JPS5845448B2 - Fuhouwaji Yusibun Sun Exo Saibuts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous unsaturated resin dispersion,
More specifically, the present invention relates to a dispersion composition of an unsaturated resin in a vinyl monomer.

Conventional unsaturated resins, especially unsaturated resins that are subjected to light irradiation curing, electron beam irradiation curing, etc., are focused on low pollution, and it is essential that they have as high a solids content as possible and a low viscosity that can be painted. there were.

However, in order to achieve high solid content and low viscosity, conventional methods have been used to lower the molecular weight of unsaturated resins, resulting in a significant drop in film performance, curing properties, etc., and the balance between solid content, viscosity, and performance cannot be achieved. It was far from the realm of.

In order to satisfy the above-mentioned conditions required for unsaturated resins, the present inventors have conducted extensive research and have developed a method to achieve high solids content by utilizing non-aqueous dispersions, which are currently attracting attention in the coating industry.
It has been discovered that it is possible to provide an unsaturated resin dispersion with low viscosity and excellent coating workability.

Furthermore, the present invention replaces the organic liquid as a dispersion medium with a vinyl monomer to stably disperse an unsaturated resin in the vinyl monomer, and is non-polluting with a high solid content and no emitted solvent. This made it possible to further strengthen sexuality.

That is, the present invention provides (I) in which the vinyl monomer is dissolved in an organic liquid in which the polymer formed from the monomer is not dissolved, in the presence of a dispersion stabilizer soluble in the organic liquid. A stable dispersion of a vinyl polymer obtained by polymerizing a monomer and dispersing the polymer in the organic liquid, wherein the dispersion stabilizer and/or the vinyl polymer contain a hydroxyl group, a carboxyl group, a carboxylic acid anhydride. group, epoxy group, methylol group, alkoxymethylol group, incyanate group, amide group, amino group, and chloro group, and has addition or condensation reactivity with the functional group. After producing a dispersion, a dispersion containing a polymerizable vinyl monomer as a main component is produced by reacting the dispersion with a polymerizable vinyl monomer, and then a part or all of the organic liquid is added from the dispersion to one or two kinds. The present invention relates to a non-aqueous unsaturated resin dispersion obtained by substitution with the above vinyl monomer, a non-aqueous unsaturated resin dispersion composition comprising (II) an amino resin, and (IID) a photosensitizer.

As a stable dispersion liquid in a non-aqueous dispersion system, one obtained by a conventionally known method can be used.

That is, Japanese Patent No. 317938, Japanese Patent No. 53459
No. 1, No. 458051, No. 286387, No. 416484, Special Publication No. 47-8537, No. 43-1
No. 6147, No. 47-11838, JP-A-46-52
No. 37, U.S. Patent No. 3405087, U.S. Patent No. 35515
No. 25, No. 3365414, No. 3261788, No. 3298990, No. 3382297, No. 3255135, etc.

The non-aqueous vinyl polymer dispersion is mainly about 0.1 to 0.9
Polymer particles with a particle size of microns are stably dispersed in an organic solvent mainly composed of non-polar hydrocarbons, and depending on polymerization conditions, polymer particles with a diameter of 0.1 micron or less or a dispersion medium may also be dispersed. Soluble polymers may also be present.

In general, the manufacturing method is to use a dispersion stabilizer in a dispersion medium (an organic liquid mainly composed of aliphatic hydrocarbons), and the vinyl monomer is dissolved in the dispersion medium, but the polymer is dissolved in the dispersion medium. It is obtained by polymerizing vinyl monomers that do not

The dispersion medium is mainly aliphatic hydrocarbons, that is, petroleum fractions, such as pentane, hexane, heptane,
Octane, mineral spirits, naphtha, etc. are used.

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. Acrylic polymer, polyester,
Examples include alkyd resins and cellulose derivatives, and block or graft polymers of these and vinyl monomers.

The vinyl polymer that becomes the main dispersed particles is, for example, a polymer or copolymer of styrene, an acrylic monomer, a methacrylic monomer, vinyl acetate, or the like.

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 carboxyl group, a carboxylic anhydride group, an epoxy group, a methylol group, an alkoxymethylol group, an incyanate group, an amide group, an amino group, and a chloro group.

One or more of these functional groups can be introduced.

However, when using two or more functional groups at the same time as a dispersion stabilizer and/or a functional group to be introduced into a vinyl polymer, combinations in which the functional groups easily react with each other at room temperature in a short period of time must be avoided. .

