JPS5811539A - Preparation of water-dispersed resin - Google Patents

Abstract

PURPOSE:To prepare a water-dispersed resin having excellent storage stability and useful as a paint curable in air, by esterifying a specific vinyl copolymer with a higher unsaturated fatty acid, etc., neutralizing the ester, polymerizing a radicaly polymerizable monomer in the presence of the above neutralized product, and adding water to the polymer. CONSTITUTION:100pts.wt. of a vinyl copolymer composed of 1-50(wt)% (meth) acrylic acid ester having cyclic unsaturated group and represented by the formulaI(R1 is H or CH3; R2 is group of formula II-V; R3 is H or CH3; m is 0-6; when m is 1, n is 2-5 and when m is 2-6, n is 2), 1-30% alpha,beta-unsaturated carboxylic acid, and 0-50% compound containing polymerizable unsaturated group and hydroxyl group, as constituent units, is esterified with 3-100pts.wt. of a higher unsaturated fatty acid or higher unsaturated fatty acid ester, and the reaction product is neutralized. A radically polymerizable monomer is polymerized in an organic solvent (>=10% of the polymer) in the presence of the above neutralized product, and the resultant polymer is mixed with water (1-20 times the solvent).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a water-dispersed resin with evaporation of water or solvent into the air.

In recent years, water-dispersed resins have come to be widely used in paints and adhesives41 because they are more preferable than solvent-based resins in terms of environmental protection, work environment, resource saving, etc. However, there are still various problems in terms of performance. At present, it is difficult to say that they are comparable to solvent-based FFI resins. In particular, water-dispersed resins obtained by polymerizing monomers in the presence of emulsifiers often have coating defects such as pinholes because the molecular weight of the monomer is generally extremely large. However, there are problems with water resistance, weather resistance, etc.

Alternatively, a radically polymerizable monomer is polymerized in an organic solvent in the presence of a polymer containing a hydrophilic compound such as carboxylic acid as a constituent unit, and the resulting nine polymer is neutralized with a base and water is added. A method for producing dispersion resins is known, but in this method, when a large amount of water is added to the dispersion system in the final water addition step, the dispersion in which the polymer was stably dispersed in the organic solvent Generally, the viscosity of the system gradually increases and becomes viscous, and in order to uniformly disperse such a dispersion system in water, it is necessary to take more steps and apply a higher shearing force.

In order to prevent the increase in viscosity of the polymer, it is known to reduce the amount of water added or to lower the molecular weight of the polymer, but in the former case, the original advantages of a water-dispersed resin are lost. In the latter case, the water resistance and weather resistance of the film formed from the resulting resin were impaired.

On the other hand, as a method for obtaining air-curable water-dispersible resins, for example, a method of modifying alkyd resin with semi-drying oil or drying oil is known, but the resulting oil-modified resin has poor weather resistance and drying speed. Further improvement was desired in this respect.

The present invention has been made in view of the current state of the water-dispersed resins mentioned above, and provides an industrially advantageous water-dispersed resin that has excellent storage stability, a high drying rate, and a dry film that has excellent water resistance, weather resistance, etc. 1 number of 6 provided under the conditions, starvation is the number of ships that satisfies the following relationship. An ester of acrylic acid or methacrylic acid having an unsaturated group,
An esterification reaction product of an α,β-unsaturated carboxyl copolymer having a constituent unit of 0 to 50 by weight of an unsaturated carboxyl compound and a higher unsaturated fatty acid or a higher unsaturated fatty acid ester. A method for producing a water-dispersed resin, which is characterized by polymerizing a optically polymerizable monomer in an organic solvent in the presence of the neutralized product thus obtained, and adding water to the obtained nonapolymer. Wow.

As a specific example of the ester O of acrylic acid or methacrylic acid having a cyclic unsaturated group used in the present invention, the cyclic unsaturated group is a dicyclopentenyl group (-(2I:Il)), where m in the above general formula is In case of O, 5
(si-acryloxide!j!/ri0(5.2.1.0
``)-4-7'' sen (this is 8-acryloxytricyclo( 5.2, 1.0''), cy-4-de-7'' and 9-acryloxytricyclo( 5.2).

It means both 1..Isao 6〕-4-De-7. same as below. ), 5(1)-methacryloxytricyclo[5.

