JPS6281461A - Non-aqueous dispersion type resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Industrial applications 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.

BACKGROUND OF THE INVENTION In recent years, the demand for resource saving and pollution-free technology has increased greatly even in the paint field.

In particular, high-solid paints, which are resource-saving coatings with low solvent content and high solid content, have the advantage that conventional paint manufacturing methods or painting equipment can be used as is. , seems to be suitably used.

In addition, considering measures to regulate the use of solvents due to air pollution problems, conventional high-solid paints that use large amounts of aromatic and ester solvents do not seem to be industrially desirable.

Furthermore, from the viewpoint of regulations on the use of solvents that have been tightened in recent years, non-pollution in a broad sense, and resource conservation, non-aqueous dispersible paints and non-aqueous dispersible compositions using aliphatic hydrocarbon solvents as the main solvent are being developed. Various manufacturing methods have also been proposed.

For example, Japanese Patent Publication No. 47-19404 and Japanese Unexamined Patent Publication No. 5
No. 2-138584, in which an ethylene-vinyl ester copolymer is used as a dispersion stabilizer, and an α,β-monoethylenically unsaturated monomer is polymerized in the presence of the dispersion stabilizer, thereby producing a stable non-aqueous dispersion type. It is proposed to obtain a resin composition.

However, these compositions tend to form pseudo-gels during low-temperature storage, and they do not contain ethylene, which is used as a stabilizer.
The amount of vinyl ester copolymer is 3 to 4 per polymer particle.
There was a problem that a stable dispersion liquid could not be obtained if the amount was less than % by weight.

Furthermore, the present inventors proposed a non-aqueous dispersion type resin composition containing an N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide (Japanese Patent Application Laid-open No. 1983-1973-1).
127344). In this composition, in order to obtain a stable dispersion composition, stabilizer/polymer particles = 30 to 80/
It was 70-20 (weight ratio). In other words, in order to obtain a stable dispersion silk composition, a stable removal amount of at least 30% is required, so the composition is made into a paint with a high pigment concentration and the resulting composition is applied by brushing onto the coating. When brushing, uneven brushing (uneven gloss) may occur.

Problems to be Solved by the Invention The inventors of the present invention have made intensive studies to improve the above-mentioned drawbacks, and as a result, the present inventors have developed a method that uses a specific functional group that crosslinks with the functional group in the dispersed particle component as a component of the dispersion stabilizer. By polymerizing the vinyl type monomer in the presence of a stabilizer obtained by reacting a small amount of ethylene-vinyl acetate copolymer, it is stable even during high-temperature storage or low-temperature storage. It was discovered that a composition with good properties and no brush unevenness could be obtained, and the present invention was achieved.

Means for Solving the Problems The present invention is characterized in that monomers (i) to (iv) are dissolved in each of the monomers (i) to (iv), but the vinyl copolymer obtained from (1) monomer (iii) and V) is not dissolved in fat. In a group hydrocarbon solvent, (A) i
) N of α,β-monoethylenically unsaturated carboxylic acid amide
- A monomer mixture consisting of an alkoxymethylated monomer and (ii) an α,β-monoethylenically unsaturated monomer other than the above (i) (hereinafter referred to as MA): 99 to 90% by weight , ethylene-vinyl acetate copolymer...1~
10% by weight, and the content of the ethylene-vinyl acetate copolymer in the final non-aqueous dispersion type resin composition is 0.2% by weight.
(B) (iii) α,β-monoethylenically unsaturated carboxylic acid in the presence of 15 to 35% by weight of a solvent-soluble vinyl resin dispersion stabilizer obtained by reacting to a concentration of ~2.0% by weight. A single hydroxyalkyl ester of (
iv) A monomer mixture (hereinafter referred to as (M8
)) A non-aqueous dispersion type resin composition of a vinyl polymer obtained by copolymerizing 85 to 65% by weight of the vinyl polymer.

The "aliphatic hydrocarbon solvent" used in the present invention has the following characteristics. That is, the α,β-monoethylenically unsaturated monomers (i) and (ii) described below
), (iii) and (iv) are soluble, but the copolymer obtained from the monomers (iii) and (iv) is not.

Specifically, examples thereof include aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, cycloheptane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and mixtures containing mineral spirits, aliphatic naphtha, etc. as main components. It will be done.