These combinations are Hydroxyl group and carboxylic acid anhydride group Hydroxyl group and incyanate group Methylol group and incyanate group Epoxy group and carboxyl group Epoxy group and amino group Carboxylic acid anhydride group and amino group Amino group and chlorine group Hydroxyl and chlorine groups Epoxy group and chlorine group Epoxy group and carboxylic acid anhydride group Combinations such as

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, α
- Methylstyrene, vinyltoluene, acrylic esters (methyl, ethyl, butyl, 2-ethylhexyl, octyl, cyclohexyl esters, etc.), methacrylic esters (methyl, ethyl, butyl, 2-ethylhexyl, lauryl, stearyl esters, etc.), acrylonitrile , methacrylonitrile, vinyl acetate, and long chain esters of acrylic acid or methacrylic acid (having an alkyl group with a molecular weight of 300 to 3,000 in the side chain).

In addition, when the dispersion stabilizer is an alkyd resin or a polyester, since it is produced by a reaction between an acid and an alcohol, a hydroxyl group and/or a carboxyl group can remain in the resin skeleton.

When the dispersion stabilizer is an acrylic graft polyester, the methods for introducing both the acrylic polymer and polyester can be used in combination.

When the dispersion stabilizer is a cellulose derivative, it naturally has a hydroxyl group.

In addition, when the dispersion stabilizer is decomposed natural rubber or polybutadiene, hydroxyl groups and
Carboxyl groups, carboxylic acid anhydrides, epoxy groups, etc. can be introduced.

In addition, any dispersion stabilizer that is effective as a dispersion stabilizer and has the skeletal group mentioned above in the present invention can be used as an example of a dispersion stabilizer having a functional group.

The molecular weight of these dispersion stabilizers is 1.00 in number average molecular weight.
A range of 0 to 200,000 is preferred.

If the molecular weight is less than 1,000, it loses its ability as a dispersion stabilizer, making it impossible to form a stable dispersion.

On the other hand, if it is greater than 200,000, the viscosity of the dispersion becomes high, making it 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 separation liquid is produced, this functional group is used to introduce a polymerizable unsaturated group.

In this case, the amount of the functional group is determined by the molecular weight of the dispersion stabilizer being 1,000.
The number is preferably from 0.5 to 7.0 per 0 units.If it is less than 0.5, the curing properties after introducing the polymerizable unsaturated group will be poor, and if it is more than 7.0, the polarity effect due to the functional group will occur. becomes high and its ability as a dispersion stabilizer decreases, making it impossible to produce a stable dispersion.

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 vinyl polymer as long as the functional group is introduced into the dispersion stabilizer.
When a functional group is not introduced into the dispersion stabilizer, or when a functional group is introduced into the dispersion stabilizer but it is desired to further improve the curability, a functional group is introduced into the vinyl polymer.

In this case, the amount of functional groups is the molecular weight of the vinyl polymer, which is 1.000.
The number is preferably 0.5 to 0.7 per unit, and if it is less than 0.5, the curing properties after introducing the polymerizable unsaturated group will be poor, and if it is more than 7.0, it will have a negative effect on the coating performance. give.

The molecular weight of the vinyl polymer is not particularly limited, but the number average molecular weight is usually within the common sense range of 2,000 to 1,000,
000 and less than 2,000, there is a physical problem in terms of coating film performance.
It is easy to cause chemical deterioration, and if it is thicker than 1,000,000, it will hinder the fusion of dispersed particles and cause problems in film-forming properties.

As other copolymerizable vinyl monomers, those exemplified as copolymerizable vinyl monomers in the above-mentioned dispersion stabilizer can be used.

In this way, a dispersion liquid having a functional group in either or both of the dispersion stabilizer and the vinyl polymer can be obtained.

Of course, depending on the dispersion state, the dispersion may contain polymers mainly consisting of particles, microparticles, free dispersion stabilizers, non-particulate vinyl 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. Attachment 7I C Or the polymerizable vinyl monomer having condensation reactivity may be reacted with 0.1 mol or more per 1 mol of the functional group in the dispersion, and two or more of the vinyl monomers may be used in combination. be able to.

Moreover, even if more than 1 mol is used, there is no problem because these vinyl monomers act as a crosslinking agent during curing.

During the reaction, if necessary, a known catalyst having a reaction promoting effect can be used.

