JPS6049017A - Nonaqueous 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 In detail, the present invention relates to a known thermosetting non-aqueous dispersion resin composition comprising a non-aqueous solvent dispersion of a polyester-modified vinyl polymer.

In recent years, demands for resource saving and pollution-free production have been rapidly increasing in the paint field as well.

In particular, non-solid paints, which are resource-saving paints with low solvent content and high solid content, are preferred because they can be used with conventional string manufacturing methods or coating equipment. It seems to be used in

``In recent years, considering the recent measures to restrict the use of solvents due to air pollution problems, ordinary high-solids type sabots that use a lot of aromatic and ester thread solvents are also preferred for industrial production.'' It doesn't seem like something earthy.

Furthermore, from the viewpoints of the regulation of the use of solvents, which has been further strengthened in recent years, non-pollution in a broad sense, and energy saving, non-aqueous dispersion paints using an aliphatic hydrocarbon-based d agent as the main solvent have been proposed.

However, conventionally known non-aqueous dispersion compositions of this type, such as dispersion stabilizer/dispersion particle combinations such as decomposed natural rubber/acrylic resin, acrylic resin/acrylic 4X+1 fat, oil-modified alkyd resin/acrylic resin,
Coating films obtained from thermosetting non-aqueous dispersion paints using polybutadiene/acrylic resin as a color vehicle 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, and so on. , I couldn't find it. In addition, it was not always possible to obtain sufficient performance in salt spray resistance, moisture resistance, water resistance, and secondary physical properties after each test.

In addition, non-aqueous dispersion type resin compositions using the above-mentioned combination as a color vehicle are characterized by a difference in polarity between the dispersion stabilizer component (solvated component) and the dispersed particle component (produced polymer). The solubility decreases, and therefore, the gloss obtained from the composition has a tendency to lack transparency and to have a decrease in gloss, shine, 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 coating material, it is considered to be unsuitable for exterior applications, and has been mainly used for interior applications.

1. The color vehicle is used to cure aminoformaldehyde resins, blocked isocyanate compounds, epoxy resins, methoxymethylated acrylamide resins, etc. in order to react with the functional groups in the vehicle to obtain an excellent cured coating film. You are using drugs together.

These are usually added when making paints, 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.

The present inventors have conducted four studies to improve the various drawbacks of the known techniques, and as a result, we have developed a specific functional group (hydroxyl group) that crosslinks with the functional group (hydroxyl group) in the dispersed particle component as a component of the dispersion stabilizer. By containing N-alkoxymethyl M,), it has transparency, excellent finished appearance, and hardness.
A cured coating film with excellent stain resistance can be obtained.A patent application (patent application No. 3g-9!; 3gO) was filed under all headings.
As a result of further investigation, as a component of the dispersion stabilizer,
It was discovered that a cured coating film having the same performance as the previous application could be obtained by including a functional group (hydroxyl group) that crosslinks with the functional group (N-alkoxymethyl group) in the dispersed particle component, and the present invention It was reached.

That is, the present invention provides an aliphatic compound in which the monomers (1) to QXA are soluble, but the polyester-modified vinyl copolymer obtained from the solvent-insoluble unsaturated polyester and the monomer (beating and monomer 0ψ) is not soluble. In a hydrocarbon solvent, (I) an α,β-monoethyl unsaturated carboxylic acid nohydrogysialkyl ester monomer;
) Solvent-soluble vinyl resin dispersion stabilizer obtained by copolymerizing with α,β-monoethylenically unsaturated monomers other than 30~
The N-alkoxymethylated monomer of rrr++α,β-monoethylenically unsaturated caldenic acid amide and the above (11D
A monomer mixture Sθ~95% consisting of α, β-monoethylenically unsaturated monomers other than (alα, β-unsaturated dicarboxylic acid, (b) acid components other than the previous self (at) and (C) a mixture of solvent-insoluble unsaturated polyester obtained from polyhydric alcohol with 5% to 70% SO%
This invention relates to a non-aqueous dispersion type resin composition of a polynisder-modified vinyl yarn polymer obtained by graft polymerization.

The solvent used in the present invention, that is, the above-mentioned "aliphatic hydrocarbon solvent" has the following characteristics.

α, β-monoethylenic monocle (1), which will be described later
, (11), song) and (IV) are soluble, but the ``polynisglu-modified vinyl copolymer'' obtained from monomer surface), and the unsaturated polyniscar of road and pond solvent properties is not soluble. It is.

Specifically, IJ is hexane, heptane, octane,
Aliphatic hydrocarbons such as cycloheptane, cycloheptane, meglucyclohegizan, ethylcyclohexane, dimethylcyclohexane, others, mineral spirits,
Examples include mixtures containing aliphatic naphtha as a main component.

Generally speaking, the above-mentioned "solvent-soluble vinyl resin dispersion stabilizer" used as the dispersion stabilizer of the present invention includes (1) α,β-monoethylenically unsaturated It is obtained by total polymerization of a hydroxyalkyl ester monomer of carunic acid and an α,β-monoethylenically unsaturated monomer other than (i+1) above.

