JPH0617420B2 - Vinyl resin emulsion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel emulsion polymerization composition capable of giving a coating film having improved water resistance.

BACKGROUND ART Emulsion polymerization compositions obtained by addition-polymerizing vinyl acetate, vinyl chloride, vinylidene chloride, acrylic monomers and the like in water containing an emulsifier and a polymerization catalyst have been widely used for a long time as so-called emulsion paints. Since a large amount of an emulsifier used to stably disperse water in a catalyst impairs water resistance of a coating film, improvement of water resistance has been strongly desired.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Therefore, in a synthetic emulsion, an emulsifier for dispersing resin particles in an aqueous medium is not required, or the amount thereof is reduced to such an extent that water resistance is not adversely affected. Emulsion polymerized compositions are highly desirable and it is an object of the present invention to provide such emulsion polymerized compositions.

Means for Solving the Problems According to the present invention, the above object is (In the formula, R ₁ is hydrogen or a methyl group; R ₂ is an aliphatic hydrocarbon having 2 to 10 carbon atoms which may have a substituent,
Alicyclic hydrocarbon having 6 to 7 carbon atoms, aromatic hydrocarbon having 6 carbon atoms; Or Repeating units of; _{R 3} is ethylene or propylene; R
₄ is an alkylene having 2 to 7 carbon atoms which may have a substituent; R ₅ is an alkylene having 2 to 5 carbon atoms which may have a substituent; m and n are the average number of repeating units 3 to 50% by weight of a reactive vinyl monomer having a neutralized terminal carboxyl group represented by the formula: m is 1 to 10 and n is 2 to 50; X is an inorganic or organic base; This can be achieved by an emulsion polymerization composition obtained by emulsion polymerization of 97 to 50% by weight of one α, β-ethylenically unsaturated compound in an aqueous medium.

The reactive vinyl monomer represented by the above formula [I] used for the synthesis of the emulsion polymerization composition of the present invention has the formula (Wherein R ₁ is hydrogen or a methyl group; A is Or Repeating units of; _{R 3} is ethylene or propylene; R
₄ is an alkylene having 2 to 7 carbon atoms which may have a substituent; R ₅ is an alkylene having 2 to 5 carbon atoms which may have a substituent; m and n are the average number of repeating units A value of m is 1 to 10 and n is 2 to 50), and a (meth) acrylate having a terminal hydroxyl group, (In the formula, R ₂ has 2 carbon atoms which may have a substituent.
10 aliphatic hydrocarbons, C 6-7 alicyclic hydrocarbons, C 6 aromatic hydrocarbons) are polymerized, preferably in the presence of a radical polymerization inhibitor, (In the formula, R ₁ is hydrogen or a methyl group; R ₂ is an aliphatic hydrocarbon having 2 carbon atoms which may have a substituent, an alicyclic hydrocarbon having 6 to 7 carbon atoms, an aromatic having 6 carbon atoms. Group hydrocarbons; A is Or Repeating units of; _{R 3} is ethylene or propylene; R
₄ is an alkylene having 2 to 7 carbon atoms which may have a substituent; R ₅ is an alkylene having 2 to 5 carbon atoms which may have a substituent; m and n are the average number of repeating units The compound is represented by a value of m of 1 to 10 or n of 2 to 50), and can be advantageously produced by neutralizing the compound with an inorganic or organic base X.

Examples of the (meth) acrylate having a terminal hydroxyl group represented by the formula [II] include hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate and β-propiolactone δ-valerolactone, δ-
It means a compound to which cyclic esters such as caprolactone and ε-caprolactone or cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran are added.

Examples of commercially available products corresponding to this include Praxel (FM-1) FA-1 to which hydroxyethyl (meth) acrylate and ε-caprolactone are added.
[1: 1 adduct], (FM-3) FA-3 [1: 3 adduct],
(FM-5) FA-5 [1: 5 adduct] (all of which are Daicel chemistry, registered trade name) or Blemmer PE, Blemmer PP (Nippon Yushi, registered) which is obtained by adding ethylene oxide or propylene oxide to methacrylic acid. Trade names) and the like, and those easily manufactured by those skilled in the art based on similar reactions are included.

