg 97 ° C. polyester,
Similarly, emulsion polymerization is performed, and the average particle diameter of the polymer component is 35 nm.
The emulsion composition of was prepared and evaluated in the same manner as above.

Example 3 In the production of the polyester of Example 1, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (C) was used instead. , 1,2,4,5-benzenetetracarboxylic dianhydride (C) was used in the same manner except that the same mole was used, and the number average molecular weight was 8000 and the acid value was 136 mgKOH /
g, reactive double bond amount 0.13 meq / g, Tg135
A polyester of ℃ was obtained, emulsion polymerization was carried out in the same manner to produce an emulsion composition having a polymer component having an average particle diameter of 35 nm, and the same evaluation as above was carried out.

Example 4 At the time of producing the polyester polyol of Example 1, the compounding amount of ethylene glycol (B) was changed to 0.45 mol and the esterification reaction was performed in the same manner. 5-dioxotetrahydrofurfuryl) -3
-Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (C) was added in the same manner by changing the compounding amount to 0.2 mol to give a number average molecular weight of 8000 and an acid value of 65 mg.
KOH / g, reactive double bond amount 0.15 meq / g, T
g112 ° C. polyester is obtained, emulsion polymerization is carried out in the same manner,
An emulsion composition having a polymer component having an average particle diameter of 27 nm was produced and evaluated in the same manner as above.

Example 5 The procedure of Example 1 was repeated except that 29 parts of methyl methacrylate was used instead of styrene during the emulsion polymerization to prepare an emulsion composition having an average particle diameter of the polymer component of 35 nm. It evaluated similarly to.

Example 6 The procedure of Example 1 was repeated except that 25 parts of propyl vinyl ether was used instead of styrene during emulsion polymerization.
An emulsion composition having an average particle diameter of 42 m of the polymer component was produced and evaluated in the same manner as above.

Comparative Example 1 During the production of the polyester polyol of Example 1, the esterification reaction was conducted in the same manner except that the addition of fumaric acid (A1) was omitted and 1 mol of dimethylnaphthalene dicarboxylic acid (A2) was used. Average molecular weight 8000, acid value 124 mgK
A polyester having OH / g and Tg of 115 ° C. was obtained, and emulsion polymerization was performed in the same manner to produce an emulsion composition having a polymer component having an average particle diameter of 60 nm, and the same evaluation as above was performed.

Comparative Example 2 In a reactor equipped with a stirrer, a thermometer, a nitrogen gas blow-in port and a distillation port, fumaric acid (A1) was added in an amount of 0.
05 mol, dimethylnaphthalenedicarboxylic acid (A2)
0.60 mol, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2
-0.35 mol of dicarboxylic acid anhydride (C), 0.8 mol of neopentyl glycol (B) and 0.6 mol of ethylene glycol (B) were charged all at once to add tetra-n-butyl titanate (catalyst) to dicarboxylic acid. 100 ppm was added to the acid component (A) and the esterification reaction was performed in nitrogen gas at 160 to 210 ° C. for 5 hours to distill out 98% of the theoretical amount of methanol, and further 240 ° C. and 0.00002 MPa.
Polycondensation reaction was performed for 3 hours to obtain a polyester polyol having a number average molecular weight of 3000. The esterification reaction was continued for 2 hours, but no increase in the number average molecular weight was observed. Therefore, the reaction was stopped, and the number average molecular weight was 3000 and the acid value was 120 mg.
KOH / g, reactive double bond amount 0.12 meq / g, T
A polyester having a g of 110 ° C was obtained. Emulsion polymerization was carried out in the same manner as in Example 1 to produce an emulsion composition having a polymer component having an average particle diameter of 40 nm, and the same evaluation as above was carried out.
Table 1 shows the evaluation results of the above Examples and Comparative Examples.

[0039]

[0040]

The emulsion composition of the present invention comprises a polyester polyol obtained by reacting a dicarboxylic acid component (A) containing a dicarboxylic acid compound (A1) having a reactive double bond with a diol component (B). Anhydrous (C)
In the presence of polyester in the presence of a polyester, it is obtained by emulsion polymerization of an ethylenically unsaturated compound in an aqueous medium, so that the coating film obtained from the emulsion composition is physically contacted with water or the like. It has water resistance so that the coating film will not be scraped or lost even if force is applied, and the adhesiveness to the substrate is maintained even if the coating film is left for a long time under high temperature and high humidity conditions. It exhibits an excellent effect of giving a coated film.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J011 AA05 BA04 BB09 KB29 PA23                       PA24 PA25 PA26 PA30 PA37                       PA43 PA47 PA88                 4J027 AB02 AB06 AB07 AB08 AB15                       AB16 AB17 AB18 AB23 AB24                       AB25 AB26 AJ01 AJ04 AJ05                       BA05 BA06 BA07 BA08 BA14                       BA17 BA19 CB02 CB04 CC02                       CD08                 4J038 CP091 DD191 MA08 MA10

Claims (5)

[Claims] 1. A polycarboxylic acid anhydride (C) is added to a polyester polyol obtained by reacting a dicarboxylic acid component (A) containing a dicarboxylic acid compound (A1) having a reactive double bond with a diol component (B). An emulsion composition obtained by emulsion-polymerizing an ethylenically unsaturated compound in an aqueous medium in the presence of the resulting polyester. 2. The emulsion composition according to claim 1, wherein the polycarboxylic acid anhydride (C) is a tetracarboxylic acid dianhydride. 3. The acid value of polyester is 25 to 200 mg.
KOH / g, characterized in that 1 or 2
The emulsion composition described. 4. The polyester having a reactive double bond content of 0.
It is 01-10 meq / g, It is characterized by the above-mentioned.
<3> The emulsion composition according to any one of <3> to <3>. 5. A polyester having a number average molecular weight of 3000.
It is -40,000, The emulsion composition in any one of Claims 1-4 characterized by the above-mentioned.