In this specification, the term "6-solvent soluble" refers to the property of being partially or partially soluble in the aliphatic hydrocarbon solvent. Similarly, the term "solventizable" refers to dissolving or partially dissolving in such a solvent.

The above (I) α,β-monoethylene unsaturated (hydroxyalkyl ester monomer of carboxylic acid) is a monomer mixture ( fi+ 10 (il+), 3-15 heavy conquest%
It is preferable to react at a ratio of 5 to 10% by weight.In the above range, if the amount of this component is less than 3% by weight, (χ, β-
Monoethylene citrus unsaturated Cal +1? The crosslinking reaction of the acid amide with the N-alkoxymethyl monomer and the 4-saturated polynisglue component becomes insufficient, and the solvent resistance of the coating film tends to decrease. on the other hand,/! If the total amount exceeds %, the soluble resin as a dispersion stabilizer becomes difficult to be soluble in the aliphatic hydrocarbon solvent, which is not preferable.

Specific examples of this type of monomer, i-monocarbon (1) include euhydroxyethyl (meth)acrylate, suhydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and euhydroxybutyl (meth)acrylate. ) acrylate, 3-hydroxybutyl (meth)acrylate, g-hydroxybutyl (meth)acrylate,
S-Hydroxyenthyl (meth)acrylate, O-hydroxybutyl (meth)acrylate, Neopentyl glycol mono(meth)acrylate, 3-butylene hydroxypropyl (meth)acrylate, λ-hydroxy-7-phenylethyl ( Examples include meth)acrylate, polypropylene glycol mono(meth)acrylate, and glycerin mono(meth)acrylate, and these may be used alone or as a mixture of two or more.

The component (1) is α used as one component of the distributed shunko.
, β-monoethylenically unsaturated carbonate amide N-
In addition to being necessary for the crosslinking reaction with the alkoxymethylated single song component, in order to make the cured coating film completely transparent, which is obtained from the composition of the present invention, It is essential to exist.

In the present invention, the α,I-monoethylenically unsaturated monomer (11) other than (1) I is obtained by solubilizing a vinyl resin as a dispersion stabilizer in the aliphatic hydrocarbon solvent. Any monomer can be used as long as it does so.

Particularly, it is preferable to use a part of the α,β-monoethylenic monomer represented by the general formula: .

This monomer is particularly preferred because it solubilizes the dispersion stabilizer in the solvent.

Monomers having such a specific general formula can be used as α,β-monoethylenically unsaturated monomer mixtures [(1)++*
1+), 20~go)y%; I; Used in 1 cup.

In the above range, if the amount is less than the lower limit of 20%, the effect of improving the solubility of the dispersion stabilizer in the solvent will be reduced, which is not preferable. on the other hand,
If it exceeds the upper limit of gO weight, the hardness and oil resistance I'
Coating film LJ with g-ability, etc.: This is similarly undesirable because it shows a tendency for performance to decrease.

Specific examples include d-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (
meth)acrylate, dodecyl(meth)acrylate,
Esgnov such as stearyl (meth)acrylic notebook can be mentioned. These can be used alone or as a mixture of two or more.

In addition, the above α,β-monoethylenically unsaturated monomer compound (+++3) is the hydroxyargyl ester of the α,β-monoethylenically unsaturated olecardic acid. Other units and 11 other than the single unit ((b) component) and the unit shown in the general formula ((b) component)
The compound (c) can be used in the single IJ compound mixture [m + (++)) in a range of S to 77%.

As a specific example of such a single unit (c), 'C is acrylic acid, methacrylic acid, itacon modified, maleic acid, fumaric acid, α, β-monoethylene 1 main non-main minor 1 tough AI cal+I ? Methyl (meth)acrylate, ethyl (meth)acrylate, []-propyl (meth)acrylate, isopropylthyl (meth)acrylate, SeC-butyl (meth)acrylate, t-butyl (ivy)acrylate, Isobutyl (meth)acrylate, N,IN'-dimethylamine ethyl (meth)acrylate, daringyl (meth)acrylate, cycloheginyl (meth)azirylate, phenyl methacrylate, benzyl methacrylate,
7M dialkyl esters such as dibutyl fumarate, monomers such as styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate are extinguished. One or more of these may be used as a wet amount.

In addition, as other * fj: body (c) component), N-
α,β-monoethylene 1 biodeficient U with alcoquine methyl foundation;
The single use of methylated i4i.1 is not preferable because the dispersion stabilizer dissolves in the solvent and the dispersion stabilizer becomes opaque and tends to increase in viscosity.Therefore, the use of this type of single 11 is not recommended. It's better.

Solvent-soluble vinyl resin IJt as dispersion stabilizer of the present invention
q (Hereinafter, it will be abbreviated as ``vinyl/koso'' if necessary.