On the other hand, examples of the acid anhydride represented by the formula [III] include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, hettic anhydride, and hymic anhydride. Acids, adipic anhydride, azelaic anhydride, sebacic anhydride or substituted derivatives thereof are used.

The reaction proceeds easily by simply heating and stirring these raw materials, but it is preferable to carry out in the presence of a radical polymerization inhibitor for protecting the terminal vinyl group, for example, hydroquinone monomethyl ether. Fifty
It is used in an amount of 00 ppm or less, more preferably about 500 ppm or less. The hydroxy group-containing (meth) acrylate and the acid anhydride are usually used in a weight ratio of 9:10 to 11:10.

The reactive monomer having a terminal carboxyl group described above can freely change the balance between the hydrophilic portion and the hydrophobic portion by introducing R ₂ and A alkylene chains. It can provide excellent surface activity. The present inventors obtained the above [I] obtained by neutralizing such a monomer with an inorganic or organic base.
It was found that the reactive monomer represented by the formula (1) has a far superior surface-active ability than the compound having a free carboxyl group, which is the basis of the present invention.

Therefore, in the present invention, the formula [I] (Wherein R ₁ , A, R ₂ , and X are as described above) is extremely novel because the compound is a reactive monomer and can be used as an emulsifier having a surface-active function. .

According to the invention, 3 to 50% by weight of the reactive vinyl monomer of the formula [I] together with 97 to 50% by weight of at least one α, β-ethylenically unsaturated compound in an aqueous medium. An emulsion-polymerized emulsion-polymerized composition is provided.

As the α, β-ethylenically unsaturated compound, any α, β-ethylenically unsaturated compound of the type usually used in the production of vinyl resins is preferably used, and they are roughly classified as follows.

Those having one α, β-ethylenically unsaturated bond in the molecule: 1) Carboxyl group-containing monomer such as acrylic acid, methacrylic acid, crotonic acid itaconic acid, maleic acid, fumaric acid, etc. 2) Hydroxyl group Contained monomers such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol, etc. 3) Nitrogen-containing alkyl acrylate or methacrylate Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. 4) Polymerizable amides such as acrylic acid amide, methacrylic acid amides, etc. 5) Polymerizable nitriles such as acrylo 6) Alkyl acrylate or methacrylate such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, etc. 7) Polymerizable aromatic carboxyl group For example, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, etc., 8) α-olefin, for example, ethylene, propylene, etc., 9) vinyl compound, for example, vinyl acetate, vinyl propionate, etc. Two or more α, Having β-ethylenically unsaturated bond: 10) Diene compound, such as butadiene, isoprene, etc. 11) Polymerizable unsaturated monocarboxylic acid ester of polyhydric alcohol; Polymerizable unsaturated alcohol ester of polybasic acid ; 2
Aromatic compounds substituted with one or more vinyl groups such as ethylene glycol acrylate, ethylene glycol methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylol Propane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate. Methacrylate, pentaerythritol tetramethacrylate , Glycerol dimethacrylate, glycerol diacrylate, glycerol allyloxy dimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1
-Trishydroxymethylethane dimethacrylate,
1,1,1-trishydroxymethylethane trimethacrylate, 1,1,1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane triacrylate, 1,1,1-trishydroxymethylpropane diacrylate Methacrylate, 1,1,1-
Trishydroxymethylpropane trimethacrylate,
Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate diallyl terephthalate, dialyphthalate, divinylbenzene, etc. These monomers are used alone or in combination, and emulsion polymerization is carried out according to a conventional method.

In emulsion polymerization, it is not necessary to use a surfactant or an emulsifier separately because the monomer of the above formula [I] itself has surface activity, but when the amount of the monomer [I] used is small. For these, it is preferable to use a small amount of a surfactant or emulsifier of the type usually used. Particularly preferred are, for example, Japanese Patent Application Nos. 54-110865; 55-56048; 55-116293; 53-12389.
9; 55-47652; 56-71864; 57-13053 and the like amphoteric resins. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, t-butyl oxide, and cumene hydroperoxide; azobiscyanovaleric acid,
Organic azo compounds such as azobisisobutyronitrile, azobis (2,4-dimethyl) valeronitrile, azobis (2-amidinopropane) hydrochloride; inorganics such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide Water-soluble radical initiators; redox initiators and the like are preferably used, and examples of chain transfer agents include mercaptans such as ethyl mercaptan, butyl mercaptan, and dodecyl mercaptan; halogens such as carbon tetrabromide and carbon tetrachloride. Carbonized compounds can be used. Surfactant, emulsifier, optionally used
The polymerization initiator, the ratio of the chain transfer agent used in the aqueous medium, the polymerization method, and the like can all be based on conventional techniques.

In the emulsion-polymerized composition of the present invention thus obtained, the external emulsifier is not contained, or the amount of the external emulsifier is extremely small, so that after the film formation, the low-molecular emulsifier does not remain in the film, and the film Since there are almost no low-molecular substances that solubilize the coating even after being immersed in water, the water resistance of the coating can be greatly improved as compared with conventional emulsion coatings.

The particle size of the resin particles obtained by emulsion polymerization can be easily controlled depending on the purpose of use.
Alternatively, the particle size (measured by a laser light scattering method) is adjusted to 50 to 500 by changing the amount of the monomer of the formula [I] used.
It can be freely controlled within the range of nm. It has been confirmed that the amount of the reactive monomer [I] used is usually 3 to 50% by weight, preferably 10 to 30% by weight, based on all the monomers.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. Unless stated otherwise, parts and percentages are by weight.

Reference Example 1 150 parts of succinic anhydride and 385 parts of Praxel FM-1 (ε-caprolactone and 2-hydroxyethylmethacrylate in a glass reaction flask equipped with a stirrer, Dimroth, thermometer and air inlet tube) : 1
Molar adduct, manufactured by Daicel Chemical Co., Ltd.) and 500 ppm of hydroquinone monomethyl ether were charged all at once. Then, the reaction was carried out by stirring at an internal temperature of 150 ° C. for 40 minutes while sucking air through the inlet tube. After the reaction was completed, when the product was cooled to room temperature, a small amount of unreacted acid anhydride crystals were precipitated, and this was removed by filtration to obtain the desired reaction composition.

This reaction composition has an acid value of 172 and a viscosity of 250 cp (25 ° C.)
Met. When the reaction rate was determined by measuring the acid value of the reaction composition, it was 96%.

Reference Example 2 In the same reactor as in Reference Example 1, 60 parts of succinic anhydride, 440 parts of Praxel FM-5 (5: 1 mol adduct of ε-caprolactone and 2-hydroxymethacrylate, manufactured by Daicel Chemical Industries) and 500pp for the total amount charged
A batch of m-hydroquinone monomethyl ether was charged. Then, while introducing air, the internal temperature of 150 ℃ 60
The reaction was carried out by stirring for a minute. After the completion of the reaction, when the product was cooled to room temperature, a small amount of unreacted acid anhydride crystals were precipitated, which were removed by filtration to obtain the desired reaction composition.

The reaction composition is a semi-solid (25
℃). The reaction rate was 96% as measured by the same method as in Reference Example 1.

Reference Example 3 In the same reaction apparatus as in Reference Example 1, 98 parts of maleic anhydride, 480 parts of Praxel FM-3 (3: 1 mol adduct of ε-caprolactone and 2-hydroxymethacrylate,
(Manufactured by Daicel Chemical Industries, Ltd.) and 500 ppm of hydroquinone monomethyl ether were charged all at once. Then, the reaction was carried out by stirring at an internal temperature of 150 ° C. for 60 minutes while introducing air.

The reaction composition had an acid value of 103 and a viscosity of 350 cP (25 ° C.). The reaction rate was measured by the same method as in Reference Example 1, and it was 95%.

Reference Example 4 Using the same reactor as in Reference Example 1, 154 parts of tetrahydrophthalic anhydride and 420 parts of Blemmer PE-350 were used.
(7-9: 1 mol addition product of ethylene oxide and methacrylic acid, made by NOF CORPORATION) and 500 ppm with respect to the total amount charged
The above hydroquinone monomethyl ether was charged all at once. Then, the reaction was carried out by stirring at an internal temperature of 150 ° C. for 60 minutes while introducing air.

The reaction composition had an acid value of 103 and a reaction rate of 96%.

Reference Example 5 Using the same reactor as in Reference Example 1, 148 parts of phthalic anhydride, 400 parts of Bremmer PP-1000 (5.5: 1 mol adduct of propylene oxide and methacrylic acid, manufactured by NOF CORPORATION) and total 500 ppm of hydroquinone monomethyl ether was charged all at once. Then, the reaction was carried out by stirring at an internal temperature of 150 ° C. for 60 minutes while introducing air.

The reaction composition had an acid value of 108 and a viscosity of 300 cP (25 ° C.). The reaction rate was 95%.

Example 1 280 parts of ion-exchanged water was previously charged into a glass reaction flask 1 equipped with a stirrer, a Dimroth, a thermometer, a dropping funnel and a nitrogen introducing tube, and then the reactive unit amount synthesized in Reference Example 1 100% of body dimethyl ethanolamine
A mixture of 12 parts of the neutralized product, 18 parts of methyl methacrylate, 18 parts of n-butyl acrylate, 16 parts of ethylene glycol dimethacrylate and 34 parts of styrene was stirred for 2 hours at a flask internal temperature of 80 ° C. using a dropping funnel. Dropped. The initiator is 4,4'-azobis-
Emulsion polymerization was carried out by neutralizing 1 part of 4-cyanovaleric acid with an alkali and then simultaneously adding a solution dissolved in 20 parts of ion-exchanged water separately from the above mixed monomer.

The reaction product had a solid content concentration of 25% by weight, and the emulsion particle diameter measured by a laser light scattering method was 200 nm.

Example 2 In a reactor similar to that of Example 1, ion-exchanged water 2 was previously added.
After charging 80 parts, 20 parts of 100% neutralized product of the reactive monomer dimethylethanolamine synthesized in Reference Example 2,
A mixture of 16 parts of methyl methacrylate, 32 parts of n-butyl acrylate and 32 parts of styrene was added dropwise using a dropping funnel at a flask internal temperature of 80 ° C. for 2 hours with stirring. The initiator was prepared by dissolving 1 part of ammonium persulfate in 20 parts of ion-exchanged water, and was added dropwise separately from the above mixed monomer to carry out emulsion polymerization.

The reaction product had a solid content concentration of 25% by weight, and the emulsion particle diameter measured by a laser light scattering method was 80 nm.

Example 3 In a reactor similar to that of Example 1, ion-exchanged water 2 was previously added.
After charging 80 parts, 15 parts of 100% neutralized dimethylethanolamine of the reactive monomer synthesized in Reference Example 3,
A mixture of 17 parts of methyl methacrylate, 34 parts of n-butyl acrylate and 34 parts of styrene was added dropwise with stirring using a dropping funnel at a flask internal temperature of 80 ° C. for 2 hours. The initiator was prepared by dissolving 1 part of ammonium persulfate in 20 parts of ion-exchanged water and simultaneously dropping it separately from the above mixed monomer to carry out emulsion polymerization.

The reaction product had a solid content concentration of 25% by weight, and the emulsion particle diameter measured by a laser light scattering method was 150 nm.

Example 4 In a reactor similar to that of Example 1, ion-exchanged water 2 was previously added.
After charging 80 parts, 16 parts of 100% neutralized dimethylethanolamine of the reactive monomer synthesized in Reference Example 4,
A mixture of 17 parts of methyl methacrylate, 34 parts of n-butyl acrylate and 33 parts of styrene was added dropwise using a dropping funnel at a flask internal temperature of 80 ° C. for 2 hours with stirring. As an initiator, after neutralizing 1 part of 4,4'-azobis-4-cyanovaleric acid with an alkali, a solution dissolved in 20 parts of ion-exchanged water is added dropwise simultaneously with the above mixed monomer. Emulsion polymerization was carried out.

The reaction product had a solid content concentration of 25% by weight, and the emulsion particle diameter measured by a laser light scattering method was 250 nm.

Example 5 In a reactor similar to that of Example 1, ion-exchanged water 2 was previously added.
After charging 80 parts, 15 parts of 100% neutralized dimethylethanolamine of the reactive monomer synthesized in Reference Example 5,
A mixture of 17 parts of methyl methacrylate, 34 parts of n-butyl acrylate and 34 parts of styrene was added dropwise with stirring using a dropping funnel at a flask internal temperature of 80 ° C. for 2 hours. As an initiator, after neutralizing 1 part of 4,4'-azobis-4-cyanovaleric acid with an alkali, a solution dissolved in 20 parts of ion-exchanged water is added dropwise simultaneously with the above mixed monomer. Emulsion polymerization was carried out.

The reaction product had a solid content concentration of 25% by weight, and the emulsion particle diameter measured by a laser light scattering method was 180 nm.

Comparative Example 1 Ion-exchanged water 2 was previously added in the same reactor as in Example 1.
After charging 70 parts, 7.5 parts of Emal O (sodium laurate, manufactured by Kao), 20 parts of methyl methacrylate,
A mixture of 20 parts of n-butyl acrylate and 20 parts of styrene was used, and the temperature inside the flask was 80 ° C using a dropping funnel.
Was added dropwise with stirring for 2 hours. Also, the initiator is 4,
After 1 part of 4'-azobis-4-cyanovaleric acid was neutralized with an alkali, emulsion dissolved in 20 parts of ion-exchanged water was dropped simultaneously with the mixed monomer.

The reaction product had a solid content concentration of 25% by weight, and the emulsion particle diameter measured by a laser light scattering method was 150 nm.

Example 6 Each of the synthetic resin emulsions obtained in Examples 1 to 5 and Comparative Example 1 was flow-coated on a glass plate and then dried by heating at 100 ° C. for 5 minutes. Next, a water resistance test of the emulsion coating film was performed by immersing these glass plates in water having a water temperature of 20 ° C.

The results are shown in Table 1.

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Claims (1)

[Claims] 1. Formula (A) (In the formula, R ₁ is hydrogen or a methyl group; R ₂ is an aliphatic hydrocarbon having 2 to 10 carbon atoms which may have a substituent,
Alicyclic hydrocarbon having 6 to 7 carbon atoms, aromatic hydrocarbon having 6 carbon atoms; Or Repeating units of; _{R 3} is ethylene or propylene; R
₄ is an alkylene having 2 to 7 carbon atoms which may have a substituent; R ₅ is an alkylene having 2 to 5 carbon atoms which may have a substituent; m and n are the average number of repeating units 3 to 50% by weight of a reactive vinyl monomer having a neutralized terminal carboxyl group represented by the formula: m is 1 to 10 and n is 2 to 50; X is an inorganic or organic base. ) A vinyl resin emulsion obtained by emulsion polymerizing 97 to 50% by weight of at least one α, β-ethylenically unsaturated compound in an aqueous medium.