Broadly speaking, the [solvent-soluble vinyl resin dispersion stabilizer] used as the dispersion stabilizer of the present invention is, in the aliphatic hydrocarbon solvent, (i) α, β-monoethylenically unsaturated carbon N-alkoxymethylated monomer of acid amide, (・ii) the above (
α, β-monoethylenically unsaturated monomers other than i) and (
v) It is obtained by polymerizing with an ethylene-vinyl ester copolymer.

In this specification, the term "solvent soluble" refers to the property of being dissolved or partially dissolved in the aliphatic hydrocarbon solvent.

In the present invention, (i) the N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide is
In the monomer mixture ((i) + (ii) or MA), 5
It is preferable to react in a proportion of ~30% by weight, preferably 8-25% by weight. In the above range, the component is 5
When the composition of the present invention is used as a thermosetting composition, α, β-
The crosslinking reaction between the monoethylenically unsaturated carboxylic acid and the hydroxyalkyl ester component becomes insufficient, and the solvent resistance of the coating film tends to decrease. In addition, during the polymerization reaction process during the production of non-aqueous dispersion type resin compositions, the chemical bonding reaction between the α,β-monoethylenically unsaturated carboxylic acid and the hydroxyalkyl ester component in the dispersed particle component becomes poor, resulting in a stable dispersion. It becomes difficult to obtain the composition. On the other hand, if it exceeds 30% by weight, gelation occurs in the polymerization reaction step during the production of a stable dispersion, which is undesirable.

Specific examples of the component (1) include N-methoxymethyl (
meth) acrylamide, N-ethyloxymethyl (meth)
Acrylamide, N-n-propoxymethyl (meth)acrylamide, N--isopropoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, N-3ec-butoxymethyl (meth)acrylamide, N-t- α,β-monoethylenically unsaturated saturated carboxylic acid amide-alkoxymethylated products such as butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide; or these N-
Examples include methylol compounds.

These may be used alone or as a mixture of two layers 1-.

The component (i) is α, β,
- It causes a chemical bonding reaction with the hydroxyalkyl ester component of monoethylene saturated carboxylic acid, and is indispensable for obtaining a stable dispersion composition.

Furthermore, when the composition of the present invention is used as a thermosetting composition, the hydroxyalkyl ester component (iii) of an α,β-monoethylenically unsaturated carboxylic acid used as one component of the dispersed particles is also used as described above. It is necessary for the crosslinking reaction.

Next, the component (ii) used in the present invention, that is, the α,β-monoethylenically unsaturated monomer i) other than the above (i), is a solvent-soluble vinyl resin as a dispersion stabilizer. can be used in any weight form as long as it is soluble or semi-soluble in the aliphatic hydrocarbon solvent.

In addition, in specific examples, α, β, β-monoethylene mer represented by the general formula % (wherein R is 1 or CIf3, and n is an integer from 6 to 18) is used in part. It is preferable.

This monomer is particularly preferred because it renders the dispersion stabilizer soluble or semi-soluble in the solvent.

91 which has such a specific general formula
β-Monoethylene 1/2 inorganic saturated substrate mixture ((i)
+(ii): Used in a proportion of 5 to 90% by weight in MA). In the above range, if it is less than the lower limit of 5% by weight, the effect of improving the solubility of the dispersion stabilizer in the solvent tends to decrease, which is not preferable. on the other hand,"
- If the content exceeds the limit of 90% by weight, it is similarly undesirable because coating film performance such as hardness and impact resistance tends to deteriorate.

Specific examples include 2-ethylhexyl (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 types.

In addition, the α,β-monoethylenically unsaturated monomer mixture (
(i>+(ii):MA) is the above α, β, β
- Other monomers (component (c)) other than the N-alkoxymethylated monomer of monoethylene saturated carboxylic acid amide and the monomer represented by the above general formula are added to the monomer mixture ((
In i) + (ii) 3, it can be used in an amount ranging from 5 to 90% 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.
Frequently monoethylenically unsaturated carboxylic acids; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 5ec-butyl (meth)acrylate , t-butyl (meth)acrylate, isobutyl (meth)acrylate, N, N'
-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl.

Examples include dialkyl esters of fumaric acid such as (meth)acrylate, phenyl methacrylate, benzyl methacrylate, and di-butyl fumarate, and monomers such as styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate. . These may be used alone or as a mixture of two types.

