JPS6025465B2 - Non-aqueous unsaturated resin dispersion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to unsaturated resins, and more particularly to dispersion compositions of unsaturated resins in organic liquids.

For secondary unsaturated resins, especially unsaturated resins that are subjected to light curing or electron beam curing, low pollution is important, and it is essential that they have as high a solids content as possible and a low viscosity that can be painted. Met.

However, in order to achieve a high solids content and low viscosity, methods have been used to lower the molecular weight of unsaturated resins, resulting in a significant drop in stiffness, curing properties, etc., and an imbalance between solid content, viscosity, and performance. The castle was far from complete. Therefore, in order to meet the conditions required for the above-mentioned unsaturated resins, the present inventors conducted intensive research and focused on the use of non-aqueous dispersions, which are currently attracting attention in the coating industry. discovered that an unsaturated resin dispersion composition with low viscosity and excellent coating workability could be provided.

0 The present invention provides 1. In an organic liquid (dispersion) that dissolves a vinyl monomer but does not dissolve a polymer formed from the monomer, a hydrocarbon-related polymer that is soluble in the organic liquid is dissolved. , acrylic polymers, polyesters, alkyd resins, cellulose derivatives, and block or graft polymers of these and vinyl monomers. A stable dispersion of a vinyl polymer in which polymer particles are dispersed, wherein either the dispersion stabilizer and the vinyl polymer have a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, an epoxy group, or a methylol group. group, alkoxymethylol group, isocyanate group, amide group,
It has one or more functional groups selected from an amino group and a chloro group, and after producing a dispersion, a polymerizable vinyl monomer is added or condensed to the functional group to form a dispersion stabilizer. A non-aqueous unsaturated resin dispersion whose main component is a dispersion obtained by introducing a polymerizable unsaturated group into one or both of vinyl polymers, an amino resin m, a non-aqueous unsaturated resin dispersion consisting of a photosensitizer, etc. This invention relates to liquid compositions.

As the stable dispersion liquid in the non-aqueous dispersion system, all those obtained by conventionally known methods can be used.

That is, Japanese Patent No. 317938 No. 534591, No. 4
58051, 286387, 416484, Special Publication No. 47-8537, No. 43-16147, No. 47-118
38 Japanese Patent Publication No. 46-5237, U.S. Patent No. 3405087,
3551525 3365414, 3261788
3298990, 3382297, 325513
5, etc., is already known. A non-aqueous vinyl polymer dispersion is one in which polymer particles having a particle size of approximately 0.1 to 0.9 microns are stably dispersed in an organic solvent mainly composed of non-polar hydrocarbons. In addition, microparticles of 0.1 micron or less and polymers soluble in dispersed soot may also be present depending on the polymerization conditions. In general, the manufacturing method is to use a dispersion stabilizer in dispersed soot (an organic liquid mainly composed of aliphatic hydrocarbons), and the vinyl monomer is dissolved in the dispersed soot, but the polymer is not dissolved in the dispersed soot. It is obtained by polymerizing vinyl monomers that do not dissolve. The separation medium is mainly aliphatic hydrocarbons, generally petroleum fractions, such as pentane, hexane, heptane, octane,
Use mineral spirits, naphtha, etc. The dispersion stabilizer is a stabilizer resin that is present on the surface of the polymer particles and forms a stabilizing layer to stabilize the dispersion state of the particles. Examples include acrylic polymers, polyesters, alkyd resins, cellulose derivatives, and block or graft polymers of these with vinyl monomers. The vinyl polymer that becomes the main dispersed particles is, for example,
These are polymers and copolymers of styrene, acrylic monomers, methacrylic monomers, vinyl acetate, etc.

A functional group can be introduced into a dispersion stabilizer and/or a vinyl polymer in the step of manufacturing the dispersion stabilizer in advance when it is introduced into a dispersion stabilizer, or in the step of manufacturing a dispersion liquid when it is introduced into a vinyl polymer. Do it in stages.

Examples of the functional groups to be introduced include a hydroxyl group, a carpoxyl group, a carboxylic anhydride group, an epoxy group, a methylol group, an alkoxymethylol group, an isocyanate group, an amide group, an amino group, and a chloro group. One or more of these functionalities can be introduced. However, dispersion stabilizer and/or
Or, when two or more types of functional groups are used together at the same time as the functional groups introduced into the vinyl polymer, if the functional groups are
Combinations that easily react in a short period of time must be avoided. These combinations include hydroxyl group, carboxylic acid anhydride group, hydroxyl group, isocyanate group, methylol group, isocyanate group, epoxy group, carboxyl group, epoxy group, amino group, carboxylic acid anhydride stem, amine/group, amino group, chlorine group, hydroxyl group, chloro group, epoxy group, Examples include a combination of a chloro group, an epoxy group, and a carboxylic acid anhydride group.