For example, in the addition reaction between a hydroxyl group and an incyanate group, tin-based compounds such as stannous chloride and methyltin dichloride, amine-based compounds such as N-methylmorpholine, zinc-based compounds, and iron-based compounds are used. In addition to tertiary amines such as triethylamine, acidic catalysts and quaternary ammonium salts can be used in the addition reaction.

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 carboxylic acid anhydride groups and epoxy groups, and acidic catalysts such as hydrochloric acid, phosphoric acid, oxalic acid, and p-toluenesulfonic acid are used in the ether exchange reactions between methylol groups and hydroxyl groups, and between methylol groups and alkoxymethylol groups. , alkaline catalysts such as potassium hydroxide and aqueous ammonia, and amine catalysts such as triethylamine and dibutylamine.

Known catalysts can be used in other reactions as well.

Here, we will provide an overview of the manufacturing process to date.

The dispersion stabilizer can be obtained by a known polymerization method, condensation method, or addition reaction method.

A stable dispersion liquid is prepared by placing an organic liquid (dispersion medium) mainly composed of aliphatic hydrocarbons and a dispersion stabilizer in a reaction container, and
After heating to 140° C., 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 weight φ based on the total amount of the vinyl monomer and the dispersion stabilizer.

If the weight is less than 0.5 da, a stable dispersion cannot be produced.

Moreover, if the weight exceeds 70%, 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 70% 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 each reaction type, but is usually 60°C.
~160°C.

In this case, care must be taken in advance to select a dispersion medium having a boiling point that does not hinder the temperature rise during the subsequent addition or condensation reaction during the production of the dispersion.

Tracking of addition or condensation reactions depends on the reaction type, acid value, incyanate value, hydroxyl value, epoxy value,
This can be carried out by adjusting the amount of reaction-eliminated fraction, etc.

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 vinyl monomer.

In this way, polymerizable unsaturated double bonds can be introduced into the dispersion in the dispersion.

Next, an organic liquid (dispersion medium) is extracted from the dispersion thus obtained.
Part or all of is substituted with one or more vinyl monomers.

This replacement method involves heating the dispersion below the boiling point of the dispersion medium, distilling off a portion of the organic liquid, and then adding the vinyl monomer.

When the boiling point of the vinyl monomer to be substituted is higher than the boiling point of the organic liquid, it is also possible to mix the vinyl monomer into the dispersion in advance and then distill off part or all of the organic liquid.

Further, while removing the organic liquid, it is also possible to replace part or all of the organic liquid while adding a vinyl monomer having a boiling point higher than that of the organic liquid.

Further, the dispersion medium may be removed by distillation under reduced pressure or under the blowing of air or inert gas.

In this case, there is no need to boil the dispersion medium, and the heating may be carried out at an appropriate temperature depending on the degree of pressure reduction or the balance between the amount of gas blown and the amount of distillation of the dispersion medium.

Examples of vinyl monomers to be substituted include styrene, α-methylstyrene, vinyltoluene, acrylic esters, methacrylic esters, acrylonitrile, methacrylate trile, acrylamide, and vinyl acetate.

As a polyvinyl compound, the molecular weight is 1,000 or less and 2 to 4.
Compounds having polymerizable vinyl groups, such as diallyl phthalate, ethylene glycol di(meth)acrylate, tetraethylol glycol di(meth)acrylate, bis-(ethylene glycol phthalate) di(meth)acrylate, bis-(diethylene glycol phthalate) di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tolylene diisocyanate and (
1= with meth)acrylic acid hydroxyalkyl ester
1 (molar ratio) adduct with trimethylolethane or trimethylolpropane, pentaerythritol tetra(meth)acrylate, and the like.

In the present invention, methacrylate and acrylate are collectively referred to as (meth)acrylate.

In this way, a stable non-aqueous unsaturated dispersion medium can be obtained in which part or all of the organic liquid is replaced with a vinyl monomer.

The unsaturated resin dispersion of the present invention can be used as it is, but stabilizers, colorants, plasticizers, saturated resins, etc. can also be mixed in as needed.

Further, from the viewpoint of adjusting viscosity, balancing performance, etc., the above-mentioned vinyl monomer may be added.

Stabilizers include polymerization inhibitors such as hydroquinone, benzoquinone, and catechols, and antioxidants such as 2,6-ditashyabutylhydroxytoluene.