) is produced by polymerizing all of the components (1) and (11) in a conventional bath solution. For example, in a mixture of a part of #L size (mixture) and a binding solvent, the remaining unit:
Initiation of polymerization with a monomer (/iz 訃品) / 411 Gold Strip F1 A method in which a monomer (mixture) and a polymerization initiator are added dropwise into a polymerization solvent, or a method in which polymerization is performed can be applied. In any case, the present invention is not intended to be limited to a specific solution polymerization method. The solvent used in the f6 liquid polymerization method is a pre-6 aliphatic hydrocarbon solvent. In addition, as a polymerization initiator, for example, benzoyl peroxide, t
Organic peroxides such as -butyl perbenzoate, t-butylno♀-ogicipenzoate, -butyl peroxyoctoate and lauroyl peroxide, or azo compounds such as azobisisobutyronitrile are used.

These polymerization initiators may be used alone or in combination as appropriate.

In the present invention, if necessary, a chain transfer agent such as dodecyl mercaptan, Ω-ethylhexyl thioglycolate, 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 which is bath-dissolved (or partially dissolved) in the aliphatic hydrocarbon obtained as described above, (ir+α.

N-alkoxymethylated monomer of β-monoethylenically unsaturated carpanic acid amide, its composition other than θ cutting ia (+ii), α, β-monoethylenically unsaturated monomer, and aliphatic hydrocarbon system A non-aqueous dispersion of a polyester-modified vinyl polymer is obtained by graft polymerizing an unsaturated polyester component that is insoluble in a mortar.

The non-aqueous dispersion of the polyester-modified vinyl polymer is mixed with α,β-monoethylenically unsaturated carboxylic acid contained in the dispersion stabilizer during coating film formation. In order to carry out a crosslinking reaction (self-crosslinking reaction) with the hydroxyargyl ester monomer (1) of carbonic acid, it is necessary to contain an N-alkoxymethyl group in the dispersed particles.

Therefore, an N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carbonated amide (ii+1 is
Use for historical purposes.

By the way, the sheep type ++1++ has strong polarity. Therefore, a copolymer containing this monomer as one component is resistant to bath dissolution in aliphatic hydrocarbon-based d-media, and is therefore suitable for forming dispersed particles.

In addition, such a single Y1. The i' form is α, β-monoethylenically unsaturated #i, Lt form mixture c +**o +cv+
), used within the range of s~:l-weight%.

In the weight range in the mixture,
If the amount is less than 3% by weight, the crosslinking reaction of the α,β-monoethylenically unsaturated carpanic acid used as a component of the dispersion stabilizer with the hydroxyargyl ester component will be insufficient, and the This is not preferred because the solvent resistance of the resulting coating film becomes low.

On the other hand, if the weight exceeds 25% and is used for one time, the r
This is not a good idea as it involves digitization.

The components (specific examples of songs include N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-propoxymethyl (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, IN -n-cytoxymethyl (meth)acrylamide, N-sec-butoxymethyl (meth)acrylamide, Nt-cytoxymethyl (meth)acrylamide, IN-butoxynotyl (meth)acrylamide, etc. α,β-monoethylene N-alkogysimethylated products of sexually unsaturated orocarinic acid amides; or these N-
Examples include methylol compounds. These may be used alone or as a mixture of two or more.

In addition, the α,β-monoethyl unsaturated carbyl?
Monomers other than N-alkoxymethylated monomers of acid amide (ψ is 76" to 9 in monohk, monomer mixture [(song + track)]
Use within the range of 5'tit%.

Specific examples of lψ include (f) such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
, β-7-horn ethylene 1 biounsaturated 41] carmethyl (meth)acrylate, ethyl (meth)acrylate, n-
Propyl (meth)acrylate, -t,t-butyl (meth)acrylate, isopnal (meth)acrylate,
n-hexyl (meth)acrylate, d-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, trigacil (
Alkyl esters of acrylic acid or methacrylic acid such as meth)acrylate and stearyl (meth)acrylate; other N,N'-dimethylaminoethyl (meth)
Acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, dialkyl esters of fumaric acid such as dibutyl fumarate, styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, vinyl acetate, etc. can be mentioned. These ti
Depending on the purpose and purpose of use of the silk silk for paint, seven or more types may be used in combination as appropriate.

Furthermore, as the pre-Fje monomer monomer V5, it is better to avoid using a hydroxyalkyl ester monomer of α,β-monoethylenically unsaturated caldicic acid because it causes thickening during the production of dispersed particles.

In the present invention, the "polynisyl-modified vinyl resin polymer" used as a dispersed particle component is an unsaturated polyester that is insoluble in aliphatic hydrocarbon solvents (hereinafter referred to as "bath-insoluble unsaturated polyester"). , the monomer (11
It is obtained by grafting D and monomer -■, and thus the resulting coating film can have all of the flexibility and excellent coating appearance of polyester resin. Solvent-insoluble unsaturated polynisolyl, which is used in Europe, is obtained from a polybasic acid (which may be combined with a monobasic acid if necessary) and a polyhydric alcohol through a conventional condensation reaction. gall1
7.Any substance that is insoluble in aliphatic hydrocarbons is f.
It is functional for historical purposes.

