JPH01254703A - Production of non-aqueous dispersion type resin for coating compound - Google Patents

Abstract

PURPOSE:To obtain a non-aqueous dispersion type resin for coating compound in a state of dispersion having excellent dispersion stability, by polymerizing a specific polymerizable unsaturated monomer in an organic solvent containing aliphatic hydrocarbon as an essential ingredient in the presence of a compound containing specific building block. CONSTITUTION:In an organic solvent containing aliphatic hydrocarbon as an essential ingredient, 5-70 pts.wt. a compound containing at least one building block expressed by the formula (R1 is aliphatic monohydric alcohol residue containing 4-22C alkyl, ester diol residue containing 4-22C alkyl or polyol residue of vinyl copolymer containing hydroxyl group, etc.; R2 is alkylene or alkylene containing cyano group) per one molecule is polymerized with 95-30 pts.wt. polymerizable unsaturated monomer which is soluble although the polymer thereof is insoluble to said organic solvent [e.g., methyl (meth)acrylate or crotonic acid] to afford the aimed resin.

Description

[Detailed explanation of the invention] [Industrial use field] The present invention is one or more of one or more in one molecule, regarding the new manufacturing method of non -hydrated distributors for paint. A specific polymeric azo initiator containing a residue of a polycondensation compound is used as a total dispersion stabilizer to make the copolymer insoluble in a specific organic solvent in which all aliphatic hydrocarbons are essential. It consists of polymerizing the monomers.

A dispersion of polymer particles useful as a paint? Relating to a method of manufacturing.

[Prior art and problems to be solved by the invention] In recent years, this type of non-aqueous dispersion m-resin has been developed because it has relatively little negative impact on the environment due to the use of non-polar weak solvents, and because it is a particle system, it has a low viscosity. Because it has characteristics such as exhibiting thixotropic behavior and being easy to apply thickly, it is also superior to conventional solvent-based resins and emulsion-based resins and exhibits full psychotherapeutic performance. Yes, metal painting 1,
In particular, it is beginning to be used in a wide variety of applications, including painting the exterior panels of automobiles and buildings.

By the way, in the conventional method for preparing a non-aqueous dispersion type resin, the monomer is soluble in the solvent in which the dispersing resin is dissolved, but the polymer obtained from the monomer is A common method is to completely polymerize a mixture of monomers in which the monomers are insoluble and form particles. Polymerization active sites occur in a part of the molecules of the incorporated dispersion resin, that is, the dispersion stabilizer, and a polymer that is insoluble in the above organic solvent (hereinafter referred to as an insoluble polymer) is obtained. As a very small portion of the vinyl monomer reacts with such polymerization active sites, the so-called soluble polymer portion based on the dispersion stabilizer and the insoluble polymer portion based on the vinyl monomer are separated. A block copolymer or graft copolymer will be formed,
At the same time, most of the vinyl monomers subjected to one polymerization reaction do not participate in such block copolymerization or graft copolymerization, but instead undergo single polymerization to form an insoluble polymer. Therefore, all of these polymers are in a mixed form.

As described above, conventional non-aqueous polymer dispersions have a low content of the above-mentioned block copolymer or graft copolymer, which has good dispersion stability, and are obtained by the above-mentioned monopolymerization. Because it has a high content of child-soluble polymers,
Moreover, this insoluble polymer is simply dispersed in an organic solvent or a so-called organic liquid containing the solvent through physical secondary bonding with the block copolymer or graft copolymer, and therefore Non-aqueous polymer dispersions have a problem of poor dispersion stability.

In particular, when the non-aqueous polymer dispersion obtained as described above is used as a coating film-forming component, a serious problem tends to occur.

That is, the above-mentioned block copolymer or graft copolymer and insoluble polymer cannot maintain monodispersion stability unless strong secondary bonding is achieved by physical intermolecular forces. The types of vinyl monomers that can be used to form polymer particles are extremely limited, and a monomer that can form a highly polar and rigid polymer must be selected.

However, the coating film obtained from a non-aqueous polymer dispersion prepared under such restrictions cannot be uniform because the dispersion itself does not melt under sufficient pressure and flow.