The ethylene-vinyl acetate copolymer (v) used in the synthesis of the solvent-soluble vinyl resin dispersion stabilizer in the present invention is preferably one that is soluble or semi-soluble in the aliphatic hydrocarbon solvent at room temperature.

Specifically, an ethylene-vinyl acetate ester copolymer containing 30 to 50% by weight of vinyl acetate is particularly preferred. The ethylene-vinyl acetate copolymer is a monomer mixture (M,
) in the range of 1 to 10% by weight relative to 99 to 90% of heavy needles, and in the final non-aqueous dispersion resin composition of 0.2 to 2.
Use at a ratio that gives 0% overlapping.

In the above range, if it is less than the lower limit of 0.2% by weight, the effect of improving varnish stability and brush unevenness tends to decrease, which is not preferable. On the other hand, if the content exceeds the upper limit of 2% by weight, it is similarly undesirable because it tends to cause aggregation (regel) when stored at low temperatures and tends to reduce the stability of the varnish during low temperature storage.

Any ethylene-vinyl acetate copolymer can be used as long as it is soluble or semi-soluble in the aliphatic hydrocarbon solvent at room temperature. Specific examples of the components include: Mitsui-DuPont Polychemical Co., Ltd.'s product names: Evaflex 150, 40, and 40 ), RB-1
) etc.

The solvent-soluble vinyl resin dispersion stabilizer of the present invention is produced by a conventional solution polymerization method.

For example, a method in which the remaining monomer (mixture) and a polymerization initiator are dropped into a mixture of a part of the monomer (mixture) and a polymerization solvent, and then polymerized, or A method in which a polymerization initiator is dropped and polymerized is applicable.

On the other hand, the ethylene-vinyl acetate t i polymer can be produced by mixing the ethylene-vinyl acetate t i in a polymerization solvent in advance, and adding the monomer (mixture) and a polymerization initiator dropwise to polymerize the mixture, or by pre-mixing the ethylene-vinyl acetate t i in a part of the polymerization solvent. A dissolved vinyl acetate copolymer may be used by mixing it with the polymer (mixture).

In any case, the present invention is not intended to be limited to a particular method, such as a solution polymerization method.

As the solvent used in this solution polymerization method, the aliphatic hydrocarbon solvent mentioned above is used. Examples of the polymerization initiator include benzoyl peroxide, t-butylverhenzoate, t-butylperoxybenzoate,
Organic peroxides such as t-butyl peroxyoctoate and lauroyl peroxide, or azo compounds such as azobisisobutyronitrile are used. Further, these polymerization initiators may be used alone or in combination of two or more.

In the present invention, if necessary, a chain transfer agent such as dodecylmelfcaptan, thioglycol M-2-ethylhexyl, carbon tetrachloride, etc. may be used to adjust the molecular weight.

In the present invention, in the presence of a vinyl resin as a dispersion stabilizer dissolved (or partially dissolved) in the aliphatic hydrocarbon solvent obtained as described above, A mixture of a hydroxyalkyl ester monomer (iii) of a saturated carboxylic acid and another α,β-monoethylenically unsaturated monomer (iv) is copolymerized to obtain a non-aqueous dispersion type of vinyl polymer. The purpose is to obtain a resin composition].

The above non-aqueous solvent dispersion of the vinyl polymer contains an N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide contained in the above-mentioned dispersion stabilizer, that is, (i) In order to chemically bond and react with the components, it is necessary to contain hydroxyl groups in the dispersed particles. Therefore, as a component in the monomer mixture ((iii) + (iv) or Ms), the hydroxyalkyl ester monomer (i
ii) Use wo.

By the way, the monomer (iii) has strong polarity. Therefore, a copolymer containing this monomer as one component is difficult to dissolve in an aliphatic hydrocarbon solvent, and is therefore suitable for forming dispersed particles.

Incidentally, such monomers are used in α-, β-
in monoethylenically unsaturated monomer mixture (Ma), 3 to 3
Use within the range of 0% by weight.

[Incidentally, 1. The monohydroxyl value of the non-aqueous solvent dispersion of the vinyl polymer" refers to the hydroxyl group value in the dispersed particles (i.e., the copolymer of monomer (ii) and monomer (iv)). The total value of the dispersion stabilizer component and the hydroxyl value of the dispersion stabilizer component. ] In the above weight ratio range, when the tti-ii compound is 3% or less, when the composition of the present invention is used as a thermosetting composition, the reaction process with the crosslinkable dose substance (i) This is not preferable because the crosslinking density becomes low and the solvent resistance of the coating film becomes low. In addition, when producing a non-aqueous dispersion type resin composition of vinyl polymer, especially during the polymerization reaction process, the crosslinkable monomer (1
) is undesirable because the chemical bonding reaction with the dispersion composition becomes poor and the stability of the final dispersion composition obtained is therefore reduced.

On the other hand, if the amount exceeds 30% by weight, the non-aqueous solvent dispersion of the vinyl polymer will have a high viscosity, which will impede workability. In addition, the crosslinking density of the coating film after the thermosetting reaction becomes too high, which tends to reduce the flexibility, water resistance, etc. of the coating film, which is also undesirable.

Specific examples of this type of monomer (iii) used in the present invention include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (
meth)acrylate, 5-hydroxypentyl(meth)
Acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono (meth)acrylate, 3-but-1-xy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol Mono (meth)acrylate, glycerin mono (meth)
Examples include acrylates, and these may be used alone or as a mixture of two or more.

In addition, in the presence of a solvent-soluble vinyl resin dispersion stabilizer, the above-mentioned (iii) α, β-
The quasi-mercury other than the hydroxyalkyl ester of monoethylenically unsaturated carboxylic acid, that is, the component (iv), is used in an amount of 70 to 97% by weight in the monomer mixture (MB).

Specific examples of the monomer (iv) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, etc.
, β-monoethylenically unsaturated carboxylic acids; methyl (meth)acrylate, ethyl (meth)acrylate, n-
Propyl (meth)acrylate, isopropyl (meth)
Acrylate, n-butyl (meth)acrylate, se
c, -(meth)acrylate, t-butyl(meth)acrylate, isbutyl(meth)acrylate, n-hexyl(meth)acrylate, 2-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'-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, Hensyl Examples include dialkyl esters of fumaric acid such as methacrylate and dibutyl fumarate, styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate.

The above monomers may be used depending on the purpose and use of the coating composition.
You may use one species or a combination of two or more as appropriate.

Furthermore, polyfunctional unsaturated monomers may be used in an amount of 5% or less in the monomer mixture (Ml 2 ). Specific examples of the monomer include divinylbenzene, bis(meth)acrylogine ethyl phosphate, trimethylolpropane tri(
Examples include meth)acrylates, and these may be used alone or as a mixture of two or more.

In the present invention, the non-aqueous solvent dispersion of the vinyl polymer is composed of the monomers (iii) and (iv) in the presence of 15 to 35% of a solvent-soluble vinyl resin as a dispersion stabilizer. It is obtained by copolymerizing a monomer mixture (Mg) of 85 to 65 mt@%. In the above range, if the amount is less than 15% by weight, it becomes difficult to obtain a stable (final target product, non-aqueous solvent dispersion). On the other hand, if the amount exceeds 35% by weight, the unevenness of the brush after applying the N1 composition (unevenness)
This is undesirable because it tends to be low.

The copolymerization temperature is determined by the type of polymerization initiator and polymerization solvent used. im usually about 50℃~200℃
The temperature is preferably between about 60°C and 150°C.

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

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

The non-aqueous solvent dispersion of the vinyl polymer of the present invention thus obtained has good stability even during high-temperature storage or low-temperature storage, and has good brushability.

Blue, when used as a thermosetting composition, the non-aqueous dispersion resin composition of the present invention may optionally contain a known catalyst for promoting crosslinking reaction (self-crosslinking), as well as epoxy resin, cellulose resin, etc. It is also possible to use one or more types of coating film-forming resins such as resins, polyester resins, alkyd resins, amino resins, and blocked isocyanate compounds.

Furthermore, 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.

Such organic solvents include hydrocarbon solvents such as heptane, octane, mineral spirits, toluene, and nitosylene, alcohol solvents such as propyl alcohol and butanol, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, etc. Organic solvents such as ketone solvents, alcohol esters, and ether esters are used, and there is no particular restriction on the type of solvent as long as it does not impair the stability of the non-aqueous dispersion.

In addition, the non-aqueous dispersion type resin composition of the present invention may optionally contain inorganic or organic coloring pigments, metal powder pigments such as aluminum flakes, extender pigments, and additives normally used in paints. can be used.