-1, α,β-unsaturated dicalcium 1? Use phosphoric acid for one period. This component contains 7 to 10 parts of unsaturated polyester.
i:%, preferably used at a ratio of % to 100%. In the range specified by M, if the component is less than /weight i + t%, the polyvarnish as a dispersed particle component 7 - IA=
Vinyl'+IJ IJt7 When produced, it was not sweet enough for the α,β-monoethylenically unsaturated single-stitch mixture, and therefore the polyester modification was insufficient, so the product was made of unsaturated polynisglu and α,β-monoethylenically unsaturated The composition was a blend of the copolymer obtained from the monomer mixture [(m+ + Ql. Due to the difference in reactivity, the coating ability, especially the adhesion, tends to decrease. On the other hand, when this component exceeds 10% by weight, α,β-monoethylenically unsaturated monomer C (ii
i) + Gluation occurs during the graft reaction with (isu), which is not preferable.

Specific examples of the components include fumaric acid, maleic acid (anhydride), itaconic acid, glutaconic acid, citraconic acid (anhydride), etc., and a glaze or a mixture of two or more of these may be used.

In the synthesis of the unsaturated polynisglue used in the present invention, preferably 2q
The reaction is carried out at a rate of ~69% by weight. Specific examples of the components include (anhydrous) phthalic acid, isophthalic acid, (anhydrous) trimellitic acid, (anhydrous) biromellitic acid, tetrahydro (anhydrous) phthalic acid f, l, hexahydride IIJ (anhydrous) phthalic acid, methyl chloride. trihydrophthalic anhydride, methylhexahydrophthalic anhydride, hymic anhydride, succinic anhydride, adipic acid, succinic acid, benzoic acid,
Tertiary benzoic acid, isononanoic acid,
Examples include versatic acid (C), and these may be used alone or in a mixture of two or more.

In the synthesis of the unsaturated polyester used in the present invention, the polyhydric alcohol component is preferably 30 to 70 MKk.
% of the reaction. Specific examples of the components include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, glycerin, trimethylolethane, trimethylolethane, pentaerythritol, dipentaerythritol, butanediol, bentanediol, hexanediol, / , Hiro-cyclohexanedimethanol, (frozen) bisphenol A1 ether-/, 3-
Examples include additions of hexanediol, bisphenol A and alkylene oxide, and these may be used alone or as a mixture of two or more, and if necessary, in combination with Cardular E (Shell Chemical Co., Ltd. 31u, trade name). In addition, animal and vegetable oils and their fatty acids, petroleum resins, rosin, phenol'4 fats, epoxy resins, etc. can be used as modified raw materials for unsaturated polyesters as needed.
4 history can also be used.

The unsaturated polyester in the present invention is produced by a single-stage reaction or a multi-stage reaction by a known method.

There are no particular bIJ limitations on the reaction method.

Note that the obtained unsaturated polyester is usually solid at room temperature, so it may be difficult to handle the above-mentioned monomer curves) and/or
Alternatively, among (IV), unsaturated polyesters may be diluted and dissolved. The amount of monomer (110 and/or (Vl) used at this time is the amount of dispersed particles [
The monomers (t+a, monomer QXA and unbonded polyester) are naturally within the scope of production.

When the above-mentioned α,β-monoethylenically unsaturated monomer (11D and/or rod is used as a diluent, the reaction with the heptaunsaturated polyester whose dilution temperature is high tends to proceed and lead to dulling. In that case, in order to suppress the reaction between the unsaturated polyester and the α,β-monoethylenically unsaturated single compact 011) and/or 4Vl, the polymerization inhibitor must be added to the unsaturated polyester (solid It is preferable to add 0.069% or less with respect to In the above, if more than 0, q% by weight is added, the polymerizability during the later graft polymerization of the unsaturated polyester and the α,β-monoethylenically unsaturated monomer mixture coip + #ψ] will be significantly reduced. This is not preferable because it lowers the temperature.

However, as the polymerization inhibitor, hydroquinone,
Examples include methylhydroquinone and catechol, which may be used singly or as a mixture of two or more.

The acid value of the unsaturated polyester described in -■ of the present invention is Sθ or less (resin solid content; hereinafter, all acid values in the present invention are expressed in the same manner), and the hydroxyl value is Sθ to 2Sθ (resin solid content; hereinafter, The indication of hydroxyl value in the invention shall be the same in all cases), molecule thi
! : is a weight average molecular shortness, and ko, ooo-sθ, and 0θ0 are preferable. In addition, the blind cap average molecular weight is determined by dal permeation chromatography [Toyo Soda @Ura HLCiO type A]
(hereinafter referred to as Mt in the present invention)
It was measured in the same way as the average molecular line. ).