However, such a non-aqueous polymer dispersion or liquid may cause the insoluble polymer to coagulate and precipitate due to the high shear force applied during pigment dispersion, or may contain polar solvents with strong dissolving power for polymer particles or plasticizers. In order to solve the problem that the dispersion stability during storage becomes extremely poor when such substances are added, and there is a danger that the dispersion becomes dull or coagulates and settles, we developed a dispersion agent that acts as a dispersion stabilizer. There is also a method of increasing the concentration of polymerization active sites in the resin and causing the dispersion stabilizer to react more actively with the vinyl monomer and gold, thereby achieving dispersion stability. Accordingly, since a large amount of block copolymer or graft copolymer is contained, the insoluble polymer portion has the effect of stably dispersing a soft and less polar polymer portion. However, on the other hand, it becomes extremely difficult to control the polymerization reaction, resulting in production problems such as curdling during the reaction, or even if it does not go that far, the reaction does not proceed smoothly. Apart from that, a technology has recently been proposed in which a special peroxide catalyst called polymeric 4-oxide is used to perform block copolymerization or graft copolymerization to stabilize dispersion. However, problems remain regarding the manufacturing peculiarities and risks of such polymeric peroxides themselves.

As described above, all of the non-aqueous polymer dispersions that have been practically used up to this point have extremely narrow selection ranges of vinyl monomers that can form insoluble polymers. Moreover, there are also problems with dispersion stability itself.
Ultimately, a film-forming polymer that is satisfactory has not yet been obtained, and technical improvements are currently highly desired.

[Means for solving problems]

However, the present inventors have conducted extensive studies in view of the various drawbacks in the prior art as described above, and have found that one or more diazo bonds, two or more polycondensation compound residues, and all With the novel method of using a specific so-called polymeric azo initiator, all of the drawbacks of conventional non-aqueous polymer dispersions have been eliminated, and a method for producing a new type of dispersion for coatings has been developed. Having made this discovery, we have now completed the present invention.

That is, the present invention provides a compound (B) having one or more structural units in one molecule represented by the -form % formula % (1) in an organic solvent (A) containing an aliphatic hydrocarbon as an essential component. In the presence of 5 to 70 parts by weight, the monomer is soluble in the solvent (A), but the polymer becomes insoluble. 30
It is an object of the present invention to provide a method for producing a non-aqueous dispersion type resin for paints, which has a uniform particle size and exhibits excellent dispersion stability, by polymerizing parts by weight.

Here, the compound/substance (B) having at least one structural unit in one molecule of the above CD formula is, for example, "Kobunshi Saishu" Vol. 33, No. 3, No. 131. ~1
It is prepared by applying a low-temperature condensation reaction as described on page 40 (published in 1976).

That is, first, 2,2'-azobis(2-methylglobion [2), 4,4'-azobis(4-cyanopentanoic acid), 4,4'-azobis(4-cyanopentanoic acid), etc. Thionyl chloride is added to the terminal carboxy group compound containing a diazo bond in the molecule, represented by
The resulting diazo-bonded gold acid chloride and active hydrogen-containing compound are reacted at a low temperature of 20°C to form an acid chloride, which is then subjected to a specified purification process, to form a tertiary amine such as triethylamine. In the presence of class, 0
It is obtained by carrying out a condensation reaction at ~25°C, then performing a predetermined nitrogen treatment such as washing with water, and then drying in vacuum.

Condition 11 of the compound (B)! l-To explain in more detail, R1 in the structural unit of the above general formula [I] is
Compounds containing one or more hydroxyl groups, for example.

Aliphatic monohydric alcohol having a substituted or unsubstituted alkyl group of C4 to C2□, aliphatic dihydric alcohol having a substituted or unsubstituted alkylene group of 04 to C2□, having a substituted or unsubstituted cyclohexylene group diol, or an ester diol having a substituted or unsubstituted alkyl group of 04 to C2□; or a substituted or unsubstituted alkylene of 04 to C2□, which may partially contain a substituted or unsubstituted phenylene group polyester polyols containing groups, or polyester polyols containing substituted or unsubstituted cyclohexylene groups; and vinyl copolymers containing hydroxyl groups, which may contain all or part of substituted or unsubstituted phenylene groups. The compound is ester bonded and represents all nine residues.

Here, the above-mentioned aliphatic monohydric alcohols include n-butanol, l-butanol or t-butanol, n-octyl alcohol, L<Vi2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, Stearyl alcohol, coconut alcohol (012-C
14)'Behenyl alcohol (C18'' 22) A typical example of behenyl alcohol is 2-octyldodecanol, and the above aliphatic dihydric alcohols include 1,4-
Typical examples include butylene l'' I) nia-/L', 1,6-hexane diol, diethylene glycol, diethylene glycol, neointyl glycol, triethylene glycol, or lauryl alcohol.

