JPS6055013A - Nonaqueous resin dispersion composition - Google Patents

Abstract

PURPOSE:The titled resin composition excellent in the transparency, hardness, stain resistance, etc., of a paint film, obtained by polymerizing an N-alkoxymethyl group-containing monomer, etc., in the presence of a specified, hydroxyl group-containing dispersion stabilizer in an aliphatic hydrocarbon solvent. CONSTITUTION:The purpose nonaqueous resin dispersion composition is prepared by polymerizing 70-20wt% mixture comprising 75-97wt% monomer mixture containing an N-alkoxy-methylated alpha,beta-monoethylenically unsaturated carboxylic acid amide and 25-3wt% vinyl ester obtained from an epoxy compound and an unsaturated monocarboxylic acid in an aliphatic hydrocarbon solvent which can dissolve the above monomers but does not dissolve a vinyl ester-modified vinyl copolymer (e.g., hexane) in the presence of 30-80wt% solvent-soluble vinyl resin dispersion stabilizer containing, as a constituent, a hydroxyalkyl ester of an alpha,beta-monoethylenically unsaturated carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous dispersible resin composition. Fourth, in detail, the present invention relates to a thermosetting non-aqueous dispersion resin composition j comprising a non-aqueous solvent dispersion of a vinyl ester-modified vinyl polymer.

In recent years, demands for reducing poverty and eliminating pollution have rapidly increased in the paint field as well.

Above all, resource saving/G! High-solid type paints, which have a reduced solvent content in the composition and a high degree of solid content, are suitable for use as I paints because of the advantage that the conventional Coating #4 manufacturing method or painting equipment can be used as is. It seems that it has been done.

In addition, in recent years, air pollution has increased to 11. Considering measures to regulate the use of solvents due to the FJ issue, ordinary high-solid paints that use aromatic and ester solvents1
It seems that stuttering is common in industry.

Furthermore, in view of the recently tightened regulations on the use of solvents, non-pollution in a broad sense, and resource conservation, non-aqueous dispersion paints using aliphatic hydrocarbon solvents as the main solvent have been proposed.

However, conventionally known combinations of dispersion stabilizer/dispersed particles as this type of non-aqueous dispersion type compositions, such as decomposed natural rubber/acrylic tree +1, acrylic resin/
Coating films obtained from thermosetting non-aqueous dispersion paints using acrylic resins, oil-modified alkyd resins/acrylic resins, polybutadiene/acrylic resins, etc. as color vehicles generally do not always have sufficient physical properties. . For example, a flexible coating film may have insufficient hardness, and conversely, a hard coating film may have insufficient flexibility. I couldn't find it. In addition,
It was not always possible to obtain sufficient surface properties in terms of salt spray resistance, moisture resistance, water resistance, and secondary physical properties after each test.

In addition, in a non-aqueous dispersion type resin composition using the above combination as a vehicle, the compatibility between the dispersion stabilizer component (solvated component) and the dispersed particle component (produced polymer) is limited due to the difference in polarity between the two. Therefore, the coating film obtained from the composition has item 4, which is that the coating film obtained from the composition lacks transparency and has reduced gloss, luster, etc.

For this reason, when a non-aqueous dispersion type resin composition containing the above-mentioned combination as a color vehicle is used as a color vehicle, it is considered to be unsuitable for exterior applications, and has been mainly used for interior applications.

In addition, in order to obtain an excellent cured coating film, the color vehicle may contain amino formaldehyde resin, blocked isocyanate compound, epoxy resin, methoxymethylated acrylic resin, etc., in order to react with the functional groups in the color vehicle. A curing agent such as the following is used in combination.

These are added when making a mackerel 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 the composition becoming thicker. It was often observed that precipitation occurred due to aggregation.

In order to improve the above-mentioned defects of the known technology, the present inventors have developed a specific functional group that cross-links with the functional group (hydroxyl group) in the dispersed particle component as a component of the dispersion stabilizer. By containing (N-alkoxymethyl group), it has transparency, excellent finished appearance, and hardness of 1.
We discovered that a cured coating film with excellent needle stain resistance could be obtained and filed a patent application.

As a result of further studies, the present inventors found that by including a functional group (hydroxyl group) that crosslinks with the functional group (N-alkoxymethyl group) in the dispersed particle component as a component of the dispersion stabilizer, It was discovered that a cured coating film having performance equivalent to that of the previous application could be obtained, and the present invention was achieved.

That is, the present invention provides a vinyl ester-modified vinyl copolymer obtained from a vinyl ester, a monomer (iiD) and a monomer (1), in which monomers (1) to (1) are dissolved. (ii) α,β-monoethylene other than the above (i) Solvent-soluble vinyl resin dispersion stabilizer obtained by copolymerizing with unsaturated vesicles 30 to 80
(iii) an N-alkoxymethylated monomer of α1β-monoethylenically unsaturated carboxylic acid amide and (iv) the aforementioned 0
i1) A mixture of 75 to 97 complexes consisting of a monoethylenically unsaturated β-monoethylenyl compound other than i1), (a) an epoxy compound having one or more epoxy groups in the molecule;
b) Mixture of vinyl ester obtained from unsaturated monocarboxylic acid with 3 to 25 weight percent...@70 to
The present invention relates to a non-aqueous dispersion type resin composition of a vinyl ester renal vinyl polymer obtained by polymerizing 2ON.