In the above acid value range, if the acid value exceeds SO,
α,β-Monoethylenically unsaturated*: After the entire uL body is graft polymerized, the final P: There is a tendency for alkali resistance etc. to decrease in coating film performance. Furthermore, if the hydroxyl value is 50 degrees lower, the cross-cutting properties of the polynisder modified vinyl resin obtained by graft polymerization of α,β-monoethylenically unsaturated monomers tend to be insufficient; , there is a tendency for the water resistance of the t+ and fc@ membrane to decrease due to an increase in the number of polar groups.

Furthermore, if the average molecular weight is lower than the lower limit of 2,000, the various properties of the polyester resin cannot be fully exhibited. On the other hand, if so or ooθ is exceeded, the molecular weight of the polyester resin is too high, so if the polyester resin is modified with an α,β-monoethylenically unsaturated monomer, the resulting non-aqueous dispersion will have a very high viscosity. This is not preferable because it causes problems in terms of workability.

In the present invention, the polyester-modified vinyl resin as the dispersed particle component includes the unsaturated polyester 5-5
0% and the pre-self α,β-monoethylenic monomer (
It consists of a graft polymerization reaction product of the song and (■ year) temperature compound SO ~ SO S car mouse%.

As mentioned above, the modification property of the unsaturated polyester is in the range of S to SO weight %, preferably in the range of 7 to Da 0 weight %.

In the above, if the SM content % is too low, the advantages of polynisglu resin such as excellent curing properties, pigment dispersibility, and excellent coating film appearance cannot be fully exhibited. On the contrary, 30#E round%
If it exceeds this value, the hardness, stain resistance, etc., which are the characteristics of vinyl (v) fat, will be impaired, so it is also not preferable.

Historically, the non-aqueous dispersion of polynisglu-modified vinyl filament in the product 1 is prepared by dispersing vinyl resin [monomers (1) and (11)] 30 as a dispersion stabilizer. −
In the presence of g0*M%, the monomer (IV)
Mixture 7 consisting of I and solvent-insoluble unsaturated polynisglue
0 to 20 FM %f: Obtained by polymerization.

In the above, if the amount of the vinyl resin used as a dispersion stabilizer is less than 30 M%, it becomes difficult to obtain a stable non-aqueous solvent dispersion. On the other hand, if go exceeds i%, it becomes difficult to obtain a non-aqueous solvent dispersion, which is also not preferred.

The copolymerization temperature is determined by the polymerization initiator used and the af of the polymerization solvent. Normally 50'O~ko0θ℃
The range between bo''C and /so) is particularly preferred.

As the polymerization initiator, the above-mentioned organic peroxides or azo compounds are preferably used. Incidentally, in order to adjust the molecular layer, the chain transfer agent shown above can also be used.

The non-aqueous dispersion type resin composition of the present invention may contain, if necessary, a known catalyst for promoting the crosslinking reaction (self-crosslinking) of the polynisder-modified vinyl thread aggregate, as well as epoxy resin, cellulose thread resin, and polyester resin. It is also possible to use -tm or a combination of two or more of coating film forming resins such as , alkyd resins, amine resins, and blocked isocyanate compounds.

In addition, the composition of the present invention may contain an organic solvent, if necessary, in addition to the promoting bath medium contained in each component, to the extent that the stability of the composition I is not impaired. Like 44-
The bath medium may be the same as or different from the organic solvent contained in each component.

Examples of organic KJ agents 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 bath agents such as ethyl acetate and butyl acetate, and acetone. , ketone thread solvents such as methyl ethyl ketone, organic solvents such as alcohol ester threads, ether ester threads, etc. There is no particular restriction on the type of solvent as long as it does not impair the properties of the non-aqueous dispersion.

In addition, the non-water "defective" resin composition of the present invention may contain, if necessary, inorganic or organic coloring pigments, metal powder pigments such as aluminum flakes, extender pigments, and additives commonly used in paints. 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, curtain flow coating, shower coating, and roll coating can be used.

In addition, heat the paint using hot spray (30 to 6
It is also possible to apply the coating at a temperature of 0°C.

In addition, the composition of the present invention can be used by simply evaporating the solvent after painting (
Although it can be cured by so-called normal drying, heat curing is preferable in order to obtain a coating film with high performance. The heat curing conditions vary depending on the content of crosslinkable functional groups in the glaze product, the thickness of II, etc., but usually
A cured coating film can be obtained by heat treatment at an appropriate temperature in the temperature range of 00° C. for /θ to 110 minutes.

The cured coating film thus obtained has the flexibility and corrosion-resistant appearance of polyester resin, and the hardness and stain resistance of vinyl copolymer resin. Furthermore, the coating film has excellent secondary physical properties such as salt spray resistance, moisture resistance, and water resistance after testing.

The present invention will be explained below using specific examples.