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

Furthermore, heat the paint using hot spray (30~60℃)
It is also possible to paint it at a temperature of

As described above, the non-aqueous dispersion type resin composition of the present invention is particularly characterized by drying at room temperature, in which the solvent is simply evaporated after coating, and good coating film performance can be obtained, but even more advanced performance is required. In order to obtain a coating film having the following properties, it is heated and cured. The conditions for heat curing vary depending on the content of crosslinkable functional groups in the composition, film thickness, etc., but the heat treatment is usually carried out at a temperature of about 60 to 200° C. for about 10 to 40 minutes.

Effects of the invention The non-aqueous dispersion type resin composition obtained as a result of carrying out the present invention is as follows:
It exhibits excellent varnish stability during high-temperature storage or low-temperature storage, and excellent coating film appearance (brush unevenness).

The present invention will be explained below using specific examples.

In addition, "part" or "%" represents "weight part" or "weight %."

[Method for manufacturing vinyl resin dispersion stabilizer]

(1) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, place an ethylene-vinyl acetate copolymer [Ultracene #750 (vinyl acetate copolymer 32%
) ; Toyo Soda Kogyo ■ Manufacturer's name: 4 parts Mineral Spirito l
-163 parts were added and the temperature was raised to 80°C. Then, the following monomer and initiator mixture was added dropwise over 3 hours.

20 parts of isobutyl methacrylate, butyl methacrylate
1-17 parts, 2-ethylhexyl methacrylate 20 parts, styrene 10 parts, 2-ethylhexyl acrylate 2
5 parts, 1'8 parts of N-1-oxymethylacrylamide,
2 parts of benzoyl peroxide, 1.5 parts of arabisisobutyronitrile.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added and the reaction was continued for an additional 4 hours at the same reaction temperature. Thus, the weight average molecular weight is 47,500, and the non-volatile content is 38.
．． A 1% resin solution was obtained with a viscosity of 7.3 stix/
The temperature was 20°C. Hereinafter, this will be referred to as XA-1.

(2) In the same reaction vessel as in the synthesis of XA-1, add ethylene-vinyl acetate copolymer [Ultracene #
760 (vinyl acetate content: 42%)] and 165 parts of mineral spirit were added, and the temperature was raised to 80° C., and then the following monomer and initiator mixture was added dropwise over 3 hours.

29 parts of butyl methacrylate, 30 parts of isobutyl methacrylate, 30 parts of 2-ethylhexyl acrylate, N
-10 parts of n-butoxymethylacrylamide, 1 part of methacrylic acid, 9413.5 parts of benzoyl peroxide.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction temperature was raised to 90°C.

The reaction was then carried out for an additional 4 hours, resulting in an acid value of 7.1, a weight average molecular weight of 51,300, and a non-volatile content of 37.7%.
A resin solution was obtained. Viscosity is 6.2 stix/20
It was ℃. This is called XA-2.

(3) In a reaction vessel similar to that in which XA-1 was synthesized, add ethylene-vinyl acetate copolymer Ultracene #760 (
Vinyl acetate content: 42%)], 32 parts of toluene, and 129 parts of mineral spirit were added, and the temperature was raised to 80°C, and then the following monomer and initiator mixture was added dropwise over 3 hours.

80 parts of 2-ethylhexyl acrylate, 20 parts of Nn-butoxymethylacrylamide, 2.5 parts of benzoyl peroxide, and 1 part of azobisisobutyronitrile.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction temperature was raised to 90°C.

Next, the reaction was further carried out for 4 hours, and the weight average molecular weight was 36,
200 and a non-volatile content of 38.8%. The viscosity was 1.7 Stix/20°C. Hereinafter, this will be referred to as XA-3.

(4) In a reaction vessel similar to that in which XA-1 was synthesized, ethylene-vinyl acetate copolymer [Ultracene #760 (
After adding 25 parts of toluene and 141 parts of mineral spirit, and raising the temperature to 80° C., the following monomer and initiator mixture was added dropwise over 3 hours.

55 parts of 2-ethylhexyl acrylate, 5 parts of styrene, 24 parts of butyl methacrylate, 15 parts of N-n-butoxymethylacrylamide, 1.0 part of acrylic acid, and 3.5 parts of hensyl peroxide.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction temperature was raised to 90°C.

Next, the reaction was further carried out for 4 hours to obtain a resin solution having an acid value of 7.9, a weight average molecular weight of 39,800, and a non-volatile content of 37.3%. Viscosity is 2.9 Stix/20℃
Met. Hereinafter, this will be referred to as XA-4.

(5) In the production of XA-2, ethylene-vinyl acetate copolymer (1' flutracene #760) and N-n
-The reaction was carried out in the same manner except that 165 parts of mineral spirit was replaced with 141 parts, and 3.5 parts of benzoyl peroxide was replaced with 2.5 parts of benzoyl peroxide, and the acid value was 7.6. ,
Weight average molecular weight 25,500 and non-volatile content 37.3
% resin solution was obtained. Viscosity is 2.2 Stokes/2
It was 0°C. Hereinafter, this will be referred to as XA-5.

(6) In the production of XA-2, the reaction was carried out in the same manner except that the ethylene-vinyl acetate copolymer Ultracene #760 was omitted and 165 parts of mineral spirit was replaced with 157 parts, and the acid value was 742. , a weighted average molecular weight of 48,800, and a nonvolatile content of 37.5%. The viscosity was 5°8 Stix/20°C.

Hereinafter, this will be referred to as XA-6.

(7) In the production of XA-4, °ζ, ethylene-
6 parts of vinyl acetate copolymer (Ultracene #760) to 1
The reaction was carried out in the same manner except that 141 parts of mineral spirit was replaced with 147 parts, and the weight average molecule was 1
A resin solution of 42.100% and a non-volatile content of 37.7% was obtained. The viscosity was 3.2 Stix/20°C. Hereinafter, this will be referred to as XA-7.

Example 1 Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, 77 parts of mineral spirit and a partitioning stabilizer (XA
-1) After adding 3 parts of 1) and raising the temperature to 85°C, the following monomer and initiator mixture was added dropwise over 3 hours.

32 parts of methyl methacrylate, 22 parts of vinyl acetate, 35 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 1 part of methacrylic acid, 2.5 parts of benzoyl peroxide.

After the dropwise addition, 1.2 parts of benzoyl peroxide was added and the reaction was continued for another 6 hours at the same reaction temperature.

The reaction product was a milky white dispersion with a hydroxyl value of 31 and a nonvolatile content of 48.9%. Hereinafter, this will be referred to as PD-1.

Example 2 88 parts of mineral spirit and 66 parts of dispersion stabilizer (XA-2) were placed in a reaction vessel similar to that in which PD-1 was synthesized, and after raising the temperature to 85°C, the following monomers and The initiator mixture was added dropwise over 3 hours.

28 parts of butyl methacrylate, 3 parts of methyl methacrylate
8 parts, butyl acrylate 25 parts, 2-hydroxypropyl methacrylate 8 parts, methacrylic #1 part, benzoyl peroxide 2 parts, azobisisobutyronitrile 1 part
Department.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same temperature for 5 hours.

The reaction product was a milky white dispersion with a hydroxyl value of 25 and a nonvolatile content of 49.6%. Hereinafter, this will be referred to as PI)-2.

Example 3 88 parts of mineral spirit and 66 parts of dispersion stabilizer (XA-2) were placed in a reaction vessel similar to that in which PD-1 was synthesized, and after raising the temperature to 85°C, the following monomers and The initiator mixture was added dropwise over 3 hours.

25 parts of methyl methacrylate, 18 parts of vinyl acetate, 10 parts of styrene, 35 parts of butyl acrylate, 12 parts of 2-hydroxyethyl methacrylate, 2.5 parts of benzoyl peroxide, 1.0 part of azobisisobutyronitrile.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same reaction temperature for 6 hours. The reaction product is a milky white dispersion with a hydroxyl value of 42 and a non-volatile content of 48.
．． It was 8%. Hereinafter, this will be referred to as PD-3.

Example 4 78 parts of mineral spirit and 0 parts of dispersion stabilizer (XA-3) were placed in a reaction vessel similar to that in which PD-1 was synthesized, and after raising the temperature to 85°C, the following monomers were added. The body and initiator mixture was added dropwise over a period of 3 hours.

44 parts of methyl methacrylate, isobutyl methacrylate
1-10 parts, 30 parts of ethyl acrylate, 15 parts of 2-hydroxypropyl methacrylate, 1 part of acrylic acid, 1.5 parts of benzoyl peroxide.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same reaction temperature for 5 hours.