When introducing a functional group into a dispersion stabilizer, if the dispersion stabilizer is an acrylic polymer, it may be copolymerized with a vinyl monomer having the respective functional group, such as those shown in Table 1. .

Other copolymerizable vinyl monomers include styrene, Q
- Methylstyrene, vinyltoluene, acrylic acid esters (methyl, ethyl, butyl 2-ethylhexyl, octyl, cyclohexyl ester, etc.), methacrylic acid esters (methyl, ethyl, butyl, 2-ethylhexyl, lauryl, stearyl ester, etc.), acrylonitrile, methacrylonitrile , long mirror esters of vinyl acetate and acrylic acid or methacrylic acid (molecular weight 3 in the side chain)
00 to 3,000 alkyl groups, polyester groups, etc.). Table 1 also shows that when the dispersion stabilizer is an alkyd resin or a polyester, hydroxyl groups and/or carboxyl groups can remain in the resin skeleton because they are produced by a reaction between an acid and an alcohol.

When the dispersion stabilizer is an acrylic grafted polyester, the introduction methods for the acrylic polymer and polyester can be used in combination. When the dispersion stabilizer is a cellulose derivative, it naturally has a hydroxyl group. Furthermore, when the dispersion stabilizer is decomposed natural rubber or polybutadiene, hydroxyl groups, carboxyl groups, carboxylic acid anhydrides, epoxy groups, etc. can be introduced by utilizing the double bonds and active hydrogen in the skeleton.

The molecular weight of these dispersion stabilizers is 1000 in number average molecular weight.
A range of 200,000 to 200,000 is preferable.

If the molecular weight is less than 1000, the dispersion stabilizer loses its ability to form a stable dispersion. Also, 20
When it is larger than 0000, the viscosity of the dispersion becomes high,
It becomes difficult to achieve high solid content and low viscosity, which is one of the characteristics of the present invention. The dispersion stabilizer may not contain any functional groups as long as the functional groups are introduced into the vinyl polymer, but if the vinyl polymer does not contain any functional groups or the vinyl polymer has no functional groups, Even if it is contained, if it is desired to further improve the curability, the above-mentioned functional group is introduced into the dispersion stabilizer, and after the dispersion is produced, this functional group is utilized to introduce a polymerizable unsaturated group. In this case, the amount of the functional group is 0.5-7. M hard is preferable, 0
．． If it is less than sealing, the curing properties after introducing the polymerizable unsaturated group will be poor, and 7. If the amount is more than 10%, the polar effect due to the functional group becomes high and the ability as a dispersion stabilizer decreases, making it impossible to produce a stable dispersion. 0 On the other hand, when introducing a functional group into a vinyl polymer, it can be easily introduced by using the vinyl monomers shown in Table 1 in the step of producing a dispersion.

Of course, it is not necessary to introduce a functional group into the pinyl polymer if a functional group is introduced into the dispersion stabilizer, but if a functional group is not introduced into the dispersion stabilizer, or when the dispersion stabilizer is Even if a functional group is introduced into the vinyl polymer, if it is desired to further improve the curability, the functional group is introduced into the vinyl polymer.

In this case, the functional zero group weight is the molecular weight of the vinyl polymer, 1000.
0.5 to 7 per unit. If the hardness is less than 0.3 hardness, the curability after introducing the polymerizable unsaturated group will be poor, and 7. If the amount is higher than that of Kawago, it will have a negative effect on the performance of the coating film. The molecular weight of the vinyl polymer is not particularly limited, but it is usually within a common sense range of 2,000 to 10
If it is less than 2,000, physical and chemical deterioration of coating film performance is likely to occur, and if it is greater than 1,000,000, the fusion of dispersed particles will be hindered and problems will arise in film-forming properties. As other copolymerizable vinyl monomers, those exemplified as copolymerizable vinyl monomers in the above-mentioned section on dispersion stabilizers can be used.

In this way, it is possible to obtain a dispersion liquid in which either or both of the dispersion stabilizer and the vinyl polymer have a functional group.