(9) The above-mentioned diols having all substituted or unsubstituted cyclohexylene groups include 05 or more cycloalkyl groups or substituted cycloalkyl groups, such as cyclohexane dimetatool and hydrogenated bisphenol A.
etc. are representative examples.

Furthermore, the aforementioned ester diols or various polyester polyols include aliphatic monohydric alcohols, aliphatic dihydric alcohols, cyclohexylene group-containing diols, aliphatic carboxylic acids and/or diols, respectively. Alternatively, compounds having a number average molecular weight of 200 to s, o o o, which are obtained by condensation polymerization of an alicyclic carboxylic acid as a main component together with a nectonic acid component compound, may be mentioned. Of course, fatty acids such as inphthalic acid and aromatic carboxylic acids such as phthalic anhydride or some of their anhydrides can be used in combination.

The aliphatic carboxylic acid mentioned above is adipic acid.

Representative examples include azelaic acid and sepacic acid.On the other hand, representative examples of the alicyclic carboxylic acids mentioned above include cyclohexine-based carboxylic acid, as well as hexahydrophthalic anhydride and tetrahydroanhydride. Anhydrides of alicyclic carboxylic acids such as phthalic acid are also representative.

Furthermore, the aforementioned hydroxyl group-containing vinyl copolymer has a number average molecular weight of 800 to 20.
Examples include compounds containing one or more hydroxyl groups in one molecule within the range of 000; The vinyl monomers shown in Table 1 are completely polymerized in the presence of a transfer agent and a hydroxyl group-containing polymerization initiator such as azobiscyanointanol. It is something.

An organic solvent (A) containing an aliphatic hydrocarbon solvent as an essential component
) are dispersed in N! In order to obtain aggregate particles, that is, dispersed particles, is it necessary to use a C4 or higher alkyl group? It is necessary to select a monomer having (meth)acrylic acid ester as a main component so that the method of the present invention can be carried out to meet the objectives of the present invention.

In order to obtain a uniform and stable dispersion system, the n
A polymeric azo initiator which is sufficiently soluble in a specific organic solvent, especially R4 in the structural unit of general formula CI''l shown above.
The entire structure must be designed by itself.

As long as these nine conditions are satisfied, the component compounds constituting all of R4 are not particularly limited.

On the other hand, R2 in the structural unit shown in the above-mentioned one form CI]
represents an alkylene group or an alkylene group containing all cyano groups, but the component compound used to make up all of this R2 is a compound having a diazo bond, a carboxyl group, and gold in one molecule, and such A typical compound is

2.2'-azobis(2-methylpropionic acid), 4.
4'-azobis(4-cyanobencunic acid) makut-14
, 4'-azobis(4-cyanobencunic acid), etc., as mentioned above, are diazo bond-containing terminal carboxyl group compounds.

The polymerizable unsaturated monomer (C) polymerized in an organic liquid in the presence of the compound (B) obtained as described above will be explained in detail. The monomer (C) is once dissolved in an organic liquid, and then polymerization is initiated by the so-called polymer azo initiator, which is the compound (B), that is, block polymerization is initiated to form particles. Therefore, there is a correlation between the organic solvent (A) compared to the organic liquid for polymerization and the monomer (C).

In fact, Table 1 itself shows this relationship.

1st Soluble lower alkyl (meth) Acrylates such as ethyl acetate and butyl acetate Ester lower fatty acid vinyl Methyl ethyl ketone, cyclohexano ester
Ketones such as allylglycidylny
Methyl alcohol, ethyl alcohol
Lower alcohols such as higher alkyl (meth) esters, ketones, acrylates, aromatic higher fatty acid vinyls such as toluene and xylene, hydrocarbons,
Aliphatic-1fCri fatty acid formula x Hydrogen steride, butyl alcohol.

4-ethyl alcohol, hexyl alcohol, high R alcohol aromatic vinyl monomers, esters, ketones, aromatic hydrogen hydroxyl group-containing vinyl monoalcohol analogs, carboxyl group-containing vinyl monomers as shown on the left. Organic liquids that are insoluble in monomer polymers such as n-hexane, rhohebutane, n-octane, petroleum benzine, ligroin, and
Mineral spirits, petroleum naphtha.