The reaction product was a milky white dispersion with a hydroxyl value of 46 and a non-volatile content of 49.8%. Hereinafter, this will be referred to as PD-4.

Example 5 80 parts of mineral spirit and 89 parts of dispersion stabilizer (X/-4) were placed in a reaction vessel similar to that in which Pr)-1 was synthesized, and after raising the temperature to 85°C, the following monomers were added. The body and initiator mixture was added dropwise over a period of 3 hours.

22 parts of methyl methacrylate, 8 parts of styrene, 8 parts of butyl acrylate, 30 parts of ethyl acrylate, 1.17 parts of 2-hydroxypropyl methacrylate, 15 parts of vinyl acetate, and 1.5 parts of benzoyl peroxide.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same reaction temperature for 6 hours.

The reaction product was a milky white dispersion with a hydroxyl value of 50 and a nonvolatile content of 48.8%. Hereinafter, this will be referred to as l) D-5.

Comparative Example 1 In Example 2, 66 parts of the dispersion stabilizer (XA-2) was replaced with ethylene-vinyl acetate copolymer (Ultracene #7).
60) Add 1.88 parts of Mineral Spirito to 2.1 parts to 10 parts.
4 parts, 2 parts of benzoyl peroxide and 1 part of azobisisobutyronitrile were added to 1 part of azobisisobutyronitrile.
．． Reactions were carried out in the same manner except that part 7 was used. As a result, a polymer precipitated on the liquid interface from about 40 minutes after the start of dropping, and after 60 minutes, a considerable amount of what appeared to be polymer crystals had adhered to the stirring rod. Dripping start 90
After a few minutes, we stopped adding the monomer and checked the inside of the system.
It was found that the polymer was agglomerated and a stable dispersion composition could not be obtained.

Hereinafter, this will be referred to as PI)-6.

Comparative Example 2 The reaction was carried out in the same manner as in Example 5 except that 89 parts of the dispersion stabilizer (XA-4) was replaced with 88 parts of (XA-7). The reaction product was a milky white dispersion with a hydroxyl value of 50 and a nonvolatile content of 48.3%.

Hereinafter, this will be referred to as Pr)-7.

Comparative Example 3 In Example 4, dispersion stabilizer (XA-3) 1) 0
The reaction was carried out in the same manner except that 172 parts of mineral spirit, 64 parts of mineral spirit and 1.5 parts of benzoyl peroxide were replaced. The reaction product was a milky white dispersion with a hydroxyl value of 39 and a non-volatile content of 49.7%.

Hereinafter, this will be referred to as PD-8.

Comparative Example 4 The reaction was carried out in the same manner as in Example 2 except that 66 parts of the dispersion stabilizer (XA-2) was replaced with 67 parts of (XA-6). The reaction product was a milky white dispersion with a hydroxyl value of 25 and a nonvolatile content of 49.3%. Hereinafter, this will be referred to as PD-9.

Comparative Example 5 In Example 2, 66 parts of the dispersion stabilizer (XA-2) was replaced with 67 parts of (XA-5), 2 parts of hensyl peroxide and 1 part of azobisisobutyronitrile were replaced with 1.5 parts of benzoyl peroxide. The reaction was carried out in the same manner except that the parts were changed.

The reaction product was a milky white dispersion with a hydroxyl value of 25 and a non-volatile content of 49.5%.

Hereinafter, this will be referred to as PI)-jO.

Comparative Example 6 In Example 4, 78 parts of mineral spirit was added to 1
) 7 parts, dispersion stabilizer (XA-3) 1) 0 parts, acid value 1), hydroxyl value 101, oil length 30% and non-volatile content 60
The reaction was carried out in the same manner except that 71.5 parts of the soybean oil-modified alkyd resin solution was used in each case. The reaction product is a milky white dispersion with a hydroxyl value of 75 and a non-volatile content of 50.
．． It was 0%.

Hereinafter, this will be referred to as PD-1).

Non-aqueous dispersion type resin compositions (1) D-1 to 5) of the present invention obtained as described above and comparative compositions (PD-7 to 1)
) was made into a paint as follows.

54 parts of non-aqueous dispersion type resin composition, 20 parts of titanium dioxide,
6 parts of talc, 10 parts of precipitated barium sulfate, 4 parts of white carbon, and 12 parts of mineral spirit were added, and after kneading and dispersing for 30 minutes in a paint shaker (1500 rpm), 8 parts of mineral spirit was further added, and the mixture was stirred and mixed. It was used as a trial paint.