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 an unsaturated resin dispersion. It is also possible to dissolve it in the vinyl monomer during production of the dispersion and distribute it in the dispersed particles (mainly in the polymer particles) of the produced dispersion.

Examples of the saturated resin include vinyl resin, acrylic resin, alkyd resin, epoxy resin, and urethane resin.

The amount of the photosensitizer is suitably in the range of 0.01 to 10 weight φ based on the total amount of the resin and vinyl monomer in the unsaturated resin dispersion.

Examples of photosensitizers include benzoin, benzyl, benzoin alkyl ether (alkyl group CnH2n+1.
benzoin compounds such as n=1 to 18), azo compounds such as 2,2-azobisisobutyronitrile, 2-phenylazo2,4dimethyl 4-methoxyvaleronitrile, and 2-phenylazo-2,4-dimethylvaleronitrile; Examples include sulfur-based compounds such as diphenyl disulfide and tetramethylthiuram monosulfide, and photosensitizing aids such as benzophenone, anthraquinone, and 1,5 dinitroaisotraquinone can also be used in combination.

Further, the amine resin is added in an amount of 5 to 200 weight φ based on the resin content (including vinyl monomer) of the dispersion.

Amino resins include amide resins used for general paints.
Examples include formaldehyde resin and amine-formaldehyde resin.

As the irradiation source of the present invention, devices that emit heat rays at the same time as ultraviolet rays can be used, such as various high-pressure mercury lamps and arc lamps used in conventional photocuring paints.

It is permissible to add an organic solvent to the dispersion of the present invention, ie, a thinner for adjusting viscosity or a solvent as a film coalescing agent.

According to the present invention, part or all of the dispersion medium of a dispersion, generally called a non-aqueous dispersion, is replaced with a vinyl monomer to introduce polymerizable unsaturated double bonds into the dispersion. Since it is an emulsion, it has a high solid content and low viscosity, and also has good coating workability, and the molecular weight of the polymer can be made high regardless of the viscosity.

Therefore, compared to the conventional method in which vinyl monomer is dissolved in unsaturated resin as a crosslinking agent and viscosity modifier, the amount of vinyl monomer used is small and a high-performance coating film can be obtained. be able to.

This matter is a great advantage from the standpoint of eliminating pollution.

That is, in the case of conventional unsaturated resins that are used dissolved in volatile vinyl monomers, there is a serious problem of air pollution and other pollution caused by the volatilized vinyl monomers.

In order to solve these problems, attempts have been made to use vinyl monomers with high boiling points and low volatility generation, but conventional unsaturated resin solutions tend to have high viscosity because they have little action as viscosity modifiers. However, in order to improve workability, it is necessary to use a large amount of vinyl monomer, and the compatibility is also poor.

In contrast, according to the present invention, the amount of vinyl monomer used is small, so even when volatile vinyl monomers are used, the amount that evaporates is small and there is little risk of pollution.

Furthermore, even when high-boiling vinyl monomers are used, the emulsion has a high solid content and low viscosity, making it easy to work with. It has the feature of smoothing the painted surface because it acts as a chemical agent.

Furthermore, conventional unsaturated resins with low molecular weight and low viscosity not only have poor curing properties for the entire film, but also have poor curing properties in air due to oxygen damage. This was a major factor hindering the development of

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. It has good drying properties and curing properties, and excellent film performance.

Furthermore, when applying a thick coating as a coating film, conventional unsaturated resins tend to sag and have drawbacks in painting workability, but with the non-aqueous unsaturated resin dispersion according to the present invention, even when applied thickly, a film can be formed. It showed good paint workability, with good adhesion and an excellent metallic paint finish.

In addition, compared to conventional unsaturated resin solutions, it has a higher molecular weight and is particulate, so it can exhibit superior coating film performance at least in terms of unsaturation.

In addition, there is a limit to the concentration of pigment added in conventional photocurable paints, and compared to conventional thermosetting paints, pigment concentrations that are only about 115 to 1/10th of the thickness of 50P or more have been put into practical use. In the present invention, by using an amino resin, the paint can be cured satisfactorily even with a pigment concentration comparable to that of conventional thermosetting paints.

The dispersion composition of the present invention can be applied to metal products such as steel plates, plastics, wood, plywood, paper, leather, and the like.

Furthermore, depending on the object to be coated, which has a complicated shape, or the back side of the object, there may be a shaded area that is not directly exposed to ultraviolet rays, but by adding an amine resin, heat curing can be expected in this area as well.