2, 1.0".6]-4-decene (universal name, dicyclopentenyl methacrylate), 8 (91-acryloxytricyclo(5.2.1.O"°6)-2-methyl-4
-decene, 8(II)-acryloxytricyclo[5.

2,1.0"-')-3-methyl-4-decene,
8 till -methacryloxytricyclo(5.2
．． 1.0"・6]-2-methyl-decene, 8(11-methacryloxytricyclo(6,2.1.0"l@)
- 3-methyl-4-decene and the like.

In addition, when Peng in the above general formula is 1, 2-dicyclopentenoxyethyl acrylate (1 CH, CH-CO-C, H, 0), 2-dicyclopentenoxyethyl methacrylate, 2 -dicyclopentenoxypropyl (meth)acrylate (the term refers to 2-dicyclopentenoxyethyl acrylate and 2-dicyclopentenoxypropyl methacrylate. The same applies hereinafter), 3-dicyclopentenoxy Isobutyl (meth)
acrylate, 3-dicyclopentenoxyneopentyl (meth)acrylate, etc., and when m is 2 to 6, diethylene glycol-seno-dicyclopentenyl ether acrylate O ethylene glycol-sono-dicyclopentenyl ether Methacrylate, triethylene glycol mono-dicyclopentenyl ether (meth)acrylate, tetraethylene glycol mono-dicyclopentenyl ether (19) acrylate, pentaethylene glycol mono-dicyclopentenyl (meth)acrylate, hexaethylene glycol Examples include monodicyclopentynyl ether (meth)acrylate.

Further, as the cyclic unsaturated group possessed by the ester represented by the above general formula, examples include the dicyclopentenyl group K, for example -0
10, @1 etc. is given as a specific example in the case of tm m O! +41-acryloxy-1-cyclopentene, 3(4)-methacryloxy-1-cyclopentene, 4
(Il-acryloxy-1-cyclohexene%411+
-Methacryloxybicyclo(2,2,1)-2-heptene, 5(·)-methacryloxybicyclo(2,2,1)-
Examples include 2-heptene.

Among these esters, 8 (匍-1 chloroxytrisic a (5,2,1,0''·') -4-f' 4 !
! > , @ 1ll-methacryloxytricyclo[5
゜l, Oj@) 4-dacene and 2-dicyclopentenoxyethyl (meth)acrylate are III
K is used.

In general, the ester having 1 to 6 in the above general formula is)
Rishi9o (51', IJ"...)-3-7'senol' (common name, dicyclopentenyl 1 to 2-l, HO
), tricycloC51,1゜08...]] Methyl-3-decen-ol HO2-1 + cyclopenten-1-ohk, cyclohexen-1-ol, 2-
Methylcyclohecan-1-ol, bicyclo(12,
1)-2-hebutenol, bicyclo(12,1)-3
%]! It is produced by a method of reacting and esterifying K(meth)acrylic acid.

The vinyl copolymer used in the present invention contains the ester represented by the above general formula in an amount of 1 to 50% by weight (hereinafter, q indicates weight). If it is less than 1 inch, the resulting water-dispersed resin will have poor air curability, and therefore only a film with poor water resistance can be formed. Consistency is not expressed. On the other hand, if the amount is more than 50, the film formed by the water-dispersed resin is likely to be colored, resulting in poor weather resistance.

Further, the vinyl copolymer of the present invention contains α,β-unsaturated carboxylic acid in the range of 1 to 30 to have hydrophilicity, and has the acid of general KIO-1005. The amount of unsaturated carboxylic acid depends on the amount of the compound containing a 4-unsaturated group and a hydroxyl group, but l
When the amount is less than 30, the stability of the water-dispersed resin obtained after polymerizing a radically polymerizable monomer in the presence of such a vinyl copolymer becomes poor, and when it is more than 30, the water-dispersed resin becomes unstable. The film formed by this will have poor water resistance.

As the α,β-unsaturated carboxylic acid such as keratin, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cylindrical acid, maleic acid, fumaric acid, etc. are preferably used.

Furthermore, the vinyl copolymer has a hydrophilic and non-on moiety, and in order to enable an esterification reaction with higher unsaturated fatty acids, etc., which will be described later, a compound containing a polymerizable unsaturated group and a hydroxyl group is added. may be contained as a structural unit.