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

[Method for producing vinyl resin dispersion stabilizer]

(1) 10 θ parts of mineral spirit was placed in a reaction vessel equipped with a stirrer, a thermometer, a 4×J lower funnel, and a cooling tube, and the temperature was raised to a total of 90″0.Then, the following f4i 1
n: body repair initiator (U mixture i'1 for 3 hours)
i4j down.

26.5 parts of inbutyl dimethacrylate, 7 parts of nee ethyl dimethacrylate, styrene SA+iX, 2~
2 parts of ethylhexyl acrylate, 2 parts of euhydroxypropyl methacrylate, 7.5 parts of methacrylic acid, azobisisobutyronitrile, 2. S Miyako.

After the reaction was completed, 2 parts of azobisisonotyronitrile was added, and the reaction was further carried out at the same reaction temperature for S hours. Thus, the acid value is B, the hydroxyl value is 7, and the weight average molecular weight is 3'?
, 900. A resin solution with a nonvolatile content of 49 and 7% was obtained, and the viscosity was 27.9 Stokes and e/20'CJ.
There was C. This was set as 80-/.

(2) In a reaction vessel similar to that in which AO-/ was synthesized,
After adding 700 parts of mineral spirit and raising the temperature to 0°C, the following container and initiator mixture were added dropwise over 3 hours.

2 parts of isobutyl methacrylate, g parts of dihydrogynethyl methacrylate, 70 parts of ethylhexyl methacrylate, parts of methacrylic acid, parts of benzoyl oxide, s parts.

After the dropwise addition was completed, 2 parts of benzoyl parent oxyside was added and the reaction was carried out at the same reaction temperature for 5 hours, resulting in an acid value of 7.9, a hydroxyl value of 35, and a page weight average molecular weight of 0. ,io
A resin solution with a non-volatile content of SO 0/% was obtained.

The viscosity was 3/Stokes-Boys 720°C. This was designated as fAθ-).

(3) In a reaction vessel similar to that in which the pre-self AO-/ was synthesized,
After adding 700 parts of mineral spirit and raising the temperature to 70C, the following monomer and initiator mixture was added dropwise over a total of 3 hours.

5 parts of methyl methacrylate, 37 parts of isobutyl methacrylate, 4'5' of ethylhexyl acrylate, styrene, 1, 2, 1, 2, 1, 2, 3, 3, 3, 3, 3, 4, 5, 5 parts of ethylhexyl acrylate.
, @I, acrylic acid/part, pensoylno-8-ogicide 2 parts.

71 After the completion of the homogenization, 1 l of benzoyl oxoxide was added, and the reaction was further carried out at the same temperature for S hours to give an acid value of 7.
0, hydroxyl value, weight: average molecule is 413, 00,
A resin solution with a nonvolatile content of 79.9% was obtained. The viscosity was 2zθ stix JJe/koθ°C. This was set at 80-3.

(g) In a reaction vessel similar to that in which 〇-no was synthesized above,
After adding 700 parts of mineral spirit and raising the temperature to 90°0, the following monomer and initiator mixture was added dropwise over 3 hours.

Methyl methacrylate Otsu part, Ni-ethylhexyl acrylate 35 parts, Styrene IO part, Ni-ethylhexyl methacrylate/7 parts, Isobutyl methacrylate-1-20
parts, 10 parts of λ-hydroxyethyl acrylate, methacrylic v, 2 MI<1 penzoyl peroxide
Part 5.

After the dropwise addition, benzoyl (-oxide/1.2 parts) was added and the reaction was carried out for an additional 3 hours at the same reaction temperature to give an acid value of 11.1 l, a hydroxyl value of 11.1 l, and an average molecular weight of Higashiba. ,
A 7% resin solution with qθθ and non-volatile content is prepared as R4. The key is viscosity. S Stokes Boyds/20°C. This was designated as AO-1'.

[How to use # for unsaturated polynisgur]

(C) Unsaturated polynisglue Na/ (hereinafter abbreviated as HP-/) Isophthal (R32,
3 parts, adipine #/shio,/part, fumaric acid 3.0 parts, neopentyl glycol, 2,2.9i, trimethylolpropane/7. Then, 9.3 parts of Cardura-E (trade name, manufactured by Shell Chemical Co., Ltd.) was charged, and the temperature was raised to 2g 0"0 in a nitrogen gas atmosphere, and then the reaction was carried out at the same reaction temperature for about 7 hours.

After that, it was cooled to / g O"C!, and hydroquinone was added to the unsaturated polyester (solid content) in an amount of 0.01%. It was further cooled to 720" o1, and styrene was added so that the nonvolatile content was 6%. diluted with This was HP-/bound.

The acid value of the Unsaturated Polyester 1 is g, 3, the hydroxyl value is /Otsube, and the average molecular weight of the molding sand is 1, . It cost 900.

-) Unsaturated polyester glue h+a, 2 (hereinafter HP-:l
77.5 parts of inphthalic acid, phthalic anhydride / 7-5 ffL-
f Dipine m/s, q part, fumar 17.0 parts, neointhyl glycol 36.5 parts, trimethylol 101761
All g parts were charged and the temperature was raised to 241 parts C under 4 solid nitrogen atmosphere. Then 7. at the same temperature. After reacting for the left time, /gO''
Cool to 0 and convert hydroquinone into unsaturated polyester (
It was added in an amount of 0.1% by weight based on the solid content.

Furthermore, it was cooled to iao℃ and the non-volatile content was removed. % with styrene. This was named HP-co.

Incidentally, the unsaturated polynisglue has an acid value of 7. o1 hydroxyl value 7
0. The weight average molecular weight was 27.10θ.

U) Unsaturated polyester 11kL3 (hereinafter abbreviated as HP-3) In a reaction vessel similar to that in which the HP-/ was synthesized, 7.3 parts of methylhexahydrophthalic anhydride and 76 parts of isophthalic acid were added.
．． 0 parts, adipic acid llAg parts, fumaric acid tt, o parts,
20 parts of neopentyl glycol, 13.0 parts of hydrogenated bisphenol A, and 10 parts of trimethylol were charged and reacted in a nitrogen atmosphere at 0°C for 3 hours until the acid value was about 0. At this point, the pressure in the system is reduced further by approximately 7
The reaction continued for hours.

After that, the inside of the system was returned to normal pressure and cooled to igo'a,
Cabukol was added in an amount of θ, 1% based on the unsaturated olopolyester (solid content). Then, it was cooled to 720° C. and diluted with methyl methacrylate so that the nonvolatile content was θ%. This was designated as 1-IP-3.

Incidentally, the acid value of the unsaturated polynisder is 7. The s1 hydration group value was iiiy, the weight average molecular weight was ii, and toθ.

Example Unsaturated oropolyester NaI (hereinafter abbreviated as HP-p) Phthalic anhydride 32. Otsube, adipic acid 7g, 7 parts, 77/' acid 3
-0 parts, neopentyl glycol 29. ! ; part, trimethylolpronoson/lI part, pentaeris IJ)
- Prepare 2 parts of Ruco, under nitrogen gas atmosphere: 1llo
The temperature was raised to ``O''. After reacting at the same temperature for about a period of time, the mixture was cooled to /gO''O, and 0.02% by weight of hydroquinone was added based on the unsaturated polyester (solid content). Furthermore, it was cooled to 12θ°C and diluted with styrene so that the nonvolatile content was 0%. This was designated as HP-4.

The unsaturated polyester has an acid value of 9, a hydroxyl value of 23, and an average molecular weight of 9. It was A00.

Example 1 772 parts of mineral spirit and dispersion stabilizer CA were placed in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and cooling tube.
Add 202 parts of O-/ ) and check the temperature? After raising the temperature to θ℃,
The following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

36 parts of methyl methacrylate, S part of isobutyl methacrylate, G part of styrene, 1411 parts of methacrylate, N-n
-butoxymethylacrylamide 170 parts, unsaturated polyester (HP-/) Hiro θ part, dodecylmercaptan θ,
2 parts, 2.0 parts of benzoyl 9-oxide, 0 parts of azobisisobutyronitrile.

After the dropwise addition was completed, 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 is a milky white dispersion with an acid value of 10. θ, water! ! ii
The 2-base value was 4t3, and the non-volatile content was 13.3%.

The obtained non-water composition was sealed with PD-/.

Example 750 parts of mineral spirit and a dispersion stabilizer <AO-3) were added to a reaction vessel similar to that in which PD-/ was synthesized.
After adding A/part and raising the temperature to 90°0, the following mixture of monomer, unsaturated polyester and initiator was added dropwise over 3 hours.

15 parts of unsaturated polyester (HP-2), 37 parts of methyl methacrylate. ! %'ll, 15 parts of N-n-butoxymethylacrylamide, 2 g of styrene, 3 parts of 2-ethylhexyl methacrylate, methacrylic rM/,
−'r part, dodenlumel force putan 0. ．． 2 M, part of penzoyl peroxide, part of azobisisobutyronitrile.

rl, ii Lower 4% temporary penzoylno 9-oxide/
, 2 parts were added and the reaction was carried out at the same temperature for a period of S hours.

The reaction product is a milky white dispersion with an acid value of 7 and a hydroxyl value/g.
1 and non-volatile content II-da, 9%.

The resulting non-aqueous dispersion type resin composition was designated as 4po-2.

Example 3 Mineral spirit 15. t, 5 parts, dispersion stabilizer (AO-2>3
After the temperature was raised to f and wa o'o, the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

1 part of methyl methacrylate, 15 parts of inbutyl methacrylate, 2 parts of styrene, unsaturated polyester (hp
-3l20 parts, Ω-ethylhexyl acrylate dog part,
Nn-butoxymethylacrylamide/2 parts, methacrylic acid/part, benzoyl peroxide 3 parts, azobisisobutyronitrile 0.2 parts.

After the dropwise addition was completed, λ part of benzoyl oxide 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 7. 'l, hydroxyl value 27, and nonvolatile content 1l 11.7%.

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

Example G In the preparation of the above PD-3, a dispersion stabilizer (AO-co)
The reaction was carried out in the same manner except that y-oo parts were replaced with 766.5 parts of mineral spirit. The reaction product was a milky white dispersion with an acid value of 7, an S1 hydroxyl value of 2 g1 and a non-volatile fraction of 5.2%.

The obtained non-aqueous dispersion type resin composition was designated as PD-da.

Example 5 The above pD/ff: Mineral spirit/3'lAi part, dispersion stabilizer CAO-g) were placed in a reaction vessel similar to that used for synthesis.
After adding 301 parts and raising the temperature to 90'O, 11 portions of the following monomer, unsaturated 4·o ester and initiator mixture were added over 3 hours.

3 parts of methyl methacrylate, 6 parts of inbutyl methacrylate, unsaturated polyester (HP-'A, 25i,
77 parts of Nt-butoxymethylacrylamide, 2 g of styrene, 3 parts of benzoyl peroxide, 0.2 parts of azobisin butyronitrile.

After the dropwise addition was completed, 7.2 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 an acid value of 7, a hydroxyl value of 37, and a non-volatile content of lI! It was f,o%.

The obtained non-aqueous dispersion type resin composition was PD-, 5-bound.

Comparative Example/In Example 5, unsaturated polyester (HP-3
) and N-t-butoxymethylacrylamide,
The reaction was carried out in the same manner except that 1 part of methyl methacrylate, 1 part of styrene, and 1 part of ethyl acrylate were added as monomer components. The reaction product is a milky white dispersion with an acid value of 3, a hydroxyl value of ivy, and a nonvolatile content of ty.
-11,g%.

The obtained non-aqueous dispersion type resin composition was designated as PD-B.

Comparative Example U In the above Example λ, 730 parts of mineral spirit was added to 7 parts VC, dispersion stabilizer (AO-, ?) 2 parts/part money,
It was replaced with 277 parts of a soybean oil-modified alkyd resin solution having an acid value of 10%, a hydroxyl value of 10%, an oil length of 30%, and a non-volatile content of 0%. Using a nail, the following monomer 191 compound and an initiator mixture were mixed and reacted in the same manner. Methyl methacrylate 37.5
1 part, 3 parts of ethyl methacrylate, 70 parts of ethyl acrylate, 70 parts of a-hydroxyethyl methacrylate, 3 g parts of styrene, methacrylic v/1, 1B, penzoyl peroxide/part.

The reaction product is a milky white dispersion with an acid value io, g, a hydroxyl value 76 and a non-volatile content lI! i, 7%.

The obtained non-aqueous dispersion type resin composition f: was designated as PD-7.

The non-aqueous dispersion type resin compositions of the present invention (PD-/~3) and comparative examples (PD-A~7) obtained as described above were layered on mild steel) Ji (0, gX'70yJ/! The seeds were air-sprayed to a heart thickness of 30 to 35 microns, left at room temperature for 20 minutes, and then heat-dried at 760° C. for 20 minutes.

The results of the coating film performance comparison test of the obtained test pieces are shown in Table 7.

(Note/) Visual judgment ○Includes Bright × Opaque (Note 2) Visual judgment ○No yellowing × Yellowing (Note 3) Mitsubishi Lead Fiber Un
Using i, apply it to the paint film at an angle of t5° and press lightly forward until it has a hardness of lead that leaves no traces of lead on the paint film.

(Note) Goban tape peeling test.

(Note 5) Based on Erichsen testing machine.

(Note B) According to JIS-5lIoθ, B, /3.38 method.

(Note 7) Moisture resistance test <SOoo, 97%R1-1<)
/, 20 hours later, Goban's tapeno crites.

◎ 100/10θ~9! ;/100 0 9g/10θ~g! ;/100 △ glI/100~Otsu θ/100 -Z-
After 700 hours of testing with 2377), the cross-cut portion was peeled off.

◎ (Peeling width: one width) θ~/, 0 throat○ (#:#
) /, /~λ, OtamΔC〃:#), 2. /~3
．． 0III+Ix (tt:s)a, /1ryn or more (Note 9) Water resistance: After immersion in water flowing at θ℃ for s days,
Double eye tape... crit test.

◎ /θ0/100~Zo left/100 0 9'/-/100~♂J7// 00Δ g<ti
ioo~OtsuO/10θX! ;9/100~0/100 (Note 10) Each non-aqueous dispersion type resin composition (in the comparative example, melamine resin was mixed) was kept in a constant temperature bath at 3θ°C, and the particles were It indicates the number of days until changes such as sedimentation, phase separation, or significant increase in viscosity are observed.

It is clear from the comparative test results that the coating film obtained from the non-aqueous dispersion type resin composition of the present invention has excellent transparency, no yellowing, and good hardