JPS6044516A - Non-aqueous dispersion type resin composition - Google Patents

Abstract

PURPOSE:To obtain titled composition capable of giving coating film free from yellowing with excellent transparency, hardness and stain resistance, by copolymerization, in a solvent, of an unsaturated monomer mixture containing monomer carrying specific functional group in the presence of a specific solvent- soluble vinyl resin stabilizer. CONSTITUTION:The objective composition can be obtained by copolymerization, in the presence of (A) 30-80wt% of a solvent-soluble vinyl resin stabilizer prepared by copolymerization between (i) an alpha,beta-monoethylenic unsaturated carboxylic acid hydroxyalkyl ester (e.g., 2-hydroxyethyl acrylate) and (ii) another unsaturated monomer (pref. lauryl acrylate), of (B) 70-20wt% of a mixture consisting of (iii) an N-alkoxymethylated unsaturated carboxylic acid amide (e.g., N-methoxymethyl acrylamide) and (iv) another unsaturated monomer (e.g., acrylic acid) in an aliphatic hydrocarbon solvent dissolvable for the monomers (i)-(iv) but indissolvable for the copolymer from the components (iii) and (iv).

Description

[Detailed description of the invention] The present invention relates to a non-aqueous dispersion type resin composition.

More specifically, the present invention relates to a non-aqueous dispersion type resin composition comprising a dispersion of a vinyl polymer in a non-aqueous solvent.

In recent years, there has been an increasing demand for resource saving and pollution-free technology in the paint field as well.

In particular, solid-type paints, which contain less solvent and have a high concentration of solids in their compositions, are preferred as resource-saving paints because they can be used with conventional paint manufacturing methods or painting equipment. It seems to be used in

Furthermore, in consideration of measures to regulate the use of solvents due to air pollution problems, ordinary solid-type paints that use large amounts of aromatic or ester solvents do not seem to be industrially preferable.

Unfortunately, in view of the stricter regulations on the use of solvents in recent years, non-pollution in a broad sense, and resource conservation, non-aqueous dispersion paints that use aliphatic hydrocarbon solvents as their main solvents have been proposed. However, conventionally known non-aqueous dispersion type compositions of this glaze include combinations of "dispersion stabilizer/dispersion particles", such as decomposed natural rubber/acrylic resin, acrylic resin/acrylic resin, and oil. Modified alkyd resin/acrylic resin,
Non-aqueous dispersion type resin compositions consisting of a combination of polybutadiene/acrylic resin, etc., have a tendency of decreasing compatibility between the dispersion stabilizer component (solvating component) and the dispersion particle component (produced polymer) due to the difference in polarity between the two. Therefore, the coating film obtained from the composition lacks transparency, and therefore tends to have poor gloss and luster.

In this way, when a non-aqueous dispersion type resin composition containing the above combination as a color vehicle is used for paint purposes, it is not suitable for exterior use and is often used mainly for interior use. It is.

In order to obtain an excellent cured coating film, the color vehicle is made of amine formaldehyde resin, blocked isocyanate, epoxy resin, methoxymethylated acrylamide tsukuda etc. Use together with curing agent. These are blended when making a paint, but during long-term storage, the functional groups in the non-aqueous dispersion and the functional groups in the curing agent gradually react, resulting in a thickened composition. ,
It was often observed that precipitation occurred due to aggregation.

As a result of intensive studies to improve the above-mentioned drawbacks, the present inventors discovered that a specific functional group (N-alkoxymethyl group) that crosslinks with the functional group (hydroxyl group) in the dispersed particle component was used as a component of the dispersion stabilizer. By containing it, it has transparency (
As a result, they discovered that a cured coating film with an excellent finished appearance, hardness, and stain resistance could be obtained.
However, as a result of further studies, the present inventor has found that by introducing a hydroxyl group that crosslinks with the N-alkoxymethyl group in the dispersed particle component as a component of the dispersion stabilizer, It has been discovered that a non-aqueous dispersion type resin composition having coating film performance equivalent to that of the present invention can be obtained, and the present invention has been achieved.

That is, in the present invention, monomers (1) to (V) are dissolved, but monomer (IiU
,! : (V) In an aliphatic hydrocarbon bath medium in which the vinyl copolymer obtained from ) Said (1
) Solvent-soluble vinyl resin stabilizer obtained by copolymerizing with α, β-monoethylenically unsaturated monomers other than
- In the presence of 30 to go% by weight, 011) an N-alkoxymethylated monomer of an α,β-monoethylenically unsaturated carboxylic acid amide, and 4V) an α,β-monoethylenic monomer other than the above 011) A monomer mixture consisting of an unsaturated monomer...
...Relates to a non-aqueous dispersion type resin composition of a vinyl polymer obtained by copolymerizing 70 to 2[theta]%.

The aliphatic hydrocarbon solvent used in the present invention exhibits the following characteristics. That is, α, which will be described later,
β-monoethylenic monomers (1), (i+), Tsukuda) and (V) are soluble, but the copolymer obtained from the monomers C11) and 1■ is not soluble. be.

Specifically, for example, aliphatic hydrocarbons such as hexane, hegetane, octane, cyclohexane, cycloheptane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and mixtures containing mineral spirits, aliphatic naphtha, etc. as main components are used. Can be mentioned.

Generally speaking, the solvent-soluble vinyl resin used as the dispersion stabilizer of the present invention is composed of (1) α,β-7noenoenoethylenically unsaturated carboxylic acid loxyalkyl The ester monomer (11) is obtained by copolymerizing with an α,β-monoethylenically unsaturated monomer other than the above (1).

In this specification, the term "solvent soluble" refers to a compound that is soluble or partially soluble in the aliphatic hydrocarbon solvent.
means. Similarly, the term "solubilized in a solvent" refers to dissolving or partially dissolving in such a solvent.

Therefore, the above (1) hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated carboxylic acid is added to the monomer mixture C ( 1) + (ID) Medium 3~lSM
% by weight, preferably from 5 to 70% by weight.

When the component is 3 M fA:% or less within the above range, α is used as a component of the dispersed particles described below.

The crosslinking reaction of the β-monoethylenically unsaturated carboxylic acid amide with the N-alkoxymethylated monomer component tends to be insufficient, and as a result, the solvent resistance of the resulting coating film tends to decrease. Furthermore, if the content exceeds 15% by weight, it is not preferable because it becomes difficult to solubilize in aliphatic hydrocarbon solvents.

Specific examples of this Yuzu jIl citrus fruit (1) include suhydroxyethyl (meth)acrylate, co-hydroxyglobil (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and co-hydroxybutyl (meth)acrylate.
Acrylate, 3-hydroxybutyl (meth)acrylate, terhydroxybutyl (meth)acrylate, S
-Hydroxypentyl (meth)acrylate, -Hydroxyhexyl (meth)acrylate, Neopentyl dalicol mono(meth)acrylate, 3-butoxy-2
-Hydroxypropyl (meth)acrylate, co-hydroxy-7-phenylethyl (meth)acrylate, polyglopylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, etc., which can be used singly or as a mixture of two or more. May be used as

The component (1) is α used as a component of the dispersed particles,
β-monoethylenically unsaturated cal? This is essential for the crosslinking reaction between the N-alkoxymethylated single resistant component Q11) of the acid amide. Further, in order to make the cured coating film obtained from the composition of the present invention transparent, it is essential that the G11l DM component is present in the composition at the same time.

The component (11) used in the present invention, namely the above (1)
) other than α,β-monoethylenically unsaturated mononucleotides (11)
As long as the solvent-soluble vinyl resin as a dispersion stabilizer is solubilized in the aliphatic hydrocarbon solvent,
Any monomer can be used.

In addition, in specific examples, α, β-monoethylenic monomers represented by the general formula CH2” C-C00CoH2o+ 1 (wherein R is H or CH, and n represents an integer of 6 to /g) It is preferable to use a portion of the monomer.This monomer is particularly preferable because it solubilizes the dispersion stabilizer in the solvent.

Monomers having such a specific general formula are α.

β-monoethylenically unsaturated monomer mixture ((1) + (l
i)) Use at a ratio of 20 to 20 to 50%. In the above range, if the amount is less than the lower limit of 20M amount%,
This is not preferable since the effect of improving the solubility of the dispersion stabilizer in the solvent tends to decrease.

-10,000, if the upper limit of gOMft% is greater than the hardness,
It is also unfavorable because it shows a tendency for coating film performance such as impact resistance to deteriorate.

Specific examples include coethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (
meth)acrylate, dodecyl(meth)acrylate,
Examples include esters such as stearyl (meth)acrylate. These can be used alone or as a mixture of two or more.

porcelain, the α,β-monoethylenically unsaturated single resistant mixture (
(1) +(it):l is any other monomer other than the hydroxyalkyl ester monomer of the α,β-monoethylenically unsaturated carboxylic acid and the monomer represented by the general formula (Component (iii)) is added to the monomer mixture [(11
+ (If)) in a range of 5 to 77% by weight.

Specific examples of such monomers include α- and β-monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
Monoethylenically unsaturated carboxylic acids; methyl (meth)azilylate, ethyl (meth)acrylate, n-globil (meth)acrylate, isogucobyl (meth)acrylate, n-butyl (meth)acrylate, 5ee-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, N, N'-
Dialkyl esters of fumaric acid such as dimethylaminoethyl (meth)acrylate, dalicidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, di-butyl fumarate, styrene, vinyltoluene, α-methylstyrene, Examples include monomers such as (meth)acrylonitrile and vinyl acetate. These may be used alone or as a mixture of two or more.

The other IJA polymer (H component) is an α,β-monoethylenically unsaturated local compound containing an N-alkoxymethyl group. It is preferable to exclude the use of N-alkoxymethylated monomers of Nune amide, since this makes it difficult for the dispersion stabilizer to dissolve in the solvent and also causes bacteria to increase viscosity.

The solvent-soluble vinyl resin as a dispersion stabilizer of the present invention is
Manufactured by normal solution polymerization method. For example, single;:
The remaining monomer (mixture) and a polymerization initiator are dropped into a mixture of a part of the monomer (mixture) and a combined solvent, and the monomer ( A method in which a mixture (mixture) and a polymerization initiator are added dropwise and polymerized is applicable.

In any case, the present invention is not intended to be limited to a specific solvent polymerization method.

The solvent used in this solution polymerization method is the aliphatic hydrocarbon solvent described above. Moreover, as a polymerization initiator, for example,
Pennzoilno! -oxide, 1-butylperbenzoate, t-butylperoxybenzoate, t-butylperoxyoctoate, lauroyl peroxide, and other organic peroxides, or azo compounds such as azobisisobutyronitrile. Further, these polymerization initiators may be used alone or in an appropriate mixture of two or more.

In the present invention, if necessary, a chain transfer agent such as dodecylmercagutan, coethylhexyl thioglycolic acid, and soybean chloride may be used to adjust the molecular weight.

In the present invention, in the presence of vinyl resin as a dispersion stabilizer dissolved (or partially dissolved) in the aliphatic hydrocarbon obtained as described above, A mixture of N-alkoxymethylated monomer of cardenic acid amide (IiD Tosono et al. +7) and α,β-monoethylenically unsaturated monomer -■ is copolymerized to produce a "vinyl non-aqueous solvent dispersion". The purpose is to obtain.

The non-aqueous solvent dispersion of the above-mentioned vinyl-based monomer is composed of α,β-7noenoenoethylenically unsaturated carboxylic acid loxyalkyl ester monomer contained in the dispersion stabilizer, that is, (1
) component in the dispersed particles to react (self-crosslink) with the component.
- It is necessary to contain an alkoxymethyl group. Therefore, N-alkoxymethylated monomer 01υ of α,β-monoethylenically unsaturated cargonamide is used as one component in the RL polymer mixture ((iil) + (φ)).

By the way, the polymer ((()) has strong polarity.Therefore, a comonomer containing this monomer as one component cannot be dissolved in an aliphatic hydrocarbon-purple solvent, thus forming dispersed particles. It is suitable for

The N-alkoxymethylated monomer of α, β-monoethylenically unsaturated carboxylic acid amide is α.

β-monoethylenically unsaturated monomer mixture ((iil)
+lψ] Middle 5-30T1. Amount %, preferably dg-,25
Use within a weight range of 1%.

In the above weight range, when the monomer is less than 5% by weight, α used as a component in the dispersion stabilizer,
This is preferred because the crosslinking reaction of the hydroxyalkyl ester component color of the β-monoethylenically unsaturated carboxylic acid is insufficient, and the solvent resistance of the resulting coating film is therefore low. On the other hand, if it is used in an amount exceeding 30% by weight, it is not preferable because it causes gluing during the reaction.

Specific examples of the component 611) include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)
Acrylamide, N-n-glopoxymethyl (meth)acrylamide, N-isogropoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, N-8Qe-ethoxymethyl (meth)acrylamide, N- - N-alkoxymethylated products of α,β-monoethylenically unsaturated carboxylic acid amides such as butoxymethyl (meth)acrylamide and N-isoethoxymethyl (meth)acrylamide; or their N-methylolated products, etc. Can be mentioned.

These may be used alone or as a mixture of two or more.

In addition, monomers other than the N-alkoxymethylated monomer of the α,β-monoethylenically unsaturated carboxylic acid amide used for copolymerization in the presence of a dispersion stabilizer, that is, (V ) component is 70 to 9,1-f in the monomer mixture
It is used within the range of fifEt%.

Specific examples of Form II (V) include α, β such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, etc.
-Monoethylenically unsaturated carbon rIli; methyl (
meth)acrylate, ethyl(meth)acrylate), n
- f lovir (meth)acrylate, f noglovir (meth)acrylate, n-butyl (meth)acrylate,
5ee-(meth)acrylate, t-butyl(meth)acrylate, isobutyl(meth)acrylate, n-hexyl(meth)azilylate, ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, Tridecyl (meth)
Acrylate, alkyl esters of acrylic acid or methacrylic acid such as stearyl (meth)acrylate; other N,N'-dimethylaminoether (meth)acrylate, dalicidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate , dialkyl esters of fumaric acid such as diptyl fumarate, styrene, vinyltoluene,
Examples include α-methylstyrene, (meth)acrylonitrile, and vinyl acetate. 2 The above monomers may be used alone or in a suitable combination of two or more, depending on the purpose and use of the coating composition.

However, as the monomer 4φ, it is better to avoid using a hydroxyargyl ester monomer of α,β-monoethylenically unsaturated orocarboxylic acid because it causes thickening during the production of dispersed particles.

The non-aqueous solvent dispersion of the vinyl polymer is a monomer mixture of the monomers 4 (Oil) and (V) in the presence of 30 to 30% by weight of a solvent-soluble vinyl resin as a dispersion stabilizer.
Obtained by copolymerizing 201%. In the above range 1,
When the amount is less than 30% by weight, it becomes difficult to obtain a stable non-aqueous solvent dispersion. On the other hand, if the amount of gO exceeds the amount of superposition, it becomes difficult to obtain a non-aqueous solvent dispersion, which is also not preferable.

The copolymerization temperature is determined by the type of polymerization initiator and polymerization solvent used. It is usually carried out at a temperature between about 50°C and 200°C, and a range between about 60°C and 1SO"CI7') is particularly suitable.

Moreover, as the heavy-@ initiator, the organic peroxides or azo compounds shown above are preferably used.

Similarly, in order to adjust the molecular weight, the chain transfer agent shown above can also be used.

In the thus obtained non-aqueous solvent dispersion of the vinyl polymer of the present invention, monomers each having a specific functional group are introduced, although the polarities of the dispersion stabilizer and the dispersed particles are different. This makes it possible to form a coating film with excellent transparency. Similarly, the non-aqueous dispersion type resin composition of the present invention includes:
Known catalysts for promoting crosslinking reactions (self-crosslinking), as well as epoxy resins and cellulose resins, if necessary.

It is also possible to use one or more types of coating film-forming resins such as polyester resins, alkyd resins, amino resins, and blocked isocyanate compounds.

Further, in addition to the organic solvent contained in each component, the composition of the present invention may further contain an organic solvent, if necessary, to an extent that does not impair the stability of the composition.

As such an organic solvent, the same organic solvent as the organic solvent contained in each component or a different one may be used.

Examples of such organic solvents include hydrocarbon solvents such as hegetane, octane, mineral spirits, toluene, and xylene, alcohol solvents such as propyl alcohol and citanol, ester solvents such as ethyl acetate and butyl acetate, acetone, and methyl ethyl ketone. ketone solvent,
Organic solvents such as alcohol esters and ether esters may not be used, as long as they do not impair the stability of the non-aqueous dispersion.
There are no particular restrictions on the type of solvent. In addition, 1"t of the non-aqueous dispersion type resin composition of the present invention, if necessary, inorganic or organic coloring pigments, metal powder pigments such as aluminum flakes, extender pigments, and additives normally used in paints are added. and can be used.

As a method for coating the non-aqueous dispersion type resin composition of the present invention, various known coating methods can be used, such as brush coating, spray coating, electrostatic coating, curtain flow coating, shower coating, and roll coating.