Specific examples of this unsaturated compound include 2-hydroxyethyl (meth)acrylate, 2-ku droxyp☆pisI
Examples include (meth)acrylate and allyl alcohol. The amount of the unsaturated compound used in the vinyl copolymer is generally kept at 50s or less, since if it exceeds 50%, the water resistance of the film formed by the water-dispersed resin will be poor.

In the present invention, in addition to the ester represented by the above general formula, α, β-unsaturated carpon iron, and a compound containing an unsaturated group and a hydroxyl group, a vinyl monomer having a continuous chain structure is used as a structural unit of 93 It may be contained within a range of less than 100%.

Specific examples of such vinyl monomers include acid alkyl esters of (meth)ac9 such as buti-acrylate and 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, etc.
Further examples include vinyl acetate, acrylate, and the like.

A vinyl copolymer whose constituent units are an ester of acrylic acid or methacrylic acid represented by the above general formula, α, β-unsaturated carboxylic acid, an unsaturated compound having a hydroxyl group and other monomers used as necessary. The combination can be obtained by copolymerizing each monomer according to a conventionally known method, but a copolymerization method is preferred.

(Left below) In this book, the above vinyl copolymer is reacted with a higher unsaturated fatty acid or a higher unsaturated fatty acid ester to undergo an esterification reaction (this is both an esterification reaction and a transesterification reaction in the new narrow sense). The product regenerated as a result of the reaction is called a varnish lPk-forming reaction product.) However, if the above-mentioned vinyl copolymer has a hydroxyl group, it is a higher unsaturated acid. Any unsaturated fatty acid ester
FLJ6 may be used. For example, an ester of an alcohol having an epoxy group and a higher unsaturated fatty acid is preferably used for a one-pot pot in which the vinyl copolymer does not contain a hydroxyl group.
Also possible are esters in which the alcohol-A-residue is a higher unsaturated alkyl.

The higher unsaturated fatty acids used in this article include alkenoic acids such as oleic acid, linoleic acid and other lukadienoic acids, hyrabonic acid, lylunic acid, gamma-lilunic acid, and ereostearic acid and other lukabolyenoic acids, and lycanic acids. Keto acids such as linoleic acid and linoleic acid are preferably used.
It will be done. These can be used alone or as a mixture, but they generally exist as glycerides in drying oils and semi-drying oils, so for example, soybean oil obtained by hydrolyzing soybean oil, which is a semi-drying oil, Commercially available mixtures of various higher fatty acids can be used, such as 11wI acid and dehydrated castor oil fatty acids obtained by hydrolyzing dehydrated castor oil, which is a drying oil.

In the present invention, a higher deficient la fatty acid ester is defined as having an Okihata-Yamoto unkojiwa bond, and having a carbon number of the monocarboxylic acid cleavage to a carbon number of the monocarboxylic alcohol residue preferably 9 or more. However, in general, esters of glycerin and higher unsaturated fatty acids, which have epoxy groups, and higher unsaturated fatty acids are preferably used.

The value of esterified polyhydric alcohols such as glycerides, the value of esterified esters of polyhydric alcohols, and partial esthetics are also available.
In addition, if the ester bond part of the diglyceride in triglyceride has a non-containing ester bond, the value of IQ & fatty acid such as tsukudanic acid, stearic acid, etc. will be added to other ester bonds. Triesters of fatty acids of the above-mentioned glycaneptides are present in fats, but oils and fats containing unsaturated fatty acid esters are Examples include drying oils such as oils, drying oils such as starch oil, synthetic drying soaps such as dehydrated castor oil, drying soaps such as dehydrated castor oil, soybean oil, string seed oil, and beef drying oils such as bran oil.

As the alcohol having an epoxy group, Glycidyl 1 Ruco # is preferably used, and as an alcohol containing an ester with Fuyawa MI Fat Stirrup, for example, Dai! Examples include oil fatty acid glycidyl ester, coconut fatty acid glycidyl ester, and the like.