Aliphatic or alicyclic hydrocarbons such as kerosene, cyclohexane, methyl cyclohexane, methyl alcohol, ethyl alcohol, rhoglobil alcohol, charcoal
Lower alcohols such as globyl alcohol (A) Alcohols, aliphatic or alicyclic aliphatic primary are alicyclic hydrocarbons, aromatic hydrocarbon esters, ketones Table 1 (2) Vinyl chloride, Pinyli chloride Ketones Den (meth) Acrylonitrile Acrylamide Dimethylformamide Dimethyl sulfoxide Butadiene Esters, ketones, aromatic hydrocarbons, aliphatic cycloaliphatic hydrocarbons Insoluble in polymers of the monomers listed on the left. or alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, aliphatic or fi-ring hydrocarbons, esters, ketones, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, etc. It is not limited to only those who exist.

Typical polymerizable unsaturated monomers (B) used in carrying out the entire method of the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. -n-propyl, lower alkyl (meth)acrylates such as isoglobyl (meth)acrylate or glycidyl (meth)acrylate ester: -n-butyl (meth)acrylate, isobutyl (meth)acrylate.

t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate,
Higher alkyls (such as 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, acrylic (meth)acrylate or stearyl (meth)acrylate)
meth)acrylates: lower aliphatic vinyl esters such as vinyl acetate or vinyl propionate; vinyl butyrate;
Vinyl caproate, vinyl 2-ethylhexanoate, vinyl lafricate, vinyl stearate or "Peopa"
Higher aliphatic vinyl esters such as (vinyl esters of branched fatty acids, manufactured by Shell, Netherlands); aromatic vinyl monomers such as styrene, vinyltoluene modi or vinylpyrrolidone; (meth)acrylamide, N-methylol ( Vinyl monomers containing amide groups such as meth)acrylamide 9 or N-methoxymethyl (meth)acrylamide; hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate or allyl alcohol Containing vinyl monomers; vinyl monomers containing cargexyl groups such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid; monomers containing acid anhydride groups such as phthalic anhydride or dodecenylsuccinic anhydride In addition, ethylene, propylene, butadiene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, mono-n-butyl fumarate, diethyl maleate, and (meth)allyl glycidyl ether.

In addition, the above-mentioned glycidyl (meth)acrylate does not belong to lower alkyl (meth)acrylates, and the above-mentioned cyclohexyl (meth)acrylate does not belong to higher alkyl (meth)acrylates, but each For convenience, it is listed as a (meth)acrylate derivative of

In addition, ethylene and propylene can be classified as α-olefins, and (meth)acrylonitrile can be classified as a type of fatty acid ester, along with the lower aliphatic vinyl esters mentioned above. would be possible.

These polymerizable unsaturated monomers (C) may be used alone or in combination of two or more types.

The organic solvent (B) used in carrying out the method for producing a non-aqueous dispersible resin for paint according to the present invention is an organic liquid containing 500 parts by weight of aliphatic hydrocarbons, With respect to the aliphatic hydrocarbon which is to be the main component of such an organic liquid, the insolubility of the insoluble polymer portion in the block copolymer as dispersed particles, that is, the dispersed t″L nonapolymer particles, respectively, is not impaired. Other organic solvents can be added to the aliphatic hydrocarbon to a certain extent, and to such an extent that the solubility of the soluble polymer portion is not impaired.

First, typical aliphatic hydrocarbons include n-hexylhydrocarbons listed in Table 1. Examples include kerosene, n-hebutane, n-octane, petroleum benzene, ligroin, mineral spirits, petroleum naphtha, and kerosene.
J (product of Exxon Chemical Co., USA), "Roas" (product of Shell Co., Netherlands), "Naphtha No. 5 or No. 6" (product of Exxon Chemical Co., USA), "
IP Solvent 1620J (Idemitsu Petrochemical ■Product)
Or "White Sol" [Kyodo Oil Product] etc.

Other organic solvents can also be used in combination within a range of less than 50% by weight based on these aliphatic hydrocarbons, but typical examples of such organic solvents include those listed in Table 1. , esters, ketones, alcohols, alicyclic hydrocarbons, and aromatic hydrocarbons.

Note that the above-mentioned "loin" is a mixture of aliphatic hydrocarbons as a main component and a small amount of aromatic hydrocarbons.