Furthermore, it is also possible to apply the paint by heating it (30 to 20°C), such as by using hot spray.

In addition, the non-aqueous dispersion type resin composition of the present invention can be formed into a film by simply evaporating the solvent after coating (so-called drying at room temperature).
In order to obtain a coating film with high performance, it is preferable to heat cure the coating film. The heat curing conditions vary depending on the content of crosslinkable functional groups in the composition, film thickness, etc.
Normal 60~. A cured coating film can be obtained by heat treatment for about 70 to 170 minutes at an appropriate temperature in the temperature range of 200°C.

The cured coating film thus obtained has excellent transparency, no yellowing, and exhibits excellent properties such as hardness and stain resistance.

The present invention will be explained below using specific examples.

Similarly, ``bu'' or ``section'' refers to ``juryu section'' or ``jubin section.''

[Method for producing vinyl resin dispersion stabilizer]

txt 700 parts of mineral spirit was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, and the temperature was raised to 9 parts°C. Then, the following monomer and initiator mixture was added dropwise over 3 hours.

Isobutyl methacrylate coro, 5 parts, -1 ethylhexyl methacrylate) 7 parts, styrene 3 parts, 2-ethylhexyl acrylate dog 3 parts, co-hydroxyzorobyl methacrylate/2 parts, methacrylic acid 7.5 parts, 2.3 parts of azobisisobutyronitrile.

After the dropwise addition was completed, 2 parts of azobisisobutyronitrile was added, and the reaction was further carried out at the same reaction temperature for 3 hours. Thus,
Acid value: 6, hydroxyl value: 6, weight average molecular weight: 39.90
0. and a resin solution with a non-volatile content lI of 9.7% was obtained,
The viscosity was 27.9 Stokes/20°C. This was designated as AO-7.

(2) Into a reaction vessel in the same manner as when AO-/ was synthesized above.

After adding 700 parts of mineral spirit and raising the temperature to 90°C, the following monomer and initiator mixture was added dropwise over 3 hours.

1 part of isobutyl methacrylate, 3 parts of euhydroxyethyl methacrylate, 7 theta parts of -1 ethylhexyl methacrylate, 1 part of methacrylic acid, 1 part of benzoyl peroxide J, S.

After completion of dropping, add penzoylno 4-oxide 1. The reaction was further carried out for S hours at the same reaction temperature, resulting in an acid value of 7.9, a hydroxyl value of 3S, and a weight average molecular weight! ;0,10
A resin solution of θ and non-volatile content Sθ,/H was obtained. The viscosity is 37. /Stokespoise/, 2θ°C. This was designated as AO-U.

(3) In a reaction vessel similar to that in which AO-/ was synthesized,
Add 700 parts of mineral spirit and raise the temperature to 2. 9θ℃
After that, the following monomer and initiator mixture was added dropwise over 3 hours.

Part S of methyl methacrylate, 37 parts of inbutyl methacrylate, 173 parts of ethylhexyl acrylate, 6 parts of styrene, 6 parts of non-hydroxyethyl methacrylate, 1 part of acrylic acid, 2 parts of benzoyl peroxide.

After the dropwise addition was completed, 0.2 part of benzoyl/'P-oxide was added and the reaction was further carried out at the same temperature for S hours to give an acid value of 9. θ
, hydroxyl value, 2, weight average molecular weight lI, ? ,4t0
0. A resin solution with a non-volatile content of 9.9 was obtained.

The viscosity was 27.0 strokes at 720°C. This was designated as AO-3.

(4) In the same manner as in the synthesis of AO-/, in the reaction vessel,
After adding 700 parts of mineral spirit and raising the temperature to 90°C, the following monomer and initiator mixture was added dropwise over 3 hours.

Methyl methacrylate Otsu part, -1-ethylhexyl acrylate 33 parts, styrene 70 parts, ethylhexyl methacrylate 77 parts, inbutyl methacrylate, 20 parts
parts, 10 parts of dihydroxyethyl acrylate, 2 parts of methacrylic acid, and 422.3 parts of benzoyl peroxa.

After the dropwise addition, 7.2 parts of benzoyl peroxide was added and the reaction was further carried out for S hours at the same reaction temperature, resulting in an acid value of /11
．． A resin solution was obtained with a hydroxyl value of l19, a weight average molecular weight of S, 9θ0, and a non-volatile content of 4t9.9. The viscosity was 29.5 strokes/2θ°C. This was designated as AO-da.

Example / After stirring, 9 g parts of mineral spirit and a dispersion stabilizer (AO
-/), and the temperature was raised to 5° C., and then the following monomer and initiator mixture was added dropwise over 3 hours.

Methyl methacrylate) 11.3*j” parts, styrene 30
parts, ethyl acrylate) + parts, N-n-butoxymethylacrylamide 70 parts, inbutyl methacrylate 77 parts
part, methacrylic acid/part, lIl, benzoyl peroxide part, azobisin butyronitrile/part.

After the dropwise addition was completed, a portion of benzoyl peroxide was added, and the reaction was further carried out at the same reaction temperature for S hours.

The reaction product is a milky white dispersion with an acid value of //, θ, and a hydroxyl value of 2.
3.3. and non-volatile content was 119.7%. This was closed OD-/.

Example 2 into a reaction vessel similar to that in which OD-/ was synthesized.

Mine, Ral Spirits) 99 parts, dispersion stabilizer (AO-3)
, 2'A/part and after raising the temperature to 9θ°C.

The following monomer and initiator mixture was added dropwise over 3 hours.

30 parts of methyl methacrylate, 5 parts of isobutyl methacrylate, 39 parts of styrene, butyl acrylate), ti,
, 5 parts of 2-ethylhexyl methacrylate, 1 part of methacrylic acid, 73 parts of N=n-butoxymethylacrylamide, part s of penzoyloxide, 0.5 part of azobisisobutyronitrile.

After the dropwise addition was completed, 7.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same temperature for S hours.

The reaction product is a milky white dispersion with acid values g, s and hydroxyl value lS.
1 and the nonvolatile content was 49.5%.

This was designated as OD-1.

Example 3 In a reaction vessel similar to that in which 00-/ was synthesized.

100 parts of mineral spirit, dispersion stabilizer (AO-2)
After adding 300 parts and raising the temperature to 90° C., the following monomer and initiator mixture was added dropwise over 3 hours.

Methyl methacrylate 3 Hirobe, inbutyl methacrylate
, ) / A; one part, 35 parts of styrene, 3 parts of coethyl-hexyl acrylate, 272 parts of N-n-cytoxymethylacrylamide, 7 parts of methacrylic acid, 3 parts of benzoyl peroxide.

After the dropwise addition was completed, 1.2 parts of benzoyl A-oxide was added, and the reaction was further carried out at the same reaction temperature for 3 hours. The reaction product was a milky-white dispersion with an acid value, a hydroxyl value of 2/2, and a non-volatile content of 1I9, 5qI). This is 0D-
It was set as 3.

In the production of the above-mentioned 0D-3, a dispersion stabilizer (AO-co) was used as an example.
The reaction was carried out in the same manner except that 1,700 parts of the sample was used. The reaction product was a milky white dispersion with an acid value of 23, a hydroxyl value of 23, and a non-volatile content of Sθ, θ. This was designated as OD-da.

Example 3 In a reaction vessel similar to that in which 00-/ was synthesized.

Mineral spirit 99 parts 5 dispersion stabilizer (AO-4t)
, 3, and the temperature was raised to 9D°C, the following monomer and initiator mixture was added dropwise over 3 hours.

31 parts of methyl methacrylate, 35 parts of styrene, 7.2 parts of inbutyl methacrylate, 7.2 parts of ethyl acrylate, 70 parts of Nt-butoxymethylacrylamide, and 3 parts of penzoylno-4-oxide.

After the dropwise addition was completed, a portion of benzoyl/'P-oxide/ was added, and the reaction was further carried out at the same reaction temperature for S hours. The reaction product was a milky white dispersion with an acid value of 9.3, a hydroxyl value of 31, and a non-volatile content of 11t, q, lI. Set this to 0
It was set as 0-5.

Comparative Example/In Example S, 99 parts of mineral spirit was added to 5
The reaction was carried out in the same manner except that Nt-butoxymethylacrylamide, which was a dispersed particle component, was replaced with 9 parts. The reaction product is a milky white dispersion with acid value/θ,
B, hydroxyl value 32 and non-volatile content is Da 9. He was on the left. This was designated as OD-B.

Comparative Example 1 In Example 1, 9g portion of mineral spirit was added to 1
To 31 parts, add 202 parts of dispersion stabilizer (AO-/) to acid value l/
, to 767 parts of a soybean oil-modified alkyd resin solution of hydroxyl value lθ/, oil length 3θ and non-volatile fraction θ, 70 parts of N-n-butoxymethylacrylamide to IO parts of co-hydroxyethyl methacrylate, and 3 parts of benzoyl peroxide. The reaction was carried out in the same manner except that each part was replaced with 1 part of azobisisobutyronitrile and 1 part of azobisisobutyronitrile was removed.

The reaction product is a milky white dispersion with an acid value of ii, o, a hydroxyl value of wolfberry, and a nonvolatile content of lI9. A.He was arrogant. Set this to 0
It was designated as D-7.

The non-aqueous dispersion resin compositions of the present invention (OD-/~S) and comparative examples (OD-4~7) obtained as described above were applied to a polished mild steel plate (θ1g x RiOx/!rO recommendation). The film thickness is 3θ~3
Air spray paint to a thickness of 3 microns, and apply 2 coats at room temperature.
After being left for D minutes, it was heated and dried at 760° C. for 20 minutes. Table 1 shows the results of the coating film performance comparison test of the obtained test pieces.

JP-A-Sho GO-44516 (9) (Note 1) Visual judgment O Transparent × Opaque (Note 2) Visual judgment ○ No yellowing × Yellowing (Note 3) Mitsubishi Pencil Unl
, apply it to the paint film at an angle of 11.1 degrees, and press lightly forward.

The hardness of the pencil does not leave any traces due to the coating.

(Note) Gopan order chishibakuri test (Note, S-) Based on Erichsen testing machine.

(Note 6) JIS-ni-! rllOθ, Otsu, /3
．． Based on the 3B method.

(Note 7) The painted surface was contaminated using magic ink [trade name: Teranishi Kagaku ■] red, blue, and black, and after being left at room temperature for 2 hours, it was wiped off with methanol to determine the degree of contamination. .

○ Hardly contaminated.

△　Contaminated.

× Significantly contaminated.

(Note g) Each non-aqueous dispersion type resin composition (however, in the comparative example, it was mixed with melamine resin) was kept in a constant temperature bath at 5θ°C, and sedimentation of 5 particles, phase separation, or significant increase in viscosity occurred. Indicates the number of days until a change is seen.

The results of the comparative test clearly show that the coating film obtained from the non-aqueous dispersion type resin composition of the present invention has excellent transparency, no yellowing, and extremely excellent hardness and stain resistance. The storage stability was also very good.

Claims (3)

[Claims] (1) Monomers (1) to 4ψ dissolve, but monomer C1
In an aliphatic hydrocarbon solvent in which the vinyl copolymer obtained from 1) and Rei is insoluble, (1) a hydroxyalkyl ester derivative of α,β-monoethylenically unsaturated acarboxylic acid; (++) Above (1)
Solvent-soluble vinyl resin stabilizer obtained by copolymerizing with other α,β-monoethylenically unsaturated monomers...
...In the presence of 30 ~ go heavy image%, (fil) α, β
- an N-alkoxymethylated monomer of monoethylenically unsaturated carboxylic acid amide, and (■) α other than the above 011),
A non-aqueous dispersion resin composition of a vinyl polymer obtained by copolymerizing 70 to 20% by mass of a mixture of ammonium and β-monoethylenically unsaturated monomer. thing. (2) Solvent-soluble vinyl resin stabilizers are (a) α, β
-Hydroxyalkyl ester monomer of monoethylenically unsaturated carboxylic acid 3 to 15% by weight (b) General formula % formula % (wherein R is H or CH, n is 6 α,β-monoethylenically unsaturated monomer represented by (representing an integer of ~1g)...
......20-10 double fire, and (c) α, β-monoethylenically unsaturated monomer other than the above (a) and (b) ......5 to The non-aqueous dispersion type resin composition according to claim (1), which is a copolymer obtained from 7'111L%. (3) α, β-monoethylenically unsaturated monomers represented by the general formula %, coethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate Claim No. 21 (non-aqueous dispersion type resin composition according to claim 21), which is at least one compound selected from acrylate and stearyl (meth)acrylate. N-alkoxymethylated monomer of acid amide and α, β-monoethylenically unsaturated monomer other than 4φ OiD,
The former 6M is 3-30% by weight, while the latter 6M is 70-qS
The non-aqueous dispersion type resin composition according to claim 1, which is a 4L polymer mixture in the proportion of M amount %.