Of course, depending on the dispersion state, the dispersion liquid may contain polymers mainly consisting of particles, microparticles, free dispersion stabilizers, unparticulated pinyl polymers, etc. (hereinafter collectively referred to as dispersion). Existing.

Subsequently, a polymerizable vinyl monomer having a group reactive with addition or condensation is reacted with the functional group in this dispersion to introduce a polymerizable unsaturated group. Table 2 shows the combinations of this introduction method. Table 2 Polymerizable vinyl monomers having addition or condensation reactivity may be reacted in an amount of 0.1 mol or more per 1 mol of functional groups in the dispersion, and two or more of the vinyl monomers are used in combination. be able to.

Moreover, even if more than 1 mol is used, there is no problem because these pinyl monomers act as a crosslinking agent during curing. During the reaction, if necessary, use known Z that has a reaction accelerating effect.
catalysts can also be used. For example, in addition reactions between hydroxyl groups and isocyanate groups, tin-based compounds such as stannous chloride and methyltin dichloride, amine-based compounds such as N-methylmorpholine, zinc-based compounds, and iron-based Z compounds are used. In the addition reaction between a carboxyl group and an epoxy group, tertiary amines such as triethylamine, as well as acidic catalysts and quaternary ammonium salts can be used.

In the dehydration condensation reaction between a carboxyl group and a hydroxyl group, an acidic catalyst such as sulfuric acid or a known esterification catalyst such as dibutyltin oxide can be used. Water acts as a catalyst between the leponic acid anhydride group and the epoxy group, and in the aether-tell exchange reaction between the methylol group and the hydroxyl group, and between the methylol group and the alkoxymethylol group, hydrochloric acid, phosphoric acid, oxalic acid, paratoluene di-sulfonic acid, etc. Acidic catalysts, alkaline catalysts such as potassium hydroxide and aqueous ammonia, and amine catalysts such as triethylamine and dibutylamine can be used. Known catalysts can be used in other reactions as well.
3 Here, we will provide an overview of the manufacturing process to date. The fractional stabilizers can be obtained by known polymerization methods, integration methods and addition reaction methods, respectively.
A stable dispersion liquid is prepared by placing an organic liquid mainly composed of aliphatic hydrocarbons (dispersed soot) and a dispersion stabilizer in a reaction vessel, and
After heating to 14,000 ℃, a mixed solution of a vinyl monomer (a dispersion stabilizer may be mixed with the vinyl monomer) and a polymerization catalyst is added dropwise over a period of 1 to 7 hours. It is obtained by continuing the reaction for 2 to 7 hours. Here, the amount of the dispersion stabilizer is 0.5 to 70% by weight based on the total amount of the pinyl monomer and the dispersion stabilizer. If it is less than 0.5% by weight, a stable dispersion cannot be produced.

If the amount exceeds 7% by weight, the dispersion system becomes a solution and loses its characteristics (high solid content, low viscosity). The concentration of the vinyl monomer and dispersion stabilizer in the dispersion is usually 30 to 7% by weight. After the dispersion is prepared, a polymerizable vinyl monomer having an addition or condensation reactivity is subsequently added into the dispersion in its entirety or by a dropwise addition method to carry out a reaction. The reaction temperature varies depending on the type of reaction, but is usually 60 to 16 psi. In this case, care must be taken in advance to select a solvent for the dispersion soot during the production of the dispersion liquid, which has a boiling point that will not hinder the temperature rise during the subsequent addition or condensation reaction. The addition or condensation reaction can be monitored based on the acid value, isocyanate value, hydroxyl value, eboxy value, amount of reaction-eliminated fraction, etc., depending on the reaction type. Further, during this addition reaction, if necessary, a known polymerization inhibitor may be added in order to prevent polymerization of the addition- or condensation-reactive polymerizable pinyl monomer. In this way, condensable unsaturated double bonds can be introduced into the dispersion in the dispersion.

The unsaturated resin dispersion of the present invention may contain vinyl monomers, polyvinyl compounds, stabilizers, colorants, plasticizers, and saturated resins (vinyl resins,
(acrylic resin, alkyd resin, epoxy resin, urethane resin, etc.) can also be mixed.

Vinyl monomers include styrene, Q-methylstyrene,
Vinyltoluene, acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile,
Acrylamide, vinyl acetate, etc. are mentioned, and multi-vinyl compounds include compounds having a molecular weight of 1000 or less and 2 to 4 polymerizable vinyl groups, such as diallyl phthalate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc. ) Acrylate, Bisou (
Ethylene glycol phthalate) di(meth)acrylate, Pis-(diethylene glycol phthalate) di(meth)acrylate, Polyethylene glycol di(meth)acrylate
Acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1:1 (mole ratio) of tolylene diisocyanate and (meth)acrylic acid hydroxyalkyl ester
Examples include addition reaction products of adducts with trimethylolethane or trimethylolpropane, and bentaerythritol tetra(meth)acrylate. In the present invention, methacrylate and acrylate are collectively referred to as (meth)acrylate. Stabilizers include polymerization inhibitors such as hydroquinone, benzoquinone, and catechols, and antioxidants such as 2,6-ditertiarybutylhydroxyltoluene. Colorants include dyes, organic pigments, and inorganic pigments. Plasticizers include low molecular weight plasticizers such as dimethyl phthalate and dioctyl phthalate, and high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers, which can also be used by being mixed into the unsaturated resin dispersion. It is also possible to dissolve the vinyl monomer during production of the dispersion and distribute it in the dispersed particles (mainly in the polymer particles) of the produced dispersion. The amount of photosensitizer is 0 based on the resin content of the unsaturated resin dispersion, or when vinyl monomer is mixed, the total amount of the resin content and vinyl monomer.
．． A range of 0.01 to 1% by weight is suitable.

Examples of photosensitizers include penzoin, benzyl, benzoin alkyl ether (alkyl group CnQn+, n=
1 to 18), azo compounds such as 2,2'-azopisisoputilonitrile, 2-phenylazo2,4dimethyl-4-toxyvaleronitrile, and 2-phenylazo2,4-dimethylvaleronitrile. ,
Examples include sulfur-based compounds such as diphenyl disulfide and tetramethylthuram monosulfide, and photosensitizing aids such as penzophenone, 1,5-dinitroanthraquinone, and anthraquinone can also be used in combination. In addition, the amino resin is added in an amount of 5 to 200% by weight based on the resin content (including vinyl monomer) of the dispersion. Examples of the amino resin include amide-formaldehyde resin, amine-formaldehyde resin, which is used for general paints. Resin can be given. As the irradiation source of the present invention, devices that emit heat rays at the same time as ultraviolet rays are used, such as various high-pressure mercury lamps and aquatic lamps used in conventional photocurable paints.

Of course, an organic solvent, ie, a thinner for adjusting viscosity or a solvent as a film fusing agent, may be added to the dispersion of the present invention at any time. According to the present invention, a polymerizable unsaturated double bond is introduced into a dispersion generally called a non-aqueous dispersion, and since it is an emulsion, it has a high solid content and a low viscosity. Moreover, the coating workability is good, and the molecular weight of the polymer can be made high regardless of the viscosity.

In addition, conventional low molecular weight, low viscosity unsaturated resins not only have poor curing properties for the entire film, but also have very poor curing properties in air due to oxygen damage, and unsaturated resins that are cured in a nitrogen atmosphere are difficult to cure. This was a major factor hindering the development of resins. However, the non-aqueous unsaturated resin dispersion according to the present invention has a high molecular weight, so internal curing is fast, and in addition to the high molecular weight, since it is an emulsion, it has a film-forming effect due to the fusion of particles, so it is hard to cure in the air. The drying and curing properties are very good, and the film performance is also very good.

Furthermore, when applying thick coatings, conventional unsaturated resins tend to sag and have disadvantages in coating workability, but with the non-aqueous unsaturated resin dispersion according to the present invention, even thick coatings are possible. It showed good coating workability, with good film adhesion and an excellent finish for metallic coatings.

In addition, compared to conventional unsaturated resin solutions, it has a high molecular weight and is particulate, so it has a low degree of unsaturation and can exhibit excellent coating performance. In addition, conventional photocurable paints have a limit to the pigment concentration that can be added, and conventional thermosetting paints have
For coatings with a film thickness of 50 μm or more, pigment concentrations of 1/5 to 1/1 degree Fahrenheit have only been put into practical use, but by using an amino resin, the present invention can achieve a pigment concentration comparable to that of conventional thermosetting paints. However, it has become sufficiently hardened. The resin dispersion composition of the present invention can be applied to metal products such as steel plates, plastics, wood, plywood, paper, leather, and the like.

Also, depending on the object to be coated, which has a complicated shape, or the back side of the object to be coated, it may be exposed to direct ultraviolet rays, resulting in shaded areas, but by adding amino resin, heat curing can occur. can.

The effects of adding this amide/resin include a thermal crosslinking reaction with the functional group of the vinyl monomer substituted in the dispersion layer and/or an excess functional group in the dispersed particles, a self-condensation reaction between the amide/resin, It has a photocuring accelerating effect due to interaction with photosensitizers, especially penzyl and penzoin compounds.
Furthermore, amino resins can also be used as pigment dispersants. The functional groups of the vinyl monomer substituted in the dispersion medium and/or the surplus functional groups in the dispersed particles (contained in the dispersion stabilizer and/or vinyl polymer) include hydroxyl groups, methylol groups, and alkoxymethylol groups. , carboxyl group, carboxylic acid anhydride group, isocyanate group, etc. are particularly effective.

Further, the non-aqueous unsaturated resin dispersion composition obtained by the present invention can be used as a coating composition itself, but can also be used as a fishing port agent-type unsaturated resin paint, in which it is generally difficult to form a matte coating. By adding Z to the composition, an erasable coating film can be easily formed. The present invention will be explained below with reference to Examples.

Parts and % mean parts by weight and % by weight. In addition, in Examples and Comparative Examples, the resin component includes vinyl monomer. Example 1 1 Preparation of dispersion The following substances were added to a flask and heated to 90 to 1000 C while nitrogen gas was passed through to dissolve well.

E Ship 551-02 Go (trade name manufactured by Eastman Chemical Company, cellulose acetate butyrate, butyl group content 55% by weight)
butyl diacetate
100 aliphatic hydrocarbons (B.P.120-14
0qo) 200 then add the following substances and make 100
The reaction was carried out at qC for 30 minutes.

t-butyl per octoate 2 parts methyl methacrylate 50 Thereafter, the following mixture was further added dropwise over 3 hours.

Methyl methacrylate 30 base part 2-
Hydroxyethyl acrylate 90 Butyl acrylate 40 t-Butyl peroctoate 1 base aliphatic hydrocarbon (BP.1
20-140 pm) 100 After aging for 2 hours, a white semi-solid dispersion was obtained, and when 10 parts of aliphatic hydrocarbon was further added while stirring thoroughly, a stable dispersion was obtained. The non-volatile content was 50%. D. Preparation of unsaturated group-introducing dispersion The following substances were added to the above-mentioned dispersion and reacted at 80°C for 4 hours to introduce unsaturated groups.

1:1 (mole ratio) addition reaction product of tolylene diisocyanate and 2-hydroxyacrylate 300 parts Hydroquinone 0.5 Butyl acetate 100 Aliphatic hydrocarbon (BP. 120-140°C) 200 Reaction is N
The CO value was tracked and the end point was 1 or less.
(Manufactured by Hitachi Chemical ■, butylated melamine, resin content 50.
0%, trade name) Add 1 Misaki HR and add titanium white to 10 H
The R-dispersed product was coated on a polished mild steel plate to a film thickness of 30 cm, and when irradiated with a 4KW high-pressure mercury lamp from a distance of 30 arc for 3 minutes, it was completely cured and a coating film with excellent adhesion was obtained.

Example 21 Production of dispersion liquid The following materials were placed in a flask and heated while passing nitrogen gas to raise the temperature to 90 to 100 qo.

Mineral Spirit 100 Ikaribe N
ISSO-PB (B-3000) 500
(Product name of Nippon Soda Co., Ltd., butadiene homopolymer one,
(Number average molecular weight: 3000) Next, the following mixed solution was added dropwise over 3 hours, followed by heating for 2 hours.

Acrylonitrile 17 Anchors Methyl methacrylate 1502-Hydroxyethyl acrylate 60 Azobisisobutyronitrile 10 The milky white stable dispersion thus obtained had a non-volatile content of 50%.

(b) Production of unsaturated group-introducing dispersion The following substances were added to the above-mentioned dispersion and reacted at the reflux temperature of mineral spirits to introduce unsaturated groups by ether exchange.

N-methylol acrylamide 52 P-toluenesulfonic acid 6.5 in about 5 hours 8.
5g of water came out.

The reaction was followed by the amount of distilled water. 1 of 10 anchors after the reaction is complete,
6-hexanediol diacrylate and 152 mineral spirits were added to make a varnish with a non-volatile content of 50%.

To this varnish (resin content), IPHR's penzoin ethyl ether and Melan 11 (manufactured by Hitachi Chemical Co., Ltd., butylated urea, resin content 60% trade name) 3-fertilization HR were added, and carbon was added to the snake HR. After adding and dispersing well, it was painted on a polished mild steel plate to a film thickness of 20 cm, and when irradiated for 60 seconds with a high-pressure mercury lamp on the side without setting, it was completely cured and had excellent adhesion. Example 31 Production method of dispersion stabilizer The following substances were placed in a flask and heated to reflux temperature, and a condensation reaction was performed until the acid value became 0.5 or less.

Pentaerythritol 816 parts Adipic acid 730 Toluene
15 Furthermore, 252 parts of tall fat and acid were added, and the condensation reaction was carried out at reflux temperature as before until the acid value became 0.5 or less.

Next, 74 parts of phthalic anhydride, boiling point range 120-140℃
4,464 parts of aliphatic hydrocarbon were added thereto, and the mixture was heated to 8.0 psi, and the reaction was carried out until the acid value reached 48.3. Do not heat above 8,000 ℃ at this stage. The condensate thus obtained had a nonvolatile content of 50%. B. Production of dispersion Next, put the following substances into a flask and heat to 90q0.

Condensate obtained in step 20 parts normal heptane 30 parts butyl acetate
13 Then, methyl acrylate 9.6 parts Styrene 10.0 Acrylonitrile 5.12-Hydroxyethyl acrylate 11.2 Acrylic acid
7.1 Azobisisobutyronitrile
A mixture of 1.5 and 1.5 was added dropwise into the flask over 3 hours, and the reaction was continued for an additional 2 hours.

The polymer solution thus obtained was milky white and had a non-volatile content of 50
%Met. m Production of unsaturated group-introduced dispersion Add less than one substance to the base of the dispersion 20 described above, and heat at 90°C.
The reaction was allowed to proceed for 8 hours.

Gridyl methacrylate 57 parts Triethylamine 0.3 Hydroquinone
0.1 reaction was tracked by acid value, and a value of 1 or less was considered the end point.

4 parts of 2-ethylhexyl methacrylate and 10 parts of trimethylolpropane triacrylate were added to 257 parts of the unsaturated group-introduced dispersion thus obtained, and then to the resulting varnish (resin content), Snake HR2,2-Azopisisobutyronitrile and Melan 26 (manufactured by Hitachi Chemical, isobutylated melamine, resin content 60%) Tsubo H
A well-dispersed solution of R titanium white 10% HR was applied to a polished mild steel plate to a film thickness of 40 mm, and irradiated for 2 minutes from a distance of 30 arc with a high-pressure mercury lamp to obtain a cured coating. The coating film had excellent physical properties and solvent resistance. Example 4 1 Production of dispersion stabilizer The following substances were placed in a flask and heated to 110°C.

butyl acetate 15 parts aliphatic hydrocarbon with a boiling point range of 120 to 14 points. 4 Then, the following mixture was added dropwise over 3 hours, and the reaction was further carried out for 2 hours.

2-ethylhexyl acrylate 73.6 parts 2-hydroxyethyl acrylate 11.6 Glycidyl methacrylate 14.2 Azopisisobutyronitrile 1.0 The obtained polymerization solution has a non-volatile content of 50%
Met.

B. Production of dispersion (B) The following substances were placed in a flask, heated to 90°C, and pressed.

Solution Obtained in (2) 1. Isobe Aliphatic hydrocarbon having a boiling point range of 160 to 180° C. 140° C. Then, the following mixture was added dropwise to the flask over 3 hours, and the reaction was further carried out for 2 hours.

Styrene 23. $part Acrylonitrile 21.72-Hydroxyethyl acrylate 95.0 Penzoyl peracid
2.1 The polymer solution thus obtained was a milky white emulsion with a non-volatile content of 50% and good storage stability. m Production of unsaturated group-introduced dispersion To 20 bases of the above dispersion, add the following compound.
The reaction was carried out at 20°C for 1 hour.

Acrylic acid 2. Triethylamine 0.01 After that, 44 parts of maleic anhydride was added and reacted at 120qC for 3 hours to measure the total acid value and half acid value, and the acid anhydride content was 95%.
The point where the above reaction occurred was defined as the end point.

Next, 64 parts of glycidyl acrylate was added, and 120q
The reaction was carried out for 1 hour at o. This was cooled, 30 parts of styrene was added, and the resulting varnish (resin content) was added with IPHR's Penzoinethyl Apure and Melan 7.
1 (manufactured by Hitachi Chemical, methylated melamine, resin content 60
% (trade name) 6 plate HR was added and applied to a polished mild steel plate to a film thickness of 40 mm, and was cured by irradiating it with light for 1 minute from a distance of 30 mm using a high-pressure mercury lamp. Example 5 1 Production of dispersion Solution obtained in Example 4-1 120 parts Boiling point 12
Pour 0 to 140 pm of aliphatic hydrocarbon 140 into a flask, overflow to 9000, and add 3 of the following mixture.
It dripped over time.

Styrene 42 parts Acrylonitrile 36 Glycidyl methacrylate 30.

82-Hydroxyethyl methacrylate 31.4 Penzoyl peroxide 2.1 After completion of dropping,
Aged for 1 hour and added 0 penzoyl peroxide.
．． 5 parts were added and aged for 2 hours.

The white, low viscosity dispersion thus obtained was approximately 50%
It had a non-volatile content of

U Preparation of unsaturated group-introduced dispersion To 20 parts of this dispersion, add 9.7 parts of acrylic acid, 0.1 part of tetraethylammonium chloride, and 0.1 part of hydroquinone, and react at 120q0 for 5 hours to increase the acid value. 1 was set as the end point.

Furthermore, 48 parts of tolylene diisocyanate and 2-hydroxyacrylate 1:1 (mole ratio) addition reaction product were added,
The reaction was carried out for 1 hour, and the end point was an NCO value of 1 or less. 5 parts of ethylene glycol diacrylate was added to the unsaturated group-introduced dispersion thus obtained, and 0.0 parts of ethylene glycol diacrylate was added to the resulting varnish (resin content). Penzoin methyl ether from Snake HR and Melan 11 from 10 Misaki HR were added, and then Cyanine Full-1 Group HR was mixed and well dispersed. Painted on a polished steel plate to a thickness of 304, and after setting for 5 minutes. Using a 4KW high-pressure mercury lamp, the skin was irradiated for 30 seconds from a distance of 30 meters. The resulting coating film was hard and had good adhesion and solvent resistance. Example 6 1 Production of dispersion stabilizer■ Put the following substances into a flask and
The dehydration condensation reaction was carried out in the reaction temperature range of .degree. C. until the acid value reached 30 to 29.

12-hydroxystearic acid 84.7 parts Monomethylsulfonic acid 0.8 toluene
Then, the following substances were added and heated to 150 oo, and an addition reaction was carried out until the acid value became 1 or less.

Glycidyl methacrylate 5.2 parts Aliphatic hydrocarbon with a boiling point range of 140-160 qC 2.1 Para-tertiary butylcatechol 0.05 Dimethyl coconut amine 0.2 The resulting condensation adduct has a terminal vinyl group with a molecular weight of about 1500-1700 It was a brown viscous liquid with a non-volatile content of 83% and an acid value of 0.8.

'B) The following substances were placed in a flask and heated to 11,000 ℃.

33.6 parts of amyl acetate 100 parts of aliphatic hydrocarbon with a boiling point range of 160 to 180 qo Then, the following substances were added dropwise into Tsukuda's flask over 3 hours.
The reaction was continued for an additional 2 hours.

Condensate adduct obtained in (2) 117 parts Glycidyl methacrylate 118.6 Azopisisobutyronitrile 1.0 The obtained polymer solution was pale and brown in color and had a non-volatile content of 50%. B. Production of dispersion: Place the following substances in a flask and heat to 80°C.

100 parts of the polymer solution obtained in Example 6, 1 [B'] Aliphatic hydrocarbon (B.P. 160-180°C) 116
Then, the following mixture was added dropwise thereto over 3 hours, and the reaction was continued for an additional 2 hours.

Butyl methacrylate 4 anchors Acrylonitrile 200 Styrene 402-Hydroxyethyl acrylate 15 Azobisisobutyronitrile 15 The obtained polymer solution is a milky white dispersion and has good storage stability.

The non-volatile content was 50%. m. Preparation of unsaturated group-introduced dispersion 15 parts of acrylic acid was added to 20 bales of the above-mentioned dispersion, and the mixture was reacted at 130°C for 4 hours.

Thereafter, 0.5 part of P-toluenesulfonic acid was added, the temperature was raised to 150 qo, and the mixture was reacted for 8 hours. The end point was an acid value of 1 or less. Water is 1. I brought out whole crab. 0.0% based on the resin content of the unsaturated group-introduced dispersion thus obtained. Kabuto HR's Pencil and 200 PHR Corban 201 SE (manufactured by Mitsui Toatsu Kagaku Co., Ltd., butylated melamine, resin content 50% trade name) were added and painted to a film thickness of 30 mm on a polished mild steel plate, and a 4KW high pressure mercury lamp was applied. Light was irradiated for 3 minutes from a distance of 30 cm. The coating was cured and had excellent solvent and water resistance. Example 7 1. Production of dispersion stabilizer The substances shown below were placed in a flask and heated to 80°C.

After producing a dispersion of 100 parts normal octane 1160 of the polymer solution obtained in the 1-leg of Example 6, the following mixture was added dropwise over 3 hours and the reaction was continued for a further 3 hours.

Butyl methacrylate - 5 anchors acrylonitrile 25 styrene
40 penzoyl peroxide
2 This product was a stable milky white liquid with a non-volatile content of 50%.

m Production of unsaturated group-introduced dispersion 4.3 parts of methacrylic acid and 0.1 part of hydroquinone were added to 20 parts of the above dispersion, and the reaction was carried out at the reflux temperature of octane, and the end point of the reaction was an acid value of 1.
The following was made.

The resin content of this product is HR's Penzoin and Ruban 91-55 (manufactured by Mitsui Toatsu Chemical ■, benzoguanamine, resin content 55%, trade name) 15 Misaki HR Titanium White 5 Eaves H
R was added and well dispersed.

When coated on a polished European steel plate to a thickness of 50 mm and irradiated with a high-pressure mercury lamp for 6 hours, it was completely cured and had excellent adhesion. Comparative Example 1 The following substances were placed in a flask, heated to 110 qo, and stirred.

Solution obtained in Example 3 20 parts aliphatic hydrocarbon with a boiling point range of 120 to 140 qo 30 butyl acetate
13 Then, the following mixture was added dropwise into the flask over 3 hours, and the reaction was further carried out for 2 hours.

Butyl methacrylate 1 Styrene base
15 Acrylonitrile
15 Glycidyl methacrylate 10 The product thus obtained was milky white and had a very high viscosity (more than 100 Stoke, 260) and could not be measured.

Also, when this product was applied, a lump appeared on the entire surface, it did not dissolve in solvents (dimethyl ketone and other good solvents), and particulate gel was observed. Comparative Example 2 The same formulation was used as in Example 1 except that Melan 20 was not added.

. This product was applied to a polished mild steel plate to a film thickness of 60 mm, and after setting it was irradiated with a 4KW high-pressure mercury lamp at a distance of 30 cm for 3 minutes, but the surface remained sticky and did not harden. Comparative Example 3 The coating of Example 7 without the addition of Reuban 91-55 was applied to a European steel plate to a film thickness of 50 mm, and when irradiated with a 4 KW high-pressure mercury lamp from a distance of 30 mm to a distance of 6 mm, the inside was not hardened at all. It caused sagging.

Claims (1)

[Scope of Claims] 1. A hydrocarbon polymer soluble in an organic liquid (dispersion medium) that dissolves the vinyl monomer but does not dissolve the polymer formed from the monomer; The vinyl monomer is polymerized in the organic liquid in the presence of a dispersion stabilizer selected from acrylic polymers, polyesters, alkyd resins, cellulose derivatives, and block or graft polymers of these vinyl monomers. A stable dispersion of a vinyl polymer in which polymer particles are dispersed, wherein either or both of the dispersion stabilizer and the vinyl polymer contain a hydroxyl group, a carboxyl group,
It has one or more functional groups selected from carboxylic anhydride groups, epoxy groups, methylol groups, alkoxymethylol groups, isocyanate groups, amide groups, amino groups and chloro groups, and after producing the dispersion, the functional groups are A non-aqueous unsaturated material whose main component is a dispersion prepared by adding or condensing a polymerizable vinyl monomer to the group to introduce a polymerizable unsaturated group of either or both of the dispersion stabilizer and the vinyl polymer. Resin dispersion II A non-aqueous unsaturated resin dispersion composition comprising an amino resin III and a photosensitizer.