Thus, the method of the present invention involves carrying out various polymerizations as described above in the presence of the compounds (B) as listed above in an organic solvent (A) containing an aliphatic hydrocarbon as a main component. 5 to 70 parts by weight of a compound (B) having at least one structural unit as shown in the general formula CI) in one molecule. In the presence of an organic solvent mainly composed of aliphatic hydrocarbons (
For A), the monomer is soluble, but the polymer of that monomer is insoluble (polymerizable unsaturated monomer (
A mixture of C) and this organic solvent (A) is used to block copolymerize these compounds (B), a so-called polymer azo initiator, with the monomer (C), thereby forming a non-aqueous A polymer dispersion, that is, a dispersion of a non-aqueous dispersion type resin is obtained.

At that time, through the block copolymerization reaction of compound (B) and monomer (C), each sequence existing between the diazo bonds in compound (B), that is, the general formula CI
) Each member constituting R4t in the structural unit represented by is solubilized in the organic solvent (A).

The copolymer from monomer (C) is incorporated into the particles and becomes T-shaped.

Thus, there is no need to use low-molecular azo initiators, peroxide catalysts, etc. that are used in conventional radical polymerization.

In carrying out the method of the present invention, the amount of the compound (B) used is 5 to 70 parts by weight, preferably 15 to 4.0 parts by weight.
A range of parts by weight is appropriate. If the amount is less than 5 parts by weight, the reaction rate of block copolymerization of compound (B) with polymerizable unsaturated monomer (C) will be too low, and sufficient dispersion stability cannot be expected. On the other hand, if it exceeds 70 parts by weight, the particle formation will not be sufficiently carried out, resulting in f'L-! In addition, both cases are unfavorable because dispersion stabilization cannot be achieved.

The temperature of the block copolymerization reaction carried out in the presence of the compound (B) is preferably in the range of 60 to 140°C, and the reaction time is preferably in the range of 6 to 18 hours.

The amount of the organic solvent (B) to be used is preferably such that the non-volatile content concentration of the resulting non-aqueous polymer dispersion, which is a non-aqueous polymer dispersion, is preferably 30 to 70% by weight. The amount may be within the range of 70 to 30% by weight in the non-aqueous polymer dispersion.

Thus, various additives such as other polymers, pigments, or fillers can be added to the non-aqueous dispersion resin dispersion obtained by the method of the present invention, as necessary. As a combination, butyl etherified melamine resin, butyl etherified benzoguanamine resin, butyl etherified urea resin, blocked polyisocyanate compound, aromatic, aliphatic or alicyclic polyepoxide,
Polyamide resin, ratio is glycidyl group, carboxyl group, hydroxyl group, incyanate group, alkoxy group or N
-Hini/I/resins containing all methylolated amide groups are typical examples, and each of these polymers has complementary functional groups to the functional groups present in the non-aqueous dispersible resin obtained by the method of the present invention. As a curing agent containing a functional group, it becomes a thermosetting coating film forming component.

As described above, in the method for preparing a non-aqueous dispersible sealant for paints of the present invention, most of the produced polymer is a polymer portion that is soluble in organic liquid, compared to the conventional method. Because it provides a block copolymer consisting of (soluble polymer part) and an insoluble polymer part (insoluble polymer part), one stable dispersion containing a high concentration of nine block copolymers is produced. It has the special feature of being able to provide a non-aqueous polymer dispersion, which is a dispersion of a non-aqueous dispersion type resin, which has an excellent ratio of properties and a uniform particle size.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples and Examples. In the following, parts and percentages are all based on weight unless otherwise specified.

Reference Example 1 [Preparation Example of Compound (B)] 200 parts of chloroform and 280 parts of stearyl alcohol were charged into a four-way flask equipped with a thermometer, a stirrer, and a reflux condenser, and then 202 parts of triethylamine was added. Then, while cooling, a mixed solution consisting of 158.5 parts of 4.4'-azobisyarintanyl chloride' and 40 parts of chloroform was added.
The mixture was added dropwise over 2 hours with stirring.

The reaction was continued for an additional 2 hours while maintaining the temperature below 20'C, and then the triethylamine hydrochloride was removed by washing with water, filtered, and vacuum dried to obtain a number average molecular weight of CMn.
>645 and the average number of diazo bonds in one molecule was 1. 380 parts of the target compound was obtained.