The solvent used in the water treatment, ie, the above-mentioned "aliphatic hydrocarbon solvent" has the following characteristics.

In other words, in the a, β-monoethylenic monocapsule described later, (
11), (iii), and (1v) are soluble, but the "vinyl ester-modified vinyl copolymer" obtained from the monomer (iii), (!V), and the hyacinthyl ester is not soluble.

Specifically, for example, hexane, hebutane, octane, cyclohexane, cycloheptane, methylcyclohexane,
Examples include aliphatic hydrocarbons such as ethylcyclohexane and dimethylcyclohexane, their compositions, mineral spirits, and mixtures containing aliphatic naphtha as a product.

Generally speaking, the above-mentioned "solvent-soluble vinyl resin dispersion stabilizer" used as the dispersion stabilizer of the present invention includes (i) a, β-7noethylenically unsaturated in an aliphatic hydrocarbon solvent. It is obtained by polymerizing a hydroxyalkyl ester monomer of carbonic acid and (ii) an α,β-monoethylenically unsaturated vesicle other than the above (i).

In this specification, the term ``solvent soluble I'' refers to the above-mentioned 1
The property of being soluble or partially soluble in aliphatic hydrocarbon solvents.

Among the above, the hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated carboxylic acid is mixed into a pressure monomer mixture [core (′i1 )], it is preferable to react at a ratio of 3 to 15 weight 1i1q6, preferably 5 to 10 weight %. In the above range, if the component is less than 3 times, the dispersion particle component described below will be expanded and the N-alkoxymethylation of β-monoethylenic nonvesicular carzeneamide will be combined with one N-alkoxymethylated compound. The crosslinking reaction becomes insufficient and the solvent resistance of the coating film tends to decrease. On the other hand, if it exceeds 15%, the solvent solubility of the stabilizer decreases, which is not preferable.

The systems of this type of stoichiometry (1) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. , 5-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-cytoxy -2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, etc. It may be used as a mixture of more than one species.

In this component, α, β-
It is necessary for the crosslinking reaction of the monoethylenically unsaturated vesicle lunamide with the N-alkoxymethylated monomer component (iii), and it also makes the cured coating obtained from the composition of the present invention transparent. Said (i) in the composition in order to have
ii) It is essential that it be present at the same time as the component. In the present invention, the α,β-monoethylenically unsaturated monomer (11) other than the above (1) may be used as a dispersion stabilizer. Any monomer can be used as long as it dissolves or partially dissolves the vinyl resin in the aliphatic hydrocarbon solvent.

In addition, in particular, the α,β-monoethylenically unsaturated monomer represented by the general formula % [in the formula, R is H or Cl-13, and n is an integer of 6 to 18] 2 is pre-used. It's good to do that.

The monomer is particularly preferred because it dissolves or partially dissolves the dispersion stabilizer in the solvent i11.

An I4i1g unit having such a specific general formula is (
1.

β-monoethylenic nonvesicle [1 unilinear mixture [medium + (i
1) It is preferable to use 20 to 80 parts by weight of the mixture. In the above range, the lower limit is 20 vertices 1ii
When the amount is less than 1, the effect of improving the solvent solubility of the dispersion stabilizer tends to decrease, which is not preferable.

On the other hand, if it exceeds the upper limit of 80% by weight, it is similarly undesirable because coating film properties such as hardness and impact resistance tend to deteriorate.

A body 9+1 Tojitewo: j1.2-ethylhexyl (
meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, dodecyl(meth)acrylate
Examples include esters such as acrylate and stearyl (meth)acrylate. These can be used individually or as a mixture of two or more.

The α,β-monoethylenically unsaturated monomer 3 mixture [(i) Toyama)] is the hydroxyalkyl ester monomer of the α,β-monoethylenically vesicular orocargen ((i) ) component) and other monomers other than the monomer (component (b)) shown in the above general formula (component (b)).
In the monomer mixture [(i)+(wi):), 5 to 77
Can be used within the range of weight 1.

Specific examples of such a monomer 0→ include α such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, etc.
β-Monoethylenically unsaturated vesicles: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acryle-h% n-butyl (meth)acrylate ,5e
c-butyl (meth)acrylate, t-butyl (meth)
Acrylate, isobutyl (meth)acrylate)% N
Dialkyl esters of fumaric acid such as I N'-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, di-butyl fumarate, styrene, vinyltoluene, α - Monomers such as methylstyrene, (meth)acrylonitrile, and vinyl acetate can be mentioned. These may be used as a mixture of two or more types.

In the same way, when an N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid adduct containing an N-alkoxymethyl group is used as the other simple substance [component (iii)]. , α, β-monoethylenically unsaturated vesicles In the coexistence of hydroxyalkyl ester monomers of carbonic acid, the dispersion stabilizer becomes difficult to dissolve in the solvent and tends to increase in viscosity. Therefore, the component (c) is α.

It is preferable to avoid the use of N-alkoxymethylated monovalent forms of β-monoethylenically unsaturated carbonic acid amides.

Solvent-soluble bone vinyl resin C as a dispersion stabilizer of the present invention Hereinafter, it will be abbreviated as "vinyl resin" if necessary. ) is produced by conventional solution polymerization of the above components and (11). For example, a method in which the remaining monopentamer (mixture) and a polymerization initiator are dropped into a mixture of a part of the monomer (mixture) and a polymerization solvent to polymerize, or a method in which the monomer (mixture) is added dropwise to a mixture of a part of the monomer (mixture) and a polymerization solvent to polymerize Also applicable are methods of dropping a polymerization initiator and polymerizing. In any case, the present invention is not intended to be limited to a specific solution polymerization method. The solvent used in this solution polymerization method is the aliphatic hydrocarbon solvent described above. Also, as a polymerization initiator,
For example, pensoyl oxide, t-butyl 4'
-benzoate, t-butyl peroxybenzoate,
Organic peroxides such as t-butylno, monooxyoctoate and lauroyl peroxide, or azo compounds such as azobisisobutyronitrile are used. 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 dodecyl mercaptan, 2-ethylhexyl thioglycolate, carbon tetrachloride, etc. may be used to adjust the molecular structure.

In the present invention, in the presence of the dispersion stabilizer 6 dissolved (or partially dissolved) in the aliphatic hydrocarbon obtained as above and the vinyl +
ii) α.

β-monoethylenic nonvesicle [1 carnic acid amide N-
Alkoxymethyl monomer, (1v) before rlrj (i
il) other α,β-monoethylenically unsaturated vesicle rigid body and vinyl ester component,
A non-aqueous dispersion of a vinyl ester-modified vinyl polymer is obtained.

The non-aqueous dispersion of the vinyl ester-modified vinyl polymer is
When forming a coating film, α, β- contained in the dispersion stabilizer
It is necessary to contain an N-alkoxymethyl group in the dispersed particles in order to cause a crosslinking reaction (self-crosslinking reaction) with the hydroxyalkyl ester single matrix (1) of monoethylenically unsaturated carboxylic acid. Therefore, as one component in the single-body mixture [(iii) + (iV)), α
, a β-monoethylenically unsaturated carboxylic acid N-alkoxymethylated monomer (iii) is used.

By the way, the monolayer body (iii) has strong polarity. Therefore, copolymers containing this monomer as one component are difficult to dissolve in aliphatic hydrocarbon solvents, and are therefore suitable for forming dispersed particles.

Similarly, such a monomer is present in a mixture of α,β-monoethylenically unsaturated vesicle monomers ((+ii) + (iV):)
Use in the range of 5 to 25 weight.

In the weight range in the above mixture, said monomer (iii)
However, if the weight is less than 5 liters, the crosslinking density decreases during the reaction process with the crosslinkable heavy body during coating film formation, which is undesirable because the solvent resistance of the coating film decreases. On the other hand, if it is used in excess of 25 weight ratios, it is preferable because gluing will occur when it is unrolled.

The component (specific examples of 11D include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)
Acrylamide, N-n-propoxymethyl (meth)acrylamide, N-inbutoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, N-sec-butoxymethyl (meth)acrylamide, N-t-butoxy N-alkoxymethylated products of β-monoethylenically unsaturated carboxylic acid amide, such as methyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide; or N-methylolated products thereof. These may be used alone or as a mixture of two or more.

In addition, in the presence of a dispersion stabilizer, the α,β-monoethylenically unsaturated carboxylic acid attenuate used for copolymerization
Monomers other than 1-alkoxymethylated monomers (1■
) is a single polymer [(II+) +-(iv)]97
It is used in the range of 75 to 95 folds.

Example of pattern 1/body (1v) [- is acrylic acid,
a, β-monoethylenic nonvesicular carzene acids such as methacrylic acid, itaconic acid, maleic acid, and fumaric acid; methyl (
meth)acrylate, ethyl(meth)acrylate, lowpropyl(meth)acrylate, isopropyl(meth)acrylate, n-ethyl(meth)acrylate%
fi@C-ethyl (meth)acrylate, [-butyl (
meth)acrylate, isobutyl(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(
Alkyl esters of acrylic acid or methacrylic acid such as meth)acrylate and stearyl (meth)acrylate; Others N,N'-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, Examples include dialkyl esters of fumaric acid such as benzyl methacrylate and diethyl fumarate, styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate.

These may be used alone or in combination of two or more depending on the intended use of the coating composition.In addition, the monomer component (1v) may cause thickening during the production of dispersed particles. It is preferable to avoid the use of hydroxyalkyl ester monomers of α,β-monoethylenically unsaturated calzenic acid.

In the present invention, the "vinyl ester-modified vinyl resin polymer" used as a dispersed particle component consists of 0 vinyl ester, the monomer (iii) and the monomer (1
■), thus generating machine 1
It is possible to impart the vaguely superior alkali resistance, acid resistance, salt water resistance, and salt water spray resistance that vinyl esters have.

The vinyl ester used in the present invention includes (a) an epoxy compound having one or more epoxy groups in the molecule; and (b)
As a reaction product of an unsaturated monocarboxylic acid, all known products can be equally used.

The vinyl ester can be synthesized by a known esterification reaction.

For example, in an air atmosphere, an epoxy compound is reacted with heat in the presence of a monomer (1v) that can be used as a solvent for the esterification reaction (hereinafter referred to as a polymerizable monomer), and then as needed. It is synthesized by diluting it with a disease agent or a polymerizable monomer.

When synthesizing these, the anti-corrosion ratio between an epoxy compound having one or more 4-4 groups in the molecule and an unsaturated monocarboxylic acid is 0.6 to 1.
It is preferable to use the amount in the range of 2 moles, but from the viewpoint of performance, the preferable range is around 1 mole.

In other years, some or most of the saturated monocargenic acid is added to other Cal+J? It is also possible to convert it with carbon tm or carboxylic acid anhydride.

Further, the amount of the polymerization inhibitor, solvent, or polymerizable monomer to be used is appropriately selected depending on the desired workability, coating performance, etc.

Examples of epoxy compounds that can be used to synthesize the vinyl ester include Pico-Tona 827, a trade name manufactured by Shell Co., Ltd., which is synthesized by the reaction of bisphenol A and epichlorohydrin or methylepichlorohydrin;
φ828, Na 834, Na 1001, φ1004, Na 10
07, Na1009, etc., product name E manufactured by Union Carbide Co.
RL 2772, Na 2774, ε and R2002, Ciba product name Araldite GV-250, ◆260,
Na280, φ6071, Na6084, Na6099, etc., Asahi Kasei Co., Ltd. product name AERΦ330, φ331, Su3
32, ◆661. 664 etc., Dainippon Ink and Chemicals (
Co., Ltd. Part name: Ebikuron φ800, Na1000, Na40
00, etc. (2) Nogelac obtained by reacting phenols and formaldehyde under an acidic or alkaline catalyst, or by reacting resol with epichlorohydrin or methylepichlorohydrin, such as the product name manufactured by Dow Chemical Co., Ltd. t) ENφ431, φ458, ◆
448 etc., Ciba product name ECN 1235, φ127
3, φ1280, Na 1290 equivalent% (3) No. Infused by reacting rhodanized phenols with epichlorohydrin or methylepichlorohydrin, for example, Dow Chemical Company Ill! it@Product name DERS511, NA542, φ5808. Product name Aralgate φ manufactured by Ciba Corporation
8011, Na80474% (4) Obtained by reacting phenols with ethylene oxide or propylene oxide, etc., and epichlorohydrin or methylepichlorohydrin, for example, manufactured by Kadenka Co., Ltd. Part name εP 4000, $4001# , can be mentioned. These may be used alone or in mixtures.

Examples of the unsaturated monocarnoic acid to be reacted with the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, etc. In addition, monoesters of vesicular 1N polycarboxylic acid such as maleic acid monoethyl ester are used. You can also do that. These may be used alone or in mixtures.

Polymerization inhibitors used in the synthesis of vinyl esters include hydroquinones such as hydroquinone, quinones such as benzoquinone, hydroquinone monomethyl ether, phenols such as α-naphthol, and organic or inorganic copper such as copper naphthenate. Examples include salts, amidines such as acetamidine acetate, and quaternary ammonium salts such as trimethylbenzylammonium chloride and laurylpyridinium chloride. These may be used alone or in mixtures. The amount of polymerization inhibitor used is reactant 1
The amount is about 0.001 to 0.5 parts by weight relative to 0.00 parts by weight, but good results are obtained with about 0.005 to 0.05 parts by weight.

3 Furthermore, tertiary amines such as triethylamine, benzyldimethylamine, and 2,4.6-)lis(dimethylaminomethyl)phenol are used as reaction catalysts for vinyl ester synthesis, and these can be used alone or in mixtures. be done.

The synthesis method B'1 of the vinyl ester is a reaction between 11 moles of epoxy of an epoxy compound and 0.6 to 1.2 moles of cal-R xyl groups of unsaturated monocarzonic acid with a particle size of 50 to 180''C.
It reacts by heating in the range of . Preferably the reaction temperature is 80-14
The temperature should be in the range of 0°C. The amount of polymerization inhibitor used in this reaction is within the range described above. Father, the amount of esterification reaction catalyst used is approximately 0 per 100 mrm/part of reactant.
．． It is sufficient to use 0.001 to 5.0 type copper parts, but good results can be obtained with about 0.005 to 1.0 parts by weight.

Further, when a solvent or a d-polymerizable threat compound is added during the reaction, it is advantageous from the viewpoint of reaction rate to use as little as possible, although it depends on the reactants. The end point of the reaction can be determined by measuring the acid value. From the viewpoint of performance, it is generally desirable that the acid 25, rs'4 value at the end of the reaction be 20 or less.

When the resulting resin reaches the end point of the reaction, a polymerization inhibitor is added if necessary and after it is completely dissolved, cooling is started. After cooling is started, a solvent or a polymerizable monomer is added as needed, and once dissolved, the mixture is cooled to room temperature.

At this time, the amounts of the solvent and polymerizable monomer to be used are determined depending on the desired viscosity, workability, curability, etc. The polymerizable monomer is usually about 10 to 70% by weight based on the total resin content. In this case, as mentioned above, monomer (iii) and a part of monomer (1) are used as a solvent for the production of vinyl ester, but such polymerizable monomers are naturally also vinyl ester-modified vinyl polymers. Since it is a raw material component of It must be in a sufficient amount. Such polymerizable monomers may be used alone or as a mixture of two or more.

Furthermore, the solvent used in the esterification reaction is
Any material may be used as long as it does not interfere with the production of dispersed particles.

6 Examples of such organic solvents include hydrocarbon solvents such as heptane, octane, mineral spirits, luene, xylene, alcohol solvents such as propyl alcohol and butyl alcohol, ester solvents such as ethyl acetate and butyl acetate, and acetone. , methyl ethyl ketone corner ketone solvent, fil! It is an organic solvent such as an alcohol ester solvent or an ether ester solvent, and there is no particular restriction on the type as long as it does not impair the stability of the non-aqueous dispersion.

The vinyl ester used in the present invention is a reaction product obtained as described above, but any commercially available vinyl ester can be used without any need for real vinyl ester.

Commercially available products include, for example, Lipoxy R802, Lipoxy R806, Lipoxy H-600 manufactured by Nippon Kobunshi Co., Ltd., and Dick Light UE manufactured by Dainippon Ink & Chemicals Co., Ltd.
-5101, UE-5210, UE-3520, etc., Tamoto Shokubai Kagaku Co., Ltd. mounting products Meiko Polatsuk RF-1001, etc., Nippon Yubika Co., Ltd. product name: Neoball 8250L1, 8250H, 8411L, 8411H, etc. Hitachi Chemical Co., Ltd.) 7 Surface product name Polyset 6000, Polyset 6100. 620
0, PS-61208, etc., Kurade Pharmaceutical Co., Ltd.'s Hibi product name: Proonate P-310, Proonate P-311, etc., Dow Chemical Co., Ltd.'s product name: Delacane 411, 41 i C, 470, 510, etc., Sumitomo Kagaku Kogyo C Co., Ltd.) back side product name Sumiup EVR-911, etc., and these can be used alone or as a mixture of two or more kinds.

In the present invention, the vinyl ester-modified vinyl resin as the dispersed particle component contains 3 to 25% of the vinyl esters.
% by weight and the α,β-monoethylenic monomer (iii
) and a monomer mixture of (1v) with 75 to 97 polymers ii [.

As mentioned above, the amount of modification of vinyl ester is 3 to 25% by weight.
and is preferably in the range of 5 to 20% by weight. In the above case, if it is less than 3% by weight, the advantages of vinyl ester resin such as excellent alkali resistance, acid resistance, salt water resistance and salt water spray resistance cannot be fully exhibited.

On the other hand, if it exceeds 255% by weight, the characteristics of vinyl resins, such as weatherability and stain resistance, may be impaired, and the viscosity may increase during the production of dispersed particles, which is also undesirable.

Furthermore, the nonaqueous solvent dispersion of the vinyl ester-modified vinyl system 1 in the product 1 of the present invention contains a dispersion stabilizer, the vinyl open side [in the monomer and in the copolymer of (11)] 30 to 80
In the presence of 11#, the monomer (it), the monomer (1
70-20 g of a mixture consisting of v) and vinyl ester
It is obtained by combining l-=4.

In the above, if the amount of the vinyl resin is less than 30 weights and 31 weights, it becomes difficult to obtain a stable non-aqueous solvent dispersion. Conversely, if the amount exceeds 800% by weight, it becomes difficult to obtain a non-aqueous solvent dispersion, which is also not preferred.

The above copolymerization temperature is determined by the type of polymerization initiator and polymerization solvent used. It is usually carried out at a temperature between 500 and 200°C, and a range of 60°C to 150°C is particularly suitable.

As the polymerization initiator, the above-mentioned organic peroxides or azo compounds are preferably used. Incidentally, in order to adjust the molecular weight to 414, it is also possible to use the above-mentioned continuous transfer agent.

The non-aqueous dispersion type resin composition of the present invention may optionally contain a known catalyst for promoting the crosslinking reaction (self-crosslinking) of the vinyl ester-modified vinyl polymer.

It is also possible to use one or more types of coating film-forming resins such as nixy resin, cellulose resin, polyester resin, alkyd resin, amine resin, and blocked isocyanate compound.

Furthermore, in addition to the organic solvent contained in each component, the composition of the present invention may contain an additional organic solvent, if necessary, to an extent that will affect the stability of the composition.

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

Organic solvents that can be used include hydrocarbon solvents such as heptane, octane, mineral spirits, toluene, and xylene, alcohol solvents such as propyl alcohol and butanol, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, etc. These include organic solvents such as ketone solvents, alcohol esters, and ether esters, and there are no particular restrictions 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 contain tj% of inorganic or organic coloring pigments, metal powder pigments such as aluminum flakes, body pigments, and additives normally used in paints, if necessary. Can be added and used.

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

Additionally, heat the paint using hot spray (50~6%).
It is possible to paint at 0°C).

Further, the composition of the present invention can be formed into a film by simply evaporating the solvent after coating (so-called drying at room temperature), but in order to obtain a coating film with high performance, it is preferable to heat cure the composition. What are the conditions for heat curing?

Containment of crosslinkable functional groups in the composition - 1 Although it varies depending on the film thickness etc., it is usually made into a cured coating film by heat treatment at an appropriate temperature in the temperature range of 60 to 200°C for 10 to 40 minutes. I can do it.

The cured coating film thus obtained has the excellent alkali resistance, acid resistance, salt water resistance, and salt water spray resistance of the vinyl ester resin, and the hardness and stain resistance of the vinyl copolymer resin. It also has coating film performance with excellent secondary physical properties after testing, such as moisture resistance and water resistance.

The present invention will be explained below using specific examples.

In addition, "part" or "regret" represents "part by weight" or "heavy weight".

[Method for manufacturing vinyl resin dispersion stabilizer]

(1) 100 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 90°C. Then, the following monomer and initiator mixture was added dropwise over 5 hours.