Apply each paint prepared in each Example and Comparative Example to a slate board (3 x 70 x 150 mm) with a brush, 2g/sheet, twice in a rotating motion, with an interval of 2 hours), at room temperature. It was dried for 7 days.

*mSho 62-814G1 (13) In addition, the non-aqueous dispersion type resin compositions (Pr)-1 and -2) of the present invention used in Examples-1 and -2 were made into paints as follows.

28 parts of titanium dioxide and 8 parts of mineral spirit were added to 70 parts of a non-aqueous dispersion type resin composition, and after kneading and dispersing for 30 minutes in a paint shaker (1,500 rpm), 7 parts of mineral spirit was further added, and the mixture was stirred and mixed. It was used as a trial paint.

Polish each of the above-adjusted paints on a mild steel plate (0.8 x 70 x 15
The film was air-sprayed to a dry film thickness of 30 to 35 μm (0 mm), left at room temperature for 20 minutes, and then heated and dried at 160° C. for 20 minutes. Table 3 shows the results of the coating film performance test of the obtained test pieces.

Table 3 Performance test results (Note 7) Using Mitsubishi Pencil Uni, 45° to the paint film.
Apply the pencil at an angle of , then press lightly forward to ensure that the pencil is hard enough to leave no traces of the pencil on the paint film.

(Note 8) Based on Erichsen testing machine.

(Note 9) JIS-5400, 6, 13, 3B
By law.

(Note 10) The painted surface was contaminated using magic ink [trade name: Teranishi Kagaku Co., Ltd.] red, blue, and black, and after being left at room temperature for 24 hours, it was wiped off with methanol to determine the degree of contamination.

O Almost no pollution.

Δ　Contaminated.

× Significantly contaminated.

From the above comparative test results, the non-aqueous dispersion type resin composition of the present invention has excellent varnish stability during high-temperature storage or low-temperature storage, and the coating films obtained from them have
Excellent coating film appearance (brush unevenness) and non-adhesive properties.
It was also found to have excellent water resistance and alkalinity resistance.

Claims (5)

[Claims] (1) Monomers (i) to (iv) dissolve, but monomer (
In an aliphatic hydrocarbon solvent in which the vinyl copolymer obtained from iii) and (iv) is not dissolved, (A) (i) an N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide and (ii) a monomer mixture (M_A) consisting of 99 to 90% by weight of an α,β-monoethylenically unsaturated monomer other than the above (i), and (v) ethylene. - Vinyl acetate copolymer: 1 to 10% by weight, and the ethylene-vinyl acetate copolymer is contained in the final non-aqueous dispersion resin composition. (B)(
iii) a hydroxyalkyl ester monomer of an α,β-monoethylenically unsaturated carboxylic acid; and (iv) a monomer consisting of an α,β-monoethylenically unsaturated monomer other than the above (iii). Mixture (M_B) 85
A non-aqueous dispersion type resin composition of a vinyl polymer obtained by copolymerizing ~65% by weight. (2) The non-aqueous dispersion type resin composition according to claim (1), wherein the content of vinyl acetate in the ethylene-vinyl acetate ester copolymer is 30 to 50% by weight. (3) The α,β-monoethylenically unsaturated monomer mixture (M_A) in the solvent-soluble vinyl resin dispersion stabilizer is (a) N-alkoxymethyl of α,β-monoethylenically unsaturated carboxylic acid amide Chemical monomer: 5 to 30% by weight (b) Represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is H or CH_3, and n is an integer from 6 to 18) α,β-monoethylenically unsaturated monomer...
-5 to 90% by weight, and (c) α,β-monoethylenically unsaturated monomers other than (a) and (b) above...5 to 90% by weight. Claim No. 1
) The non-aqueous dispersion type resin composition described in item 2. (4) The α,β-monoethylenically unsaturated monomer represented by the general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ is 2
- At least one compound selected from ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate and stearyl (meth)acrylate. The non-aqueous dispersion type resin composition described in (3). (5) (iii) a hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated carboxylic acid; and (iv)
The α,β-monoethylenically unsaturated monomer other than the above (iii) is 3 to 30% by weight of the former (iii), and the latter (
The non-aqueous dispersion type resin composition according to claim 1, wherein iv) is a monomer mixture in a proportion of 70 to 97% by weight.