Reference Example 2 (same as above) 0224 parts of adipic acid, 236 parts of 1,6-hexanediol, and Octyk 7 k :r- were placed in a four-way flask equipped with a thermometer, a stirrer, and an air condenser.
The temperature was raised to 150'C-j, then gradually raised to 180°C over 2 hours, and then heated to 180°C for 2 hours.
The temperature was raised to 20°C over 2 hours. After reaching 220°C, the temperature was maintained for 2 hours to continue the reaction, then the temperature was lowered to 50°C, 750 parts of chloroform was added, and after the temperature was further lowered to below 20°C, 202 parts of Add triethylamine, 200 parts of chloroform,! =4
．． 4'-7 Zobiscyano (158 of ntanoic acid chloride)
．． 5 parts of the mixture was added dropwise over 2 hours.

After the reaction was completed, the same post-treatment as in Reference Example 1 was carried out to remove Mn.
is 1,800, and the average number of diazo bonds is 1.

A viscous solid target compound was obtained.

Reference Example 3 (same as above) After charging 453 parts of cyclohexibundicamenic acid and 640 parts of hydrogenated bisphenol A with gold, the same procedure as Reference Example 2 was carried out to obtain a hydroxyl value of 36.4 and 1Mn of 3.
080, a polyester resin having two hydroxyl groups in one molecule, was obtained, and then the temperature was lowered to 60°C, 1.500 parts of chloroform was added to the resin, and the temperature was lowered to 20°C while stirring thoroughly. 67.4 of triethylamine
4.4'-
A mixture of 105.7 parts of 71his'y anopentanoic acid chloride was added dropwise over 2 hours.

After that, the same post-processing as in Reference Example 1 is performed, and the size is 18.
, 200, and the average number of diazo bonds is 5.2.

The target compound in powder form was obtained.

Reference Example 4 (same as above) In addition to 224 parts of adivic acid, 222 parts of phthalic anhydride
500 parts of 1,6-hexanediol and 40 parts of dodecyl alcohol were prepared in the same manner as in Reference Example 2.
A polyester resin having a hydroxyl value of 29.2 was obtained.

Next, this polyester resin was diluted with 1,2 chloroform.
00 parts and lowered the temperature to 20°C while stirring thoroughly,
First, 45.7 parts of triethylamine was added, and then a mixture of 100 parts of chloroform and 71.7 parts of 4,4'-azobiscyanopentanoic acid chloride was added dropwise over t-2 hours.

After that, the same post-processing as in Reference Example 1 was carried out until the horse was 1,
300 and the average number of diazo bonds is 1.3 No 4
A powder-like target compound was obtained.

Reference Example 5 (same as above) In an autoclave equipped with a dropping device, chloroform
00 parts of 4,4'-azobiscyanopentanol and 200 parts of chloroform. The mixture was press-fitted for 8 hours. After this injection was completed, the same temperature was maintained for 5 hours to continue anti-Ff, thereby obtaining a solution of an acrylic copolymer having a hydroxyl value of 8.3 and 4 of 6,800.

Next, 14.9 parts of triethylamine was added thereto, followed by 40 parts of chloroform and 23.3 parts of 4.4'-
Mixture solution t-2 with azobiscyatin tantanyl chloride
After that, the same post-treatment as in Reference Example 1 was carried out, and the dance was 22.
,000 and an average number of diazo bonds of 3.5 was obtained.

Reference Example 6 (same as above) In an autoclave equipped with a dropping device, chloroform
400 parts of isobutyl methacrylate and 59 parts of n-butyl methacrylate were charged.
A mixture of 0 parts of acrylic acid, 10 parts of acrylic acid, 30 parts of 2-mercaptoethanol, and 200 parts of chloroform was injected over a period of 4 hours, and the temperature was maintained at the same temperature for an additional 4 hours to continue the reaction until the temperature reached 20°C. After the temperature drops.

Next, 20 parts of triethylamine was added to the thus obtained solution of the acrylic copolymer having a subhydroxyl value of 11.2 and an Mn of 5,100, and then 50 parts of chloroform and 31.07 parts of 4 , 4'-azobiscyanobentanoic acid chloride was added dropwise over 2 hours while cooling.

After that, all the post-treatments were carried out in the same manner as in Reference Example 1 until Mn was 9.
, 600, and the average number of diazo bonds in one molecule is 1.
Seven target compounds were obtained.

In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser,
Reference number: 50 parts of 9 compounds, 800 parts of mineral turpentine, 60 parts of styrene, 8 parts of ethyl acrylate.
0 parts, 24 parts of 2-hydroxyethyl methacrylate,
30 parts of isobutyl methacrylate and 2 parts of acrylic acid
After heating to 90°C and reacting for 1 hour, 200 parts of mineral tine and 20 parts of n-butanol were added.
0 parts, 150 parts of the compound obtained in Reference Example 1, 240 parts of styrene, 320 parts of ethyl acrylate, 120 parts of 2-hydroxyethyl methacrylate, 114 parts of isobutyl methacrylate, and 8 parts of acrylic acid. Add the dry mixture t-dropwise over 4 hours.

After the dropwise addition was completed, the same temperature was maintained for 8 hours for polymerization reaction.

6. If the polymerization reaction is continued completely, the system will become milky white as the polymerization reaction progresses.9.

'The nine-resin dispersion thus obtained had a non-volatile content of 50.2 and a Pluck-Field viscosity of 1.4 at 25°C. Is Naru. It was a non-aqueous dispersion of block copolymer resin.

Even after this product was allowed to stand at 25° C. for 6 months, the dispersion state remained stable, and no sedimentation of particles, no phase separation, and no change in viscosity was observed.

Example 2 Instead of the compound obtained in Reference Example 1, a predetermined amount of the compound obtained in Reference Example 2 as shown in Table 2 was used,
In addition, the polymerization solvent and polymerizable unsaturated monomer were changed to use the specified number as shown in the same table, the polymerization temperature was set to 85°C, and the dropping time of the monomer, etc. was set to 5. In the same manner as in Example 1 except that the time was changed, 7 tons of a dispersion of a non-aqueous dispersible resin having the property values and performance shown in the same table was obtained.

Examples 3 to 8 The raw material composition was changed as shown in Table 2, and the polymerization temperature was changed as specified in the same table, except for the following:
A block copolymerization reaction was carried out in the same manner as in Example 1,
A dispersion liquid of a non-aqueous dispersion type resin having properties and performance as shown in the table was obtained.

The property values and performance shown in the table were measured and evaluated in the following manner.

Average particle size: "Sub-micron/Mother Ticle Analyzer" Coulter Model (Coulter Mo
del) Measured using N-4f.

Stability: Pour each non-aqueous dispersion into a screw tube, use a centrifuge to 2.00 Or,
After performing centrifugation at P and M for 2 hours, the state of sedimentation was visually judged. If the sedimentation area was less than 1 drop, it was considered "good."

Items with a height of 1711 or higher are now displayed as "defective".

Viscosity...The donor viscosity at 250°C is shown for reference only.

〔Effect of the invention〕

As is clear from Table 2, the non-aqueous dispersion type resin obtained by the method of the present invention is known to be a dispersion liquid with excellent dispersion stability.

In other words, it is known that this non-aqueous dispersion type resin provides an excellent non-aqueous polymer dispersion.

Agent: Patent attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. Organic solvent (A) containing an aliphatic hydrocarbon as an essential component
Among them, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. or a residue of an aliphatic dihydric alcohol having an unsubstituted alkylene group, a residue of a diol having a substituted or unsubstituted cyclohexylene group, C_4 to C
The residue of an ester diol having a substituted or unsubstituted alkyl group called _2_2, the residue of a polyester polyol having a substituted or unsubstituted alkylene group called C_4 to C_2_2, the residue of a polyester polyol having a substituted or unsubstituted cyclohexylene group. R_
2 represents an alkylene group or an alkylene group containing a cyano group. ] The above organic solvent (A
), the monomer is soluble in the polymerizable unsaturated monomer (C
1. A method for producing a non-aqueous dispersible resin for paints, which comprises polymerizing 95 to 30 parts by weight of the following. 2. The above compound (A) is an acid chloride having a diazo bond, an aliphatic monohydric alcohol having a substituted or unsubstituted alkyl group of C_4 to C_2_2, C_4
~C_2_2, aliphatic dihydric alcohol having a substituted or unsubstituted alkylene group, diol having a substituted or unsubstituted cyclohexylene group, C_4~C_2_
Ester diol having 2 substituted or unsubstituted alkyl groups, polyester polyol having substituted or unsubstituted alkylene groups C_4 to C_2_2, polyester polyol having substituted or unsubstituted cyclohexylene groups, or hydroxyl group-containing vinyl copolymer ,
The manufacturing method according to claim 1, which is obtained by reaction with a polyester polyol which may further contain a substituted or unsubstituted phenylene group.