26.5 parts of isobutyl methacrylate, 7 parts of 2-ethylhexyl methacrylate, 15 parts of styrene, 48 parts of 2-ethylhexyl acrylate, 12 parts of 2-hydroxypropyl methacrylate, 1.5 parts of methacrylic acid, azobisisobutyronitrile 2.5 parts @ After completion of the dropwise addition, 1.2 parts of azobisisobutyronitrile was added, and the reaction was further carried out at the same longitudinal temperature for 5 hours. Kagude, acid value 6.6. Hydroxyl value 47, weight average molecular weight 1139.
900% and a non-volatile content of 49.7% was obtained, and the thickness was 27.9% per 20°C.

I mourn this as ^0-1.

(2) In a reaction vessel similar to that in which AO-1 was synthesized.

After adding 100 parts of mineral spirit and raising the temperature to 90°C, the following monomer and initiator mixture was added dropwise over 3 hours.

21 parts of isobutyl methacrylate, 8 parts of 2-hydroxyethyl methacrylate, 70 parts of 2-ethylhexyl methacrylate, 1 part of methacrylic acid, 2.5 parts of benzoyl peroxide After the completion of the O dropwise addition, 1.2 parts of penzoyl 4-oxide 2 was added. The reaction was further carried out for 5 hours at the same reaction temperature, thus obtaining a resin solution having an acid value of 7.9, a hydroxyl value of 35, a weight average molecular weight of sn and ioo, and a non-volatile content of 50.14. The viscosity was 61.1 strokes and 720°C. This was designated as AO-2.

(3) In the same reaction vessel as when AO-1 was synthesized,
After adding 100 parts of mineral spirit and raising the temperature to 90° C., the following monomer and initiator mixture was added dropwise over 3 hours.

5 parts of methyl methacrylate, 37 parts of isobutyl methacrylate, 45 parts of 2-ethylhexyl acrylate, 6 parts of ethylene, 6 parts of 2-hydroxyethyl methacrylate,
111 parts of acrylic r, 2 parts of benzylumi-9-oxide.

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, resulting in an acid value of 9.0. A resin solution having a hydroxyl value of 261, a weight average molecular weight of 45.400, and a nonvolatile content of 49.9 was obtained. The viscosity was 27.0 Stokes/20°C. This was designated as fAo-3.

(4) Synthesis of the above ^0-1 (Pour 100 parts of mineral spirit into the same reaction vessel as in 5, raise the temperature to 90°C, and then dropwise add the following monomer and initiator mixture over 3 hours. did.

Methyl methacrylate 6 parts% 2-ethylhexyl acrylate 55 parts, styrene 10 parts, 2-ethylhexyl methacrylate 17 parts, inbutyl methacrylate 20 parts
part, 2-hydroxy z-tilac lJ 1/-1-1ON
% IlysuA, 2 parts rR, 2.5 parts penzoyl oxide.

After the dropwise addition, 1.2 parts of benzoyl 9-oxide was added and the reaction was further carried out for 5 hours at the same reaction temperature.
4, 4. Hydroxyl value 49, weight average molecule 1145.9n
A resin solution with an O and non-volatile content of 49.9 was obtained. The viscosity was 29.5 Stixvoices/20°C.

This was designated as AO-4.

[Method for manufacturing vinyl ester resin]

(1) In a reaction vessel equipped with a stirrer, a temperature variable meter, and a cooling tube, 0 part (1 equivalent) of Ebizutona 10014F, 86 parts (1 equivalent) of methacrylic acid, 0.2 part of hydroquinone,
When 2.22 parts of triethylamine was charged and the reaction was carried out at 145 to 155°C for 1 hour and 10 minutes in an air atmosphere,
Since the acid value became 2.5, cooling was started, 456 parts (4511) of styrene was added at 150°C, and the reaction was completed by cooling to room temperature.

The obtained vinyl ester resin has a color number (Gardner method)
was 3, and the viscosity was 5.6 voids/25°C. This was set as V l: -1 ◎ (2) In the same reaction vessel as the one in which VE-1 was synthesized.

AER”330 561 parts (3 equivalents), acrylic acid 21
6 parts (3 equivalents), 0.2 parts of hydroquinone, 1 part, 2,4
．． 6-tris(dimethylaminemethyl)phenol3.
When 1 part was charged and the reaction was carried out at 120 to 125°C in an air atmosphere for 2 hours and 60 minutes, the acid value was 4.7, so cooling was started, and at 100°C, 336 parts of styrene 5 (r304) was added. was added and cooled by stirring at room temperature to complete the reaction.

The obtained vinyl ester resin has 8 colors.

The viscosity was 4.2 poise/25°C. This) 1. Meeting VE-
It was set as 2.

Example 1 147.5 parts of mineral spirit, 241 parts of dispersion stabilizer (AO-1), and 5 viBti were placed in a reaction vessel equipped with a stirring funnel and a cooling tube.

After raising the temperature to 95° C., the monomer, vinyl ester resin and initiator mixture described below was added dropwise over 5 hours.

Methyl methacrylate 4 n -5+: +t+% 5 parts of isobutyl methacrylate, 24.3 parts of methyl methacrylate, methacrylic H11 $11. N-n-butoxymethylacrylamide l'11g+1. Vinyl ester resin (VE-1
) 18.2M, 2.0 parts of penzoylno 4-oxide,
Azobisisobutylene (1.0 parts of 1 nitrile).

After the dropwise addition was completed, 1.2 parts of penzoylno-4-oxide was added, and the reaction was further carried out at the same reaction temperature for 5 hours.

37 QQ-6 The reaction product was a milky white dispersion with an acid value of 9.1. Hydroxyl value 31
．． and non-volatile content was 45.4%. The obtained non-aqueous dispersion type resin composition was designated as ED-1.

Example 2 into a reaction vessel similar to that in which ED-'l was synthesized.

154.5 parts of mineral spirit, dispersion stabilizer (AO-
3) After adding 301 parts and raising the temperature to 95°C, the following monomer, vinyl ester resin and initiator mixture f, 3
dripped over time.

Vinyl ester resin (VE-2) 20111. 39.5 parts of methyl methacrylate, 10 parts of N-n-butoxymethylacrylamide, 26 parts of styrene.

2-ethylhexyl methacrylate 3M, methacrylic acid 1.5 parts, dodecyl mercaptan 0.5 parts.

2 parts benzoyl peroxide, 1 part 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 temperature for 5 hours.

The reaction product is a milky white dispersion with an acid value of 9.5. Hydroxyl value 22
．． i- and non-volatile content was 45.14.

=38 The obtained non-aqueous dispersion type resin composition was designated as fED-2.

Example 3 Into a reaction vessel similar to that in which ED-1i was synthesized, 5 parts of mineral spirit I-144 and a dispersion stabilizer (AO-2) were added.
20111f, and at a total temperature of 95° C., a mixture of monophyllate, vinyl ester resin, and initiator having the following vk% was added dropwise over 3 hours.

Methyl methacrylate 5715B, 31 parts of styrene.

Vinyl ester resin (^t"Lipoxy R-806) 1
3 parts, 2-ethylhexyl acrylic l/-) 5 parts, N
-15 parts of n-butoxymethylacrylamide.

1 part of methacrylic acid, 0.4 parts of dodecyl mercaptan, 1.5 fil of benzoyl peroxide and 1.5 M% azobisisoptylonitrile.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the W was reacted at the same reaction temperature for 5 hours. The reaction product is a milky white dispersion with an acid value of 7. o.

The hydroxyl value was 22 and the nonvolatile content was 44.796.

The obtained non-aqueous dispersion type resin composition was designated as ED-3.

Example 4 In the production of ED-3, dispersion stabilizer (AO-2)
The reaction was carried out in the same manner except that 300 parts of mineral spirit and 155.5 parts of mineral spirit were used. The reaction product is a milky white dispersion with an acid value of 6.9 and a hydroxyl value of 24. and non-volatile content was 44.9%.

The obtained non-aqueous dispersion type resin composition was designated as ED-4.

Example 5 159 parts of mineral spirit and 341 parts of dispersion stabilizer (AO-4) were placed in a reaction vessel similar to that in which ED-1 was synthesized, and after raising the temperature to 95°C, the following monomers, The vinyl ester resin and initiator mixture was added dropwise over a period of 3 hours.

38.7 parts of methyl methacrylate, 8 parts of isobutyl methacrylate, vinyl ester resin (the above Lipoxy H-6
00) 7.3 parts, N-t-butoxy 9 dimethylacrylamide 12 parts, methi 1 fufu 54 parts, benzoyl peroxide 3 parts.

Dropwise, add 1.2 parts of penzoyl peroxide and react at the same reaction temperature for 5 hours. It was 1. The reaction product was a milky white dispersion with an acid value of 9.2°, a hydroxyl value of 35, and a non-volatile content of 45.096. The resulting non-aqueous dispersion type resin composition was designated as ED-5.

Comparative Example 1 In Example 5, except for the vinyl ester resin (Lipoxy H-/, 00) and N-t-butoxymethylacrylamide, 7.3 parts of styrene and 12 parts of ethyl acrylate were added as components. The reactions were all carried out under the same pressure. The reaction product is a milky white dispersion with a % acid value of 9.0. The hydroxyl value was 30 and the nonvolatile content was 44.64.

The obtained non-aqueous dispersion type resin composition was designated as ED-6.

Comparative Example 2 0 In Example 1, mineral spirit 147.5
and 241.5 parts of the dispersion stabilizer (AO-1) were replaced with 200 parts of a soybean oil-modified alkyd resin solution having an acid value of 11%, a hydroxyl value of 1o1, an oil length of 30%, and a non-volatile content of 60%. Then, the following monomer and initiator mixture was added dropwise and reacted in the same manner.

40.5 parts of methyl methacrylate, 5 parts of isobutyl methacrylate, 11 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 32.5 parts of styrene, 1 part of methacrylic M, 1 part of penzoyl oxide.The reaction product is a milky white dispersion. Acid value 9.2, hydroxyl value 7
5 and the nonvolatile content was 44.74.

The obtained non-aqueous dispersion type resin composition was designated as ED-7.

The non-aqueous dispersion resin compositions of the present invention (ED-1 to ED-5) and comparative examples (ED-6 to 7) obtained as described above were applied to a polished mild steel plate (0.8 x 70 x 15011 m) to a film thickness of 30 mm. ~
It was air-sprayed to a thickness of 35 microns, left at room temperature for 20 minutes, and then heated and dried at 160°C for 20 minutes.

Table 1 shows the results of the coating film performance comparison test of the obtained vSM pieces.

3 (Note 1) Visual judgment 0 Transparent × Opaque (Note 2) rj
Visual judgment C) Political change × Forgiveness (Note 5) Use Mitsubishi pencil LJnl (apply it to the 7% paint film at an angle V of 111745°, press it lightly in the direction of 11, and check that there are no traces left by the pencil on the membranes. It's the J period of high lead value.

(Note 4) Gopanformes Thesohacrites].

(Note 5) Based on Erichsen testing machine.

(Note 6) Based on Jls-5400, 6, 13°58 method.

(Note 7) 51f##Water? After being immersed in liquid a for 48 hours at 20°C [F], the occurrence of #IM outside the coating film and blistering was determined.

(Note 8) 3. A trowel immersed in an aqueous solution of caustic soda for 48 hours at 20°C or lower, and the appearance of the paint film and the occurrence of blisters are evaluated.

(Note 9) Moisture resistance test tuna (50℃, 97% RH) 120
After the time, I did a quick check test.

0 100/100 ~ 95/1 [105 () 94/100 ~ 85/100 8 84/1 ['ln ~ 61/In1lX 59/
1011 ~ 0/1 n [1 (Note 10) Salt water spray resistance; After subjecting the test piece with a cross cut that reached the substrate to a salt water spray tester (J I5-Z-2371) for 120 hours, the cross cut portion was Sero Ntep was peeled off.

O (peeling width: one rl) n ~ 1, Q aj
IO (#:”l To 1.1~2.0U (#:#) 2.1~3.0U x (#:#) 3.111!1 or more (attention) Water resistance: To tap water at 20℃ After soaking for 10 days,
Gopanformes Chishibacritest Q 1no/1nn~95/100 0 94/IDn~85/100 Δ 84/1nO~60/1 [111 X 59/1011~11/1011 (Note 12) Each non-aqueous dispersion type Resin composition ((lu L,
In the comparative example, a mixture of melamine resin (6) was kept in a constant temperature bath at 50° C. [7] The number of days until changes such as particle sedimentation, phase separation, or significant increase in viscosity were observed is shown.

From the above comparative test results, it is clear that the coating film obtained from the non-aqueous dispersion type resin composition of the present invention has excellent transparency, yellowing resistance, hardness If, flexibility, impact resistance, and chemical resistance. and moisture resistance,
The secondary adhesion after water resistance and salt spray resistance tests was very good, and the storage stability of one composition was also excellent under extreme pressure.

Claims (1)

[Claims] (1) Although ~(+V) in the monomer is dissolved, the vinyl ester-modified vinyl copolymer obtained from the vinyl ester, monomer (iiD) and monomer (1■) In an aliphatic hydrocarbon solvent that does not dissolve, a single hydroxyalkyl ester of α,β-monoethylenically unsaturated sulgonic acid and (ii) the α,β-monoethylenically unsaturated vesicular sulfuric acid. In a solvent-soluble vinyl resin dispersion stabilizer obtained by copolymerizing one saturated vesicle...
(iii) N-alkoxymethylation of α,β-monoethylenically unsaturated vesicle dP acid amide in the presence of 30-8o heavy f-hydrogen (IV)! ii″! A monolithic mixture 75 to 9711 consisting of one α,β-monoethylenically unsaturated vesicle other than (iii)
A mixture of (a) an epoxy compound having one or more epoxy groups in the molecule and (b) 3 to 2500 t% of a vinyl ester obtained from a vesicle 41 monocar + zenic acid...・・・――
・Non-aqueous dispersion type resin resin of vinyl ester modified vinyl polymer obtained by polymerizing 70-2011i'ff11
1 component 1° (2) solvent-soluble vinyl resin dispersion stabilizer,
(a) α,β-monoethylenic atom(hydroxyalkyl ester of carnic acid) disassembly・・・kai・@cloud・・・Φ・・・・ 3～15*ii
! '1, (b) General formula % Formula % [In the formula, R is 11 or CH3, n is an integer of 6 to 18]
...20 to 80 weights, and (c) the above (
Claim No. 1 which is a copolymer obtained from α,β-monoethylenically unsaturated vesicles other than a) and (b)... ) The non-aqueous dispersion type resin composition described in item 2. (3) The above general formula〇H=Ccooco"2n-1-
α,β-monoethylenically unsaturated vesicles designated by 1 are composed of 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate and Stearyl (meth)
A non-dispersed 7Kv resin composition according to claim (2), which is at least one compound selected from acrylates. (4) Said (iii) α,β-monoethylenically unsaturated vesicle +J? The N-alkoxymethylated phosphoric acid amide and (1) the non-β-monoethylenic nonvesicular monomers other than (iiD) are in the (iii) On the other hand, the latter (1■) is a single needle body composite with a weight ratio of 75 to 95, tp!
li:: A non-aqueous dispersion type resin composition. (5) The vinyl ester has (a) 1 mole of the epoxy group of the epoxy compound having one or more epoxy groups in the molecule, and (b) 0.6 to 1 carboxyl group of the nodule + 11 monocarboxylic acid. Claim No. 1, which is a reaction product obtained by carrying out an esterification reaction at a ratio of .2 moles.
) The non-aqueous dispersion type resin composition described in item 2.