Conventionally known methods are used for the esterification reaction between the vinyl copolymer and the fatty acid or fatty acid ester,
For example, a method is used in which a vinyl copolymer and a fatty acid or a fatty acid ester are treated as they are or in the presence of O such as an amine, a tin compound, a titanium compound, 99 mu alkoxide, or an acid. The amount of fatty acid or fatty acid ester used in the esterification reaction is such that the total amount of carboxy groups and mineral hydroxyl groups, if present, in the vinyl copolymer is at least about 10% of the esterification reaction. The current is applied in a range of 3 to 100 parts by weight per 100 parts by weight of the vinyl # copolymer. When the amount of S is less than 100 parts by weight, it is difficult to express air curing properties.Especially when the amount of Esthe K is too small, the effect of imparting flexibility to the vinyl copolymer is poor, and when the amount exceeds 100 parts by weight, the effect of imparting flexibility to the vinyl copolymer is poor. The weather resistance of the obtained water-repellent resin is decreased. The esterification reaction product of the vinyl #^ heavy pot has a molecular weight of LOG @ #10, preferably s, o.
If the weight average molecular weight is less than 9,000, the water resistance of the film, which is affected by the moisture content of the ester, will not be sufficient; A radically polymerizable monomer was polymerized in the presence of a neutralized product obtained by adding a base to the reaction product, and large IIK water was added to form a fraction of organic @1llq1K. The dispersion lk is inverted to a dispersion system in which the polymer is stably dispersed together with a solvent in water (hereinafter, the change in the state of the dispersion system to this state is called phase inversion).

), the viscosity would be extremely high, and additional work would be required to mechanically apply a high shearing force to achieve a strong strain.
1 is required.

The method of the present invention involves pulverizing the esterification reaction product with a base, and in the presence of the thus obtained neutralized product, polymerizing the chemically polymerizable monomer in a 41111m solution using a conventional method. Water is added to the Kokonoesha body.

In the presence of a neutralized product of a vinyl copolymer, the polymerizable monomer described below is polymerized.
Examples include guO''/()-ol, methyl heptarosol, butylcellosol, butypylcelosolp acetate, ethyl carpitol, acetone, methyl ethyl ketone, wI Keneth A/#I, and ξ is used alone or in combination, and the amount thereof is not particularly limited.It is possible that the solvent required for the production of the beer copolymer remains with respect to 100 parts by weight of the polymer obtained in the final hook. In the case where the total amount is 10 parts by weight or more, the total amount is usually 10 parts by weight or more.

In addition, these solvents have a range of 4J96 or less -1, preferably S to 8
When combined with the monomer tIl (described later) in a system containing 0% K, the increase in viscosity in the phase inversion step described above is
Monomers in l1l 0% [Compared to polymerization, it is much more relaxed.

However, if the amount of water exceeds 48g6, the molecular weight of the polymer tIl
l# It becomes difficult to sit.

Esterification reaction product of vinyl copolymer tl [Naturalized with group, usually after decomposing the copolymer with the above *114, for example, ammonia, triethylamine, 1A/kylamine such as triethylamine, dimethyl ethanol Amine, diethylethanolamine, triethanolamine 4IO
This is done by adding an alcohol amine and a 4# tuline base. The amount of base added is usually such that more than half of the carboxyl groups present in the esterification reaction product of the vinyl copolymer are neutralized.

In the present invention, radically polymerizable monomers polymerized in the presence of the above-mentioned neutralized substances are not particularly specified, but specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. t of glycidyl (meth)acrylate in (meth)acrylic acid alkyl ester such as acrylate, 2-ethylhexyl (meth)acrylate, etc.
Alkenyl benzenes such as styrene, α-methylstyrene, and vinyltoluene; It is used as a mixture of the above.

Furthermore, the (meth)acrylic ester represented by the above general formula ε used as a component of the vinyl copolymer can also be used, and the ester is generally used in an amount of 50% or less of the total polymerizable monomers. . If necessary, small amounts of acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, acrylamide, methacrylamide, dimethylaminoethyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide, 2-
Hydroxyethyl (meth)acrylate, 2-hydroxyprobyl (meth)1 acrylate, 2-acrylamide-! - Hydrophilic monomers such as methyl glycol dimethacrylate, styrene sulfonic acid, etc. may be used in combination, and small amounts of ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, glutylene gelicol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, etc. methacrylate,
Polyfunctional cross-linked polyacrylates such as trinotylolpropane tri(meth)acrylate and hentaerythritol tri(meth)acrylate, and diallyl tstalates.
It can also be used in combination with radical heavy potting agents such as benzoylno-only oquinide, [-butyl perbenzony], di-t-1-tyl-oquinide, cumenehydronoquinide, azobis. Inbutyronitrile is not particularly created, and any conventionally known inbutyronitrile may be used.

The amount of the above neutralized product used is approximately 5 to tj of the total amount of this neutralized product and the radically polymerizable monomer! ! 96s, preferably about 5-805M. If the amount of the neutralizer used is too small, the water-dispersed resin obtained by polymerizing the monomer in the presence of the neutralizer will have poor stability and sufficient air curability. This is because the film formed by the water-resistant resin is largely responsible for its water resistance.

The neutralized product of the vinyl copolymer thus obtained contains a graft copolymer in which a portion of the radically polymerizable monomer is graft-polymerized to the neutralized product. It is thought that the weight average molecular weight of such a graft polymer is F14000 to 30G, range II of 0...
KToru is good. If the weight average molecular weight is less than 400, the degree of curing of the resulting water-dispersed resin will be low, and
The final coating film does not have sufficient tkit aqueous 1,
On the other hand, if the number is greater than 000, the viscosity is too high and painting workability is poor, and the density and concentration must be made unnecessarily small.

The amount of water added to the polymer consisting of a neutralized product of such a vinyl copolymer may be adjusted as appropriate;
In order to take advantage of the water content of the rice, it is preferable to increase the amount of water and reduce the amount of organic solvent. It is also possible to obtain a water-dispersed resin with good dispersion stability, and for overcharging, Kyo is added so that the weight of water is 1 to 10 times that of the solvent. This good fractional stability of 凭净 is mainly due to the singular tk
A radically polymerizable monomer is added to the neutralized product of the esterification reaction product of a vinyl copolymer with a (meth)ac IJ#lI ester tS component having a ll-like unvalued group and a higher unsaturated fat or ester. A graft copolymer bottle whose body is graft-polymerized.

This is thought to be due to. In other words, it is thought that the dispersion properties of Moisture Inhibitor III & by this J1 method are developed by graft polymerization of the monomer to the above vinyl copolymer, but the unique characteristics present in the above vinyl copolymer are It is presumed that the cyclic unsaturated group allows the monomer to be easily and smoothly digested, resulting in better dispersion properties.
It is assumed that Il in the Takatake fatty acid or higher fatty acid ester introduced into the Ii polymer exerts the IiN activity and contributes to the above-mentioned dispersibility. be done.

The method of the present invention is JII preparation as described above, and since the monomer is polymerized in an organic medium in the presence of a neutralized product of the esterification reaction product of the vinyl copolymer, it is neutralized with a base. The degree of viscosity increase upon gradual addition of water to the resin dispersion and phase inversion is significantly reduced compared to the case where an uncoated vinyl copolymer is layered. Therefore, according to the present invention, phase inversion is easy even when the molecular weight of the neutralized product of the vinyl coelectronic polymer is large, and in some cases, it is possible to omit the puncturing process using *m methods such as Decylpur. Ru.

In addition, 5tiait obtained by the method of the present invention has good storage stability and pigment transferability due to excellent moisture stability, and furthermore, it has a cyclic undesirable group of the ester represented by the above general formula and the above fatty acid or K due to the air curing nature of the chain unsaturated bond portion of the fatty acid ester.

The air curing speed is high, and the final film formed has excellent water resistance and weather resistance.

It should be noted that the method of the present invention can be used to convert Honbukin** to electric warmer #istrongl1
IIIL When used as a paint for drying, etc., a known metal desiccant may be used in the appropriate amount.
You can also modify it by adding s, ta, etc. Additionally, pigments that can be dispersed in water may be added.

The present invention will be explained below with reference to Example t#/. In addition, in the following examples, 4I [evaluation of physical properties, etc. was performed as follows.

(1) Acid value Nienol 7Thalein was determined by neutralization titration using %alN potassium hydroxide ethanol minato using an indicator.

(Weight average molecular weight: sample sg6 tetotsuhydro7
? Concerning the solution, it was determined by gel permeation chromatography.

(3) Keishun base value: The amount of acetic acid required to esterify the hydroxyl groups in the sample mu was determined and expressed as the f number of potassium hydroxide required to neutralize it.