The effects of adding this amino resin include a thermal crosslinking reaction with the functional group of the vinyl monomer substituted in the dispersion medium and/or an excess functional group in the dispersed particles, a self-condensation reaction between the amine resins, and a photointensification reaction. It has a photocuring accelerating effect due to interaction with sensitizers, especially benzyl and benzoin compounds.
Furthermore, amine 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, alkoxy, and methylol groups. A carboxyl group, a carboxylic acid anhydride group, an incyanate group, etc. are particularly effective.

The present invention will be explained below with reference to Examples.

"Part" means "Part by weight".

In Examples and Comparative Examples, the fat content also includes vinyl monomer.

Example 1 1) Preparation of dispersion The following substances were added to a flask, and heated and stirred to 90 to 100° C. while blowing nitrogen gas to dissolve them well.

EAB551-02 20 parts (trade name of Eastman Chemical Company product) Butyl acetate 100 Aliphatic hydrocarbons (B, P, 120-140°C) 00 Then, the following substances were added and reacted at 100°C for 30 minutes. .

t-Butyl peroctoate 20 parts Methyl methacrylate 50 Thereafter, the following mixture was added dropwise over 3 hours.

Methyl methacrylate 300 parts 2-hydroxyethyl acrylate 90 Butyl acrylate 40 t-Butyl peroctate 10 Aliphatic hydrocarbons (B, P, 120~
After aging for 2 hours, a white viscous dispersion was obtained, and when 100 parts of aliphatic hydrocarbon was added with further stirring, a stable dispersion was obtained.

The non-volatile content was 50%.

(2) Production 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 (molar ratio) addition reaction product of tolylene diisocyanate and 2-hydroxyethyl acrylate 300 parts Hydroquinone 0.5 Butyl acetate 100 Aliphatic hydrocarbons (B,
P, 120-140°C) 200 The reaction was followed by the NC0 value, and a value of 1 or less was considered the end point.

100 parts of the unsaturated group-introduced dispersion obtained in this manner was taken, heated to 140°C, 25 parts of aliphatic hydrocarbons as a dispersion medium were distilled off while blowing air, and 25 parts of methyl methacrylate was added. A stable dispersion was obtained by stirring.

The varnish made in this way contains 3PHH benzoin and butane 20 (trade name of Hitachi Chemical Co., Ltd. product,
Butylated melamine resin (resin content: 50%) IOPHR was added and titanium white was dispersed at 100 PHR. It was painted on a polished mild steel plate to a film thickness of 307', and irradiated with a 4KW high-pressure mercury lamp at a distance of 30CIrL for 3 minutes to complete the coating. It cured quickly to give a coating film with excellent adhesion.

Example 2 (1) Preparation of dispersion The following substances were placed in a flask, heated and stirred while blowing nitrogen gas, and the temperature was raised to 90 to 100°C.

Mineral spirit 1,000 parts Nl
5SO-PB (B-3000) 500 (trade name of Nippon Soda Co., Ltd. product) Next, the following mixed solution was added dropwise over 3 hours, and then aged for 2 hours.

Acrylonitrile 170 parts Methyl methacrylate 150 2-Hydroxyethyl acrylate 60 Azobisisobutyronitrile 10 The milky white stable dispersion thus obtained had a non-volatile content of 50%.

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

N-methylol acrylamide 52 parts P-
4 Luenesulfonic acid 0.5 in about 5 hours 8.
5g of water came out.

The reaction was tracked by the amount of water released.

After the reaction was completed, 100 parts of this unsaturated group-introduced dispersion was taken,
Heat to 120℃ and add mineral spirit 3 while reducing pressure.
After removing 0 parts by distillation, ■.

A stable dispersion was obtained by adding 30 parts of 6-hexanediol diacrylate and stirring.

This varnish (resin content) was added to IPHR's benzoin ethyl ether and butane 11 (products of Hitachi Chemical Co., Ltd.,
Add 30PHR (product name, butyl urea, resin content 60φ) and further add 3PHR of carbon black, and after well dispersing it, paint it on a sanded mild steel plate to a film thickness of 20P, and heat it for 60 seconds with a 2KW high pressure mercury lamp without setting. When irradiated, it was completely cured and had excellent adhesion.

Example 3 ■) Production of dispersion stabilizer (A) The following substances were placed in a flask and heated to reflux temperature, and a condensation reaction was carried out until the acid value became 0.5 or less.

Pentaerythritol 816 parts Adipic acid
730 Toluene 15 Add 2520 parts of tall oil fatty acids and oxidize to 0 at reflux temperature as before.
．． The condensation reaction was carried out until it became 5 or less.

Next, 740 parts of phthalic anhydride and 4464 parts of an aliphatic hydrocarbon having a boiling point range of 120 to 140°C were added, heated to 80°C, and reacted until the acid value reached 48.3.

Do not heat above 80°C at this stage.

The condensate thus obtained had a nonvolatile content of 50%.

■) Production of dispersion (B) Next, put the following substances into a flask and heat at 90'C.
Heat and stir.

Condensate obtained in (A) 200 parts Normandbutane 30 Butyl acetate 13 parts Methyl acrylate 9.6 Styrene
10.0 Acrylonitrile
5.12-Hydroxyethyl acrylate 11.2 Acrylic acid 7.1
A mixture consisting of 1.5 parts of azobisin butyronitrile 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.

■) Production of unsaturated group-introduced dispersion The following substances were added to 200 parts of the above dispersion, and the mixture was heated to 90°C.
The reaction was allowed to proceed for 8 hours.

Glycidyl methyl 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.

43 parts of 2-ethylhexyl methacrylate, 100 parts of trimethylolpropane triacrylate, and 1 part of hydroquinone were added to 257 parts of the unsaturated group-introduced dispersion thus obtained, and while heating to reflux temperature (100 to 120°C), Air was blown into the dispersion medium, and 100 parts of the aliphatic hydrocarbons in the dispersion medium were almost completely distilled off.

In this way, a dispersion liquid having a nonvolatile content of almost 100φ was obtained.

To this varnish (resin content), 5PHR of 2,2'-azobisisobutyronitrile and butane 26 (manufactured by Hitachi Chemical Co., Ltd., trade name, isobutylated melamine, resin content 60%) were added to 5PHR of titanium white. A well-dispersed solution containing 100 PHR was applied to a polished mild steel plate to a film thickness of 407', and was heated at a distance of 2 cm from a distance of 30 CIn using a 4 KW high-pressure mercury lamp.
It was irradiated for minutes to obtain a cured coating film.

The coating film had excellent physical properties and solvent resistance.

Example 4 ■) Production of dispersion stabilizer (A) The following substances were placed in a flask, heated to 110°C, and stirred.

Butyl acetate 15 parts Boiling range 12
Aliphatic hydrocarbon at 0 to 140° C. 84.4 Then, the following mixture was added dropwise over 3 hours, and the reaction was further carried out for 2 hours.

Lauryl methacrylate 36.8 parts 2-ethylhexyl acrylate 36.82-hydroxyethyl acrylate 11.6 glycidyl methacrylate
14.2 Azobisisobutyronitrile 1.0 The obtained polymerization solution had a nonvolatile content of 50%.

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

120 parts of the solution obtained in (A) 40 parts of aliphatic hydrocarbon having a boiling point range of 120 to 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 23.3 parts Acrylonitrile 21.72-Hydroxyethyl acrylate 95.0 Benzoyl peroxide
2.1 The polymer solution thus obtained was a milky white emulsion with a non-volatile content of 50% and good storage stability.

■) Production of unsaturated group-introduced dispersion To 200 parts of the above dispersion, add the following compound.
The reaction was carried out at 20°C for 10 hours.

Acrylic acid 2.2 parts Triethylamine 0.01 After that, 44 parts of maleic anhydride was further added and reacted at 120°C for 3 hours to measure the total acid value and half acid value, and it was found that 95% or more of the acid anhydride groups had reacted. However, that was the end point.

Next, 64 parts of glycidyl acrylate was added, and 120 parts of glycidyl acrylate was added.
The reaction was carried out at ℃ for 10 hours.

1.6 to 310 parts of the unsaturated fatty acid dispersion thus obtained.
-1150 parts of hexafushiol dimethacrylate, 50 parts of lauryl methacrylate and 0.5 part of 2,6-ditertiary-butylhydroxytoluene were added, and 130 parts of
Dispersion medium aliphatic hydrocarbon 1 by blowing air while heating to ℃
00 parts are distilled off.

60 PHR of IPHH benzoin ethyl ether and butane 71 (manufactured by Hitachi Kakai Kogyo Co., Ltd., trade name, methylated melamine, resin content 60 φ) were added to the resulting dispersion with a nonvolatile content of 100 φ, and a 40F film was applied to a polished mild steel plate. It was applied thickly and cured by irradiating it with a 4KW high-pressure mercury lamp from a distance of 30cm for 1 minute.

Example 5 ■) Production of dispersion 120 parts of the solution obtained in ■) of Example 4 Boiling point: 20
~140 °C aliphatic hydrocarbon 140 is placed in a flask,
The mixture was heated to 90°C, and the following liquid mixture was added dropwise over 3 hours.

Styrene 42 parts Acrylonitrile 36 Glycidyl methacrylate 30.82-Hydroxyethyl methacrylate 3
1.4 benzoyl peroxide 2.1 After completion of dropping, age for 1 hour, add 5 parts of benzoyl peroxide,
Time aged.

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

■) Production of unsaturated group-introduced dispersion 9.7 parts of acrylic acid, 0.1 part of tetraethylammonium chloride, and 0.1 part of hydroquinone were added to 200 parts of this dispersion, and the mixture was reacted at 120°C for 5 hours to obtain an acid value. 1 was set as the end point.

Furthermore, 48 parts of trirenine diisocyanate and 2-hydroxyacrylate 1:1 (molar ratio) addition reaction product were added, and the reaction was continued for 1 hour, and the end point was an NC value of 1 or less.

100 parts of trimethylolpropane triacrylate, 50 parts of 2-ethylhexyl methacrylate, and 0.5 parts of hydroquinone were added to the unsaturated group-introduced dispersion medium thus obtained.
The mixture was heated to 120° C., and 50 parts of aliphatic hydrocarbons were distilled off while blowing air.

0.5 PHR of benzoin methyl ether and 100 PHR of butane 11 were added to the obtained stable dispersion, and further mixed with 10 PHR of cyanine blue. The well-dispersed mixture was applied to a polished mild steel plate to a film thickness of 30 P, and then heated for 5 minutes. After setting, use a 4KW high pressure mercury lamp at a distance of 30C.
It was irradiated with rfL for 30 seconds.

The resulting coating film was hard and had good adhesion and solvent resistance.

Example 6 ■) Production of dispersion stabilizer (4) Place the following substances in a flask and heat at 130°C to 150°C.
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 s 4.7 parts Monomethylsulfonic acid 0.3 Toluene
15.0 Then, the following substances were added and heated to 150°C, 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°C 2.1 Para-tert-butylcatechol 0.05 Dimethyl coconut amine 0.2 The resulting condensation adduct has a vinyl-terminated polymer 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, heated to 110°C, and stirred.

Acetate amyl ester 33.6 parts Boiling range 1
Aliphatic hydrocarbon at 60-180°C 00 Next, the substances shown below were added dropwise into the flask (B) over a period of 3 hours, and the reaction was continued for an additional 2 hours.

Condensate adduct obtained in (A) 117 parts Glycidyl methacrylate 113.6 Azobisisobutyronitrile 1.0 The obtained polymer solution was pale brown and had a nonvolatile content of 50%.

(2) Preparation of dispersion The following materials were placed in a flask and heated to 80°C and stirred.

100 parts of the polymer solution obtained in (B) of Example 6 (■) Aliphatic hydrocarbon (B, P, 160-180°C) 16 Next, the following mixture was dropped thereon over 3 hours, and further 2 The reaction continued for hours.

Butyl methacrylate 40 parts Acrylonitrile 20 Styrene
402-hydroxyethyl acrylate 1
5 Azobisisobutyronitrile 1.5 parts The obtained polymer solution was a milky white dispersion with good storage stability.

The non-volatile content was 50%.

(2) Preparation of unsaturated group-introduced dispersion 15 parts of acrylic acid was added to 200 parts of the above dispersion and reacted at 130°C for 4 hours.

Thereafter, 0.5 part of P-)luenesulfonic acid was added, and the temperature was raised to 150°C and the reaction was continued for 8 hours.

The end point was an acid value of 1 or less.

1.8g of water was distilled out. To 200 parts of the unsaturated group-introduced dispersion thus obtained, 50 parts of 1.6-hexanediol diacrylate and 0.1 part of hydroquinone were added,
The mixture was heated to 100° C. and 50 parts of aliphatic hydrocarbons as a dispersion medium were distilled off under reduced pressure of 30+utHg.

To the resin content of the stable dispersion obtained, 0.5 PHR of benzyl and 200 PHR of Kneepan 208E (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd., butylated melamine, resin content 50%) were added to a polished mild steel plate. Painted to a film thickness of
After setting at room temperature for 5 minutes, light was irradiated for 3 minutes from a distance of 30 CrIl using a 4KW high-pressure mercury lamp.

The coating film was cured and had excellent solvent resistance and water resistance.

Example 7 (1) Production of dispersion stabilizer The substances shown below were placed in a flask, heated to 80°C, and stirred.

Polymer solution obtained in Example 6 II)-(B) 100
Part normal octane 116■) Preparation of a dispersion Next, the following mixture was added dropwise over 3 hours, and the reaction was continued for a further 3 hours.

Butyl methacrylate 50 parts Acrylonitrile 25 Styrene 40 Benzoyl peroxide 2 This was a stable milky white liquid with a non-volatile content of 50%.

■) Production of unsaturated group-introduced dispersion 4.3 parts of methacrylic acid and 0.1 part of hydroquinone are added to 200 parts of the above dispersion, and the reaction is carried out at the reflux temperature of octane, and the end point of the reaction is an acid value of 1 or less. did.

50 parts of ethylene glycol dimethacrylate and 0.1 part of hydroquinone were added to 200 parts of the unsaturated resin dispersion thus obtained, and 70 parts of normal octane was distilled out while blowing air under the boiling point of normal octane. Upon removal, a stable dispersion was obtained.

To this were added 2 PHR of benzoin based on the resin content, 150 PHR of Kneepan 9l-55 (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name, benzoguanamine, resin content 55%), and 50 PHR of titanium white, and the mixture was well dispersed.

This was coated on a polished mild steel plate to a film thickness of 50P, and 4 KV
v' When irradiated for 60 seconds with a high-pressure mercury lamp, it was completely cured and had excellent adhesion.

Comparative Example 1 The following substances were placed in a flask, heated to 110°C, and stirred.

200 parts of the solution obtained in (A) of (■) of Example 3, aliphatic hydrocarbon having a boiling point range of 120 to 140°C, 0 butyl acetate, 13 then the following mixture was added dropwise into the flask over 3 hours, The reaction was continued for an additional 2 hours.

Butyl methacrylate 10 parts styrene
15 Acrylonitrile
15 glycidyl methacrylate
10 The product thus obtained was milky white and had a very high viscosity (more than 100 Stokes, 25°C), making it impossible to measure.

Also, when this product was applied, lumps appeared on the entire surface, and it did not dissolve in solvents (dimethyl ketone and other good solvents), and particulate gel was observed.

This is thought to be because an ester addition reaction between the carboxyl group contained in the dispersion stabilizer and the glycidyl group of glycidyl methacrylate also occurred at the same time, resulting in gelation.

Comparative Example 2 A sample was prepared using the same formulation as in Example 1 (■) except that 20 butane was added.

This product was applied to a polished mild steel plate to a film thickness of 6CI, and after setting, it was irradiated with a 4KW high-pressure mercury lamp at a distance of 30crIL for 3 minutes, but the surface remained sticky and did not harden.

Comparative Example 3 Example 7I [I] without adding Kneepan 91-55 was painted on a polished mild steel plate to a film thickness of 50P, and 4K
When irradiated with a W high-pressure mercury lamp from a distance of 30 m for 60 seconds, the inside did not harden at all and some distortion occurred.

Claims (1)

[Claims] 1(I) Vinyl monomers are dissolved in an organic liquid in which the polymer formed from the monomer is not dissolved, in the presence of a dispersion stabilizer soluble in the organic liquid. A stable dispersion of a vinyl polymer obtained by polymerizing a vinyl monomer and dispersing the polymer in the organic liquid, wherein the dispersion stabilizer and/or the vinyl polymer contain hydroxyl groups, carboxyl groups, etc. , carboxylic anhydride group,
Epoxy group, methylol group, alkoxymethylol group,
A polymerizable vinyl monomer containing one or more functional groups of incyanate group, amide group, amino group, and chlorine group and having addition or condensation reactivity with the functional group is added to the dispersion liquid. After production, a dispersion mainly composed of a dispersion obtained by reaction is produced, and a part or all of the organic liquid from the after-milled dispersion is replaced with one or more vinyl monomers. An unsaturated resin dispersion composition comprising: (n) an amino resin; and (1) a photosensitizer.