JPS6334885B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful method for producing water-dispersible resins. As water-dispersible resins, various emulsions are conventionally known in the form of emulsion polymerization of polymerizable monomers in the presence of surfactants or protective colloids. It has the disadvantage of poor water resistance and corrosion resistance due to the influence of Alkyd emulsions obtained by emulsification after condensation polymerization are also known, but because of the post-emulsification, drying properties, water resistance, corrosion resistance, etc. are inferior due to the influence of the emulsifier. Therefore, in order to eliminate such shortcomings,
As a method that does not use emulsifiers or protective colloids,
For example, Japanese Patent Publication No. 51-10637 and Japanese Unexamined Patent Publication No. 54-
Techniques such as those described in Publication No. 11993 are known. First of all, in Special Publication No. 51-10637,
Water dispersion consisting of mixing a water-soluble resin with unsaturated double bonds such as maleated oil, alkyd resin, unsaturated polyester resin or epoxy ester resin with a polymerizable monomer and dropping the mixture into water for polymerization. A method for producing a synthetic resin has been proposed. However, the water-dispersible resin obtained by the above method is
Since the resin itself is water-soluble, it has the drawback of poor coating film durability and water resistance, making it impractical. Next, JP-A-54-11993 discloses a water-dispersible resin made by polymerizing a polyethylene glycol-modified alkyd resin with a polymerizable vinyl monomer to neutralize some or all of the carboxyl groups in the resin. A method of manufacturing has been described and is known. However, since this method requires polyethylene glycol as an essential component, there are restrictions on the ratio of polyethylene glycol-modified alkyd resin and vinyl polymer.Especially when the vinyl polymer component is large, stable water dispersibility is required. is difficult to obtain, and therefore the advantages of this vinyl polymer cannot be effectively utilized. However, the present invention eliminates all the various drawbacks of the prior art as described above, combines the respective advantages of alkyd resin and acrylic polymer or vinyl polymer, has excellent durability, water resistance, corrosion resistance, alkali resistance, etc. ,
It is an object of the present invention to provide a method for preparing stable water-dispersible resins. That is, the present invention includes (a) oil or fatty acid 0 to 50 parts by weight (hereinafter abbreviated as parts) (b) polyfunctional alcohol 15 to 50 parts (c) polybasic acid or its anhydride 10 to 40 parts ( d) Monobasic acid having 6 to 18 carbon atoms in one molecule 0 to 15〃 (e) Epoxy compound 0 to 50 parts per 100 parts of the total amount of components (a) to (d) and (f) Polyoxyethylene polyoxypropylene block polyether glycol having an average molecular weight of 2,000 to 30,000 2 to 15 parts per 100 parts of the total amount of components (a) to (d), components (a) to (d) are hydroxyl groups/carboxyl The base is
(g) α,β-ethylenically unsaturated monomer
15 to 85 parts of a polymerizable monomer mixture consisting of 85 to 100% by weight (hereinafter abbreviated as %) and (h) 0 to 15 parts of polyoxyalkylene glycol (meth)acrylic ester are combined with component (f). (h) Blend so that the total amount in the water-dispersible resin obtained is 3 to 20 parts, and then polymerize, and further neutralize some or all of the carboxyl groups as necessary. It is an object of the present invention to provide a method for producing a water-dispersible resin. Therefore, in the present invention, polyoxyethylene polyoxypropylene block polyether glycol (f) is essential as a component of the alkyd resin, and polyoxyalkylene is optionally used as a component of the polymerizable monomer. Glycol (meth)acrylic esters (h) are also used, or these polyoxyethylene polyoxypropylene block polyether glycols (f) and polyoxyalkylene glycol (meth)acrylic esters are used.
One of the characteristics is that it is used in combination with (h), and by doing so, the aim is to provide a method for preparing a resin with excellent water dispersibility. The sum of these components (f) and (h) in the resin obtained by the method of the present invention is 3 to 20 parts, preferably 5 to 15 parts, and the sum of these two components is 3 parts. If the amount is less than 20 parts, it is difficult to obtain a stable water-dispersible product, while if it exceeds 20 parts, the water resistance and durability will be poor. The excellent water dispersibility of the water-dispersible resin itself, which is a feature of the present invention, allows the ratio of component (f) in the alkyd resin to component (h) in the acrylic polymer to be changed depending on the degree of acrylation. let That is, when the degree of acrylation is low, more component (f) is used, whereas when the degree of acrylation is high, more component (h) is used. The alkyd resin used in carrying out the method of the present invention can be prepared by conventional manufacturing methods. For example, the above-mentioned components (a) to (f) are charged into a reaction vessel, and the esterification reaction is carried out under a nitrogen atmosphere at a temperature of 150 to 230°C until the desired acid value is reached. The acid value of the alkyd resin is suitably 30 or less, preferably 20 or less; if it exceeds 30, water resistance and alkali resistance will be poor. The component (a) used in preparing the alkyd resin is one or more selected from drying oils, semi-drying oils, and their fatty acids, and the use of the component (a) is If the amount exceeds 50 parts, water dispersibility becomes poor, which is not preferable. Representative examples of the component (a) include tung oil, tall oil, linseed oil, safflower oil, soybean oil, dehydrated castor oil, and tall oil, as well as fatty acids thereof. (b) Ingredients include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol,
1,3-butylene glycol, 1,4-butylene glycol, 2,2,4-trimethyl-1,3-
pentanediol, 1,6-hexanediol,
Examples include glycerin, trimethylolethane, trimethylolpropane, tris-(hydroxyethyl)isocyanurate, pentaerythritol or dipentaneerythritol. Typical component (c) is phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, maleic acid, fumaric acid, adipic acid, succinic acid, sebacic acid, dimer acid or trimellitic acid, and These acid anhydrides and the like. Component (d) includes benzoic acid, tert-butylbenzoic acid, isodecanoic acid, and cyclohexanoic acid. Component (e) includes bisphenol-type epoxy resins, and representative bisphenol-type epoxy resins include "Epiclon 850, 1050, 4050, and 7050" [Dainippon Ink & Chemicals Co., Ltd. ) products]. The amount of component (e) used is as described in (a) to (d) above.
If the amount exceeds 50 parts based on 100 parts of the total amount of components, it is not preferable because it tends to cause yoking in weather resistance tests. As component (f), polyoxyethylene polyoxypropylene block polyether glycol with an average molecular weight of 2,000 to 30,000 is used, but the hydrophobic molecular weight and the amount of ethylene oxide and propylene oxide added can be adjusted and combined as desired. As a result, a wide range of materials with freely changed HLB, morphology, and other characteristics can be used. Specifically, the general formula HO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H [] [However, a+c in the formula is within the range of 2 to 300. It is assumed that b is within the range of 10 to 80. ], but typical examples of the component (f) include “Pluronic L-
31, 44, 61, 62, 64 and 85, P-84, and F-68, 77 and 88'' [products of Asahi Denka Kogyo Co., Ltd.]. These can be used singly or in combination of two or more. Furthermore, as the component (f), an ethylenediamine derivative having a polyoxyethylene polyoxypropylene block polyether group and represented by the following general formula [] can also be used. [However, it is assumed that x ₁ +x ₂ +x ₃ +x ₄ in the formula is within the range of 4 to 100, and y ₁ +y ₂ +y ₃ +y ₄ is within the range of 4 to 400. ] Such ethylenediamine derivatives include "Tetronik F-701" (average molecular weight = 3000, ethylene oxide content = 10 mol%), "Tetronik F-701" (average molecular weight = 3000, ethylene oxide content = 10 mol%),
-707" (average molecular weight = 11000, ethylene oxide content = 70 mol%) and "Tetronik P-
908'' (average molecular weight = 27000, propylene oxide content = 80 mol%) [all products manufactured by Asahi Denka Kogyo Co., Ltd.] or two or more selected from
Typically used. The appropriate amount of component (f) to be used is 2 to 15 parts, preferably 3 to 10 parts, based on 100 parts of the total amount of components (a) to (d). In addition to component (h), 3 to 20 parts, preferably 5 parts.
A range of ~10 parts is appropriate. In carrying out the method of the present invention, polyoxyethylene polyoxypropylene block polyether glycol or its ethylenediamine derivative contained in the target resin is generally used as a surfactant, so polyethylene glycol It has excellent emulsifying and dispersing power compared to , and also has good pigment dispersibility as a paint vehicle. In addition, the component (f) itself also has hydrophobicity because it contains a polyoxypropylene block moiety, compared to a polyoxyethylene glycol containing only a polyoxyethylene glycol without a polyoxypropylene block moiety. Because of this, it can impart good water resistance, and when it contains an ethylenediamine derivative, the nitrogen atoms contained in the molecule of the derivative also impart adhesion to the metal substrate. Therefore, it is advantageous in terms of imparting rust prevention properties. Component (g) used in carrying out the method of the present invention includes unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid or itaconic acid; methyl acrylate; Acrylic acid esters such as ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate or 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-methacrylate Methacrylic acid esters such as propyl, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, β-hydroxyethyl methacrylate or 2-ethylhexyl methacrylate; styrenic monomers such as styrene, vinyltoluene or α-methylstyrene Including vinyl formate, vinyl acetate, vinyl propionate, acrylamide, N-methylolacrylamide, methacrylamide, acrylonitrile, vinyl stearate, divinylbenzene, diisopropenylbenzene, allyl acetate, diallyl adipate,
Examples include one or a mixture of two or more of dimethyl itaconate, diethyl maleate, allyl alcohol, vinyl chloride, vinylidene chloride, and ethylene. The component (h) used in carrying out the method of the present invention includes, for example, the general formula R ₁ :H, CH ₃ R ₂ : H, CH ₃ R ₃ : H, CH ₃ n: 5-23, and more specifically,
Polypropylene glycol monomethacrylate (R ₁ = CH ₃ , R ₂ = CH ₃ , R ₃ = H, n = 5-6; “Blenmar PP-1000” manufactured by NOF Corporation), polyethylene glycol monomethacrylate (R ₁ = _CH3 ,
R ₂ = H, R ₃ = H, n = 7 to 9; “Blenmar PE-350” manufactured by NOF Corporation), methoxypolyethylene glycol monomethacrylate (R ₁ = CH ₃ , R ₂
=H, R ₃ = CH ₃ , n = 9; "NK" manufactured by Shin-Nakamura Chemical Co., Ltd.
-ester M-9G"), methoxypolyethylene glycol methacrylate (R ₁ = CH ₃ , R ₂ = H,
R ₃ = CH ₃ , n = 23; “NK-Ester H” manufactured by the same company
-23G)). The amount of component (h) used is as follows:
A suitable range is 0 to 15%, preferably 2 to 10%, based on the total amount with component (g). However, (h)
The amount of ingredients is 3 to 20 parts in addition to ingredient (f),
Preferably, the amount is within the range of 5 to 10 parts. (f)
If the sum of both components (h) is less than 3 parts, it is difficult to obtain a stable water-dispersible resin, while if it exceeds 20 parts, there is a disadvantage that water resistance and rust prevention properties are poor. . In carrying out the method of the present invention, any polymerization method can be used to polymerize the polymerizable monomers (g) and (h) in the presence of an alkyd resin. For example, alkyd resin is dissolved in polymerizable monomers consisting of components (g) and (h), and the temperature is 0°C.
A method of proceeding with polymerization in the presence of a polymerization catalyst at ~90°C, preferably 40°C ~ 80°C, or a method in which an alkyd resin is dissolved in a water-soluble solvent, and a polymerizable monomer consisting of (g) and (h) is Examples include a method in which polymerization is carried out while dropping a polymer and a polymerization catalyst. moreover,
It is also useful to carry out emulsion copolymerization by dispersing the alkyd resin in water in advance. Polymerization catalysts that can be used in carrying out the method of the present invention include, for example, inorganic peroxide compounds such as known potassium or ammonium persulfates, hydrogen peroxide, percarbonates; acyl peroxides (such as benzoyl peroxide); ), alkyl hydroperoxides (e.g. tertiary butyl hydroperoxide, p-menthane hydroperoxide), dialkyl peroxides (e.g. di-
Organic peroxide compounds such as tertiary butyl peroxide; or α,α'-azobisisobutyronitrile compounds are used. Such inorganic or organic peroxide compounds can also be used as redox catalysts in combination with reducing agents. Such reducing agents include, for example, sodium acid sulfite, or sodium sulfite, potassium acid sulfite, potassium sulfite, sodium hydrosulfite, potassium hydrosulfite, sodium formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate and zinc formaldehyde. One or more types selected from sulfoxylates and the like can be mentioned. When dispersing the copolymer resin thus obtained in water, it is desirable to neutralize some or all of the carboxyl groups in the resin with a neutralizing agent, and the pH after neutralization is 6.5 to 9.5. , preferably within the range of 7.0 to 8.5. Such neutralizing agents include inorganic alkalis such as lithium hydroxide, potassium hydroxide, and sodium hydroxide, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-n-propylamine, and dimethyl-n-propyl. Water-soluble amines such as amines; monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine,
Examples include one or more selected from triisopropanolamine, hydroxylamine, and the like. Thus, the water-dispersible resin obtained by the method of the present invention has various characteristics compared to conventional water-dispersible resins. That is, firstly, it has the flexibility, water resistance, and adhesion that are the advantages of alkyd resin, and the high hardness, drying properties, weather resistance, and stain resistance of acrylic polymer, and secondly, it has the advantages of alkyd resin. (f) component in and (h) in acrylic polymer
The purpose is to achieve excellent water dispersibility and stability by using other components in combination. Such water-dispersible resins obtained by the method of the present invention are useful as paints. When used as a paint, it can be modified by mixing a plasticizer, acrylic emulsion, styrene-butadiene latex, water-soluble resin, etc., if necessary. When the water-dispersible resin thus obtained is used in air-drying or forced-drying paints, it is preferable to add a metal dryer to accelerate curing in the air. Such metal dryers include, for example, cobalt naphthenate, lead naphthenate, etc. Typical examples include zirconium naphthenate, manganese naphthenate, and calcium naphthenate.These are used singly or as a mixture of two or more, and the amount used is 0.05 as the amount of metal per 100 parts of resin solid content. ~0.5 part is preferred. On the other hand, when using the water-dispersible resin obtained by the method of the present invention as a baking paint, amino resin, block polyisocyanate,
A curing agent such as an epoxy resin may be added. Examples of the amino resin here include melamine resin, benzoquanamine resin, and urea resin, and other ureas can also be used. These curing agents are preferably used in an aqueous solution or water-dispersible state. The appropriate amount of the curing agent to be used is within the range of 5 to 30 parts as solid content per 100 parts of resin solid content. A paint using a water-dispersible resin obtained by the method of the present invention has excellent paint workability in airless spray paint. Conventional emulsion paints tend to foam due to the influence of emulsifiers, and conventional water-soluble paints cause sagging, both of which have drawbacks in terms of surface condition and workability.
The paint obtained using the water-dispersible resin obtained by the method of the present invention does not contain an emulsifier and is water-dispersible, so it has the advantage of being difficult to foam and sag. Moreover, such paints can be applied by brushing, dipping, air spraying, etc. Next, the present invention will be specifically explained using examples, comparative examples, applied examples, and comparative applied examples. Example 1 315 parts of safflower oil fatty acid, 316 parts of trimethylolpropane, 197 parts of isophthalic acid, 72 parts of fumaric acid and "Pluronic F-77" (=
5600, ethylene oxide content = 70 mol% and propylene oxide content = 30 mol%), a dehydration condensation reaction was carried out at 210°C for 7 hours, and the solid acid value was 25, and An alkyd resin having a viscosity (60% solution of butyl cellosolve) of M-N was obtained. 100 parts of this alkyd resin are diluted with 67 parts of butyl cellosolve and mixed with a premix consisting of 40 parts of methyl methacrylate, 5 parts of ethyl acrylate and 5 parts of "Blemmer PE-350" at a temperature of 130°C. 2 parts of tert-butyl peroxide were added dropwise over 3 hours to polymerize, yielding a resin solution with a non-volatile content of 69.5% and a viscosity of _Z4 . This was then neutralized with 3.6 parts of triethylamine and diluted with 200 parts of water to give a nonvolatile content of 35.8%, a viscosity of 4200 cps, and a pH of
A translucent emulsified dispersion of 7.5 was obtained. When 1 part of 5% cobalt naphthenate was added to 100 parts of this emulsified dispersion and applied to a glass plate, a strong coating film was formed that tested to the touch in 15 minutes and took 15 hours to harden. Obtained. Furthermore, no abnormality was observed even when this coating film was immersed in water for 24 hours. Example 2 372 parts of linseed oil and pentaerythritol
To the transesterification product obtained from 75 parts, 242 parts of phthalic anhydride and dipropylene glycol were added.
Add 100 parts to 190 until the solid acid value reaches 40.
The esterification reaction is carried out at °C, then 100 parts of "Epiclon 1050" (epoxy equivalent = 450) and "Pluronik L-64" (= 2600, ethylene oxide content = 40 mol% and propylene oxide content = 60 mol%) Add 80 parts of
After a period of reaction, an alkyd resin having a solid content acid value of 15.4 and a viscosity (60% butyl cellosolve solution) of H-I was obtained. 100 parts of this resin was diluted with 87 parts of isopropylene glycol, and an additional 55 parts of styrene, n.
- A monomer premix consisting of 35 parts of butyl acrylate, 3 parts of acrylic acid and 7 parts of "Blemmer PE-350" and 2 parts of tert-butyl peroxybenzoate are added dropwise at 130°C and polymerized. A resin solution with a nonvolatile content of 70% and a viscosity of Z ₇ was obtained. This was then neutralized and diluted with 5.5 parts of triethylamine and 186 parts of water to obtain a translucent emulsified dispersion with a nonvolatile content of 42%, a viscosity of 8500 cps, and a pH of 7.8. To 100 parts of this dispersion, add 1 part of 5% cobalt naphthenate and 3 parts of 25% lead naphthenate,
When applied to a glass plate, a coating film was obtained that tested to the touch in 8 minutes and took 7 hours to cure.After 24 hours, this coating film remained stable even after being immersed in water for 24 hours. No abnormalities were observed. Example 3 100 parts of the alkyd resin obtained in Example 2
While maintaining the temperature at 80°C, a mixture of 1.8 parts of 25% aqueous ammonia and 120 parts of water was stirred vigorously.
After dripping for 5 hours, the non-volatile content was 44.6%.
A translucent emulsified dispersion with a viscosity of 2500 cps was obtained. Add 130 parts of water to this, then 63 parts of styrene.
1 part of potassium persulfate in 50 parts of water. ,80℃
The mixture was added dropwise over 3 hours and polymerized to obtain a milky white aqueous dispersion with a non-volatile content of 40% and a viscosity of 350 cps, with very little coagulation. To 100 parts of this dispersion, 1 part and 2 parts of 5% cobalt naphthenate and 25% lead naphthenate were added, respectively, and applied to a glass plate.
A clear coating film was obtained in 12 minutes and with a curing time of 8 hours. This coating film after 24 hours is submerged in water.
No abnormality was observed even after 24 hours of immersion. Example 4 An esterification reaction was carried out at 210°C for 6 hours using 300 parts of soybean oil fatty acid, 321 parts of trimethylolpropane, 197 parts of isophthalic acid, and 100 parts of "Tetronik F-707". An alkyd resin having a solid content acid value of 15.0 and a viscosity (60% butyl cellosolve solution) of O-P was obtained. 100 parts of this resin was emulsified and dispersed with 200 parts of water containing 2 parts of triethylamine, and further 25 parts of styrene, 15 parts of n-butyl acrylate, 22 parts of methyl methacrylate and "Blemmer PE" were added.
-350'' and a solution of 1 part of potassium persulfate dissolved in 30 parts of water.
The mixture was added dropwise at 80° C. for 3 hours and polymerized to obtain a translucent aqueous dispersion with a nonvolatile content of 41.8% and a viscosity of 4800 cps. When 1 part of 5% cobalt naphthenate and 3 parts of 20% lead naphthenate were added to 100 parts of this water dispersion and applied to a glass plate, the finger test showed that it hardened in 20 minutes. A coating film that lasted 6 hours was obtained, and this coating film after 24 hours was immersed in water for 24 hours.
Although it was immersed for a certain period of time, no abnormality was observed. Comparative Example 1 315 parts of safflower oil fatty acid, 316 parts of trimethylolpropane, 197 parts of isophthalic acid, 72 parts of fumaric acid, and 30 parts of "Pluronik F-77" were dehydrated at 210°C for 7 hours. Condensation reaction,
100 parts of the alkyd resin thus obtained were diluted with 78 parts of butyl cellosolve and, at 130°C, 50 parts of styrene, 15 parts of methyl methacrylate, n
- A premix consisting of 33 parts of butyl acrylate and 2 parts of methacrylic acid and 2 parts of ditertiary butyl peroxide are added dropwise over a period of 3 hours to polymerize, resulting in a non-volatile content of 71.2% and a viscosity of A control resin solution named _Z5 was obtained. Next, 3.5 parts of triethylamine and 245 parts of water were added to this and emulsified and dispersed, resulting in a highly viscous aggregate that was insoluble in water. Comparative Example 2 Using 320 parts of dehydrated castor oil fatty acid, 226 parts of trimethylolpropane, 204 parts of phthalic anhydride, and 250 parts of "Pluronik F-77", these were subjected to an esterification reaction, and the solid content acid value was 12.5.
An alkyd resin having a viscosity of T-U was obtained. When 100 parts of this resin was emulsified and dispersed with 2.2 parts of triethylamine and 148 parts of water, the nonvolatile content was
An aqueous dispersion with a concentration of 40.8% and a viscosity of 3200 cps was obtained. Next, 50 parts of methyl methacrylate, 20 parts of n-butyl acrylate, and 30 parts of "NK-ester M-9G" were added to 100 parts of this water dispersion, and water was added.
A solution of 1 part of ammonium persulfate dissolved in 50 parts was added dropwise over 3 hours, and emulsion copolymerized at 80℃, resulting in a non-volatile content of 44.8% and a viscosity of 22,000 cps.
A control aqueous dispersion was obtained. Comparative Example 3 380 parts of linseed oil fatty acid, 330 parts of trimethylolpropane, 200 parts of phthalic anhydride, 10 parts of maleic anhydride, and "polyethylene glycol #1000" [Daiichi Kogyo Seiyaku Co., Ltd. product; average molecular weight =
1000] to obtain an alkyd resin having a solid content acid value of 12.0 and a viscosity (60% butyl cellosolve solution) of TU. Next, 100 parts of this resin and 87 parts of butyl cellosolve were heated to 130°C, and 70 parts of styrene was added thereto.
parts, 30 parts of n-butyl acrylate and tert-
Three parts of butyl peroxybenzoate were added dropwise over 3 hours to effect polymerization, and the mixture was maintained at the same temperature for an additional 3 hours. After cooling, 2 parts of triethylamine and 300 parts of water were added to the thus obtained resin solution to emulsify it, but it immediately separated into two layers. Application Examples 1 to 4 and Comparative Application Example 1 The various water-dispersible resin dispersions (that is, water dispersions) obtained in Examples 1 to 4 and Comparative Example 2 were
Using 30 parts of each as a solid content, 70 parts of "Tiepeque R-930" [Rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd.] and 55 parts of water were mixed separately and kneaded with a sand grinder. Then, 40 parts of the same aqueous dispersion was added as a solid content, and then 5 parts
A white enamel paint with a PWC of 50% was obtained by separately adding 1 part of % cobalt naphthenate and 2 parts of 24% lead naphthenate. The viscosity of each of these paints was adjusted to 500 cps, and then each paint was applied separately to a polished mild steel plate (0.8 mm x 70 cm x 150 mm), and then dried at room temperature for 48 hours. A cured coating film having coating properties as shown in Table 1 was obtained. 【table】

Claims (1)

[Claims] 1 (a) Oil or fatty acid 0-50 parts by weight (b) Polyfunctional alcohol 15-50〃 (c) Polybasic acid or its anhydride 10-40〃 (d) In one molecule Monobasic acid having 6 to 18 carbon atoms 0 to 15〃 (e) Epoxy compound 0 to 50 parts by weight based on 100 parts by weight of the total amount of components (a) to (d) and (f) Average molecular weight of 2000 ~30,000 polyoxyethylene polyoxypropylene block polyether glycol (2 to 15 parts by weight per 100 parts by weight of the total amount of components (a) to (d)), components (a) to (d) have a hydroxyl group/carboxyl group number
(g) α,β-ethylenically unsaturated monomer
15 to 85 parts by weight of a polymerizable monomer mixture consisting of 85 to 100% by weight and (h) polyoxyalkylene glycol (meth)acrylic ester 0 to 15% by weight,
Component (f) and component (h) are blended so that the sum of the components is 3 to 20 parts by weight in the resulting water-dispersible resin, and then polymerized, and if necessary, part of the carboxyl group or A method for producing a water-dispersible resin, which is characterized by completely neutralizing the resin.