(4) Storage stability of paint: ai! ! Aqueous dispersion of 4 Gg6 of 100 fK titanium oxide and 2 ft of 12% zirconium octylate were added and stirred at high speed to adjust the coating composition.

Kono paint 1m18! Add jLlliIK and 7 at SO℃.
Leave it for 9 days and then observe the presence or absence of coagulation or lumps and viscosity.If there are no abnormalities, it is considered good. If this result is good, the storage stability of the water-dispersed resin itself is considered to be good.

Ren) Coating film physical properties of the paint: 1111ml of zinc was added to the paint.
It was applied by air spray to a steel plate Kll thickness of 40sK, and dried at room temperature for 20 minutes, at 100°C for 20 minutes, and then at room temperature for 5 days to obtain a coating film.The physical properties of the coating film were evaluated according to JIS Ki.
Measured at 40eK.

l) Water-resistant coated steel plate tSoaked at 20°C for 10 days to cause swelling on the coating surface,
The seller of peeling and rust was Jimameno tJIL.

b) Impact resistance: Tested using a Danipon type impact tester with a NOOf iron tmh, and expressed as the height of the drop of the weight.

C) Gloss ・O’／　l! O' mirror box gloss was measured.

d) Using cellophane tape with 1% 10XIO glue applied to the eyes using an adhesive razor, the results of the peeling test were expressed as the remaining percentage.

(6) Painting workability (transfer): The above paint is coated with zinc.
Apply to Enoki using an airless sprayer and leave at room temperature for 2 minutes*
Snow at SO℃ I1. The appearance of scratches and pinholes on the paint film was observed. Indicate the coating thickness (V%) where no coating INK defects occur.9.

Paint workability (to)) 2. After leaving the above film at room temperature for 1 hour,
24 hours after applying the water droplets, the coating film showed some blistering, peeling, and adhesion t#F. This is an evaluation of the initial water resistance of the paint film, and is used to evaluate the drying properties of the paint.

(71If type dihydric teaching resin lf was electrically dried, and the ratio of the amount of remaining charge to the weight before drying was expressed as a percentage.

(8) Phase inversion property: Evaluation was made based on the degree of viscosity increase when phase inversion ffl was performed using a high-speed stirrer. A case where the main dispersion was obtained without significant thickening was rated as good.

il+ Pigment miscibility: 40 ft of titanium oxide was added to a water dispersion resin vessel 01 of iai* min. Dispersibility of 5 tones or less was considered good.

Reference Example 1) In 100 g of butylcellosorg, 8 (or 9)-acryloxytricyclo(t2hL O2-8]-4-
Decane 12f, acrylic acid 261.2-hydroxyethyl methacrylate) 2111 styrene 25f, 2-ethylhexyl acrylate 49f, tucryl mercabutane 4
1. Azoisobutyronitrile was added dropwise over a period of 4 ftB and stirred for 1 hour to carry out copolymerization reaction I15 to obtain a vinyl copolymer. The reaction temperature was 120°C for the initial 15 hours and 150°C thereafter. Next, soybean oil 1! Glycidyl esters of fatty acids (higher unsaturated fatty acid ester content, approximately 80
96) 82f,) ethylamine lft this anti-15MK
In addition, an esterification reaction was carried out at 150°C for 3 hours. The tai*min of the esterification reaction product of the obtained copolymer is 5
ashs, acid value was .6, hydroxyl value was AYS, and weight average molecular weight was 1.O.

Reference Examples 2 to 4 The same procedure as in Reference Example 1 was carried out except that the amount of fatty acid or fatty acid ester and other monomers under IK was changed to 1111K and the amount of barley IK was 41t, and the physical property value was 41t. Vinyl copolymer Dll and esterification reaction products B and C were melted with gtylated cellosolve.

(Margin below) Table 1 118 (also d9)-79ria*shi) IJ sill
glc&! LO'')-4 Example 1 Solution 1 of the esterification reaction product A of the vinyl copolymer obtained in Reference Example 1 [Add Ptylselon Lup 202 and diethylethanolamine L8f to 3 & 2F and heat at 100''CK for about 30 minutes. , then methyl methacrylate 21L8f,2
-Ethylhexyl acrylate 262f, styrene sa
After adding 120 f of deionized water dropwise over about 30 minutes, a water-dispersed resin was obtained. The phase inversion step at this time was easily carried out with little increase in viscosity. The properties of this water-dispersed resin and the physical properties of the resulting nine-layer film were determined in 22. It is shown in Table 3.

Example 2 Solution of esterification reaction product A 3 & 2f Kgf Lusse a Solg 20f1 Add diethylethanolamine L8F to 100
Stir at ℃ for 30 minutes.

Next, add 20f of deionized water, then add methyl methacrylate 2λ8 to 2-ethylhexyl acrylate 211F.
, styrene 30P, azoinbutyronitrile Q4F 3
The mixture was added dropwise over time and allowed to react for an additional 2 hours. As the polymerization reaction progresses, the polymer solution changes from a transparent state to a semi-transparent state.Deionized water Roof was added dropwise to this solution over a period of 80 minutes to obtain a water-dispersed resin. At this time, the phase inversion process & was performed extremely easily due to the low viscosity of the dispersion system. The properties of this water dispersion and the physical properties of the resulting coating film are shown in Table 21 and Table 3.
It was shown to.

Example 3 A water-dispersed resin was obtained in the same manner as in Example 1, except that #1 case 3LSf of esterification reaction-B obtained in Reference Example 2 was used.

Table 2 shows the properties of this water dispersion #fat and the physical properties of the resulting coating film.
, shown in Table 3.

Example 4 For dissolution of the esterification reaction product C obtained in Reference Example 3 - Aqueous dispersion lll11 was #good in the same manner as in Example 2 except that the conditions shown in the table were adopted. The properties of this water-dispersed fat and the physical properties of the resulting coating film are shown in Tables 2 and 3.

*2-8 (also #19)-acrylic acid O(5, Ll
, 0''-') indicates -4-decene.

Table 3 Shows the results of the fist evaluation method/IF value method (2).

Comparative Example Solution of the esterification reaction obtained in Reference Example 4 60PK Buta-ton Lupu JIOftJE11! O'cK heated acid butyl methacrylate) 140F, butyl acrylate 209, and t-butyl-octoate a8F were added dropwise over 3 hours and then! ! A polymer syneresis can be obtained by a dark reaction.・Next, add dimethylethanolamine 4. to this polymer.
42 and deionized water 2002 were added.

The viscosity of the dispersed thread increased significantly and the whole became a sticky substance, so the dispersed system was taken out, placed in another container, and made into a sheet using a dasilver.Forcibly dispersed by applying very strong shearing force for a long time. Let's do it.

The degree of neutralization of the water-dispersed resin is 70%, and the weighted average molecular weight of the polymer is 7λ5001, and the acid value is 20. The hydroxyl value was 12, and the drug content a was 39.7%. The pigment compatibility of the round paint obtained by adding a predetermined pigment to this paint was somewhat good, but the storage stability was poor due to precipitation of aggregates. Paint workability prisoner F14 G, @7 scratches occurred.

In addition, the performance of the obtained coating film was Fi7 in the water resistance test results.
Creases occurred, and the adhesion was 7.9/100 with Koyaku Fi5G.
The impact drop resistance was 200 ml, and the pencil hardness was HB.

”, Approved examiner Sekisui Chemical Co., Ltd. Representative: Mototoshi Numa 284-

Claims (1)

[Claims] The integer n is an integer that satisfies the following relationship. mm1f) and t! 1in=2~ss m=2~So and @
is an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group represented by nw 2°), and α
, β-unsaturated carboxylic acid 1 to 30% by weight, and polymerizable unsaturated carboxylic acid
Compound containing s'kJ group and hydroxyl group 0-50% by weight
Neutralize the esterification reaction product of vinyl #-heavy polymer having the constituent unit, higher unsaturated fatty acid or higher unsaturated fatty acid ester, and in the presence of the neutralized product thus obtained,
A method for producing a water-dispersed resin, which comprises polymerizing a radically polymerizable monomer in an organic solvent and adding water to the resulting polymer. λ The ester of acrylic acid is 8-acryloxytricyclo(5,2,1,0"=')-4decene or 9-acryloxytricyclo(5,2,1,0"・6]-4de7 The manufacturing method according to item 1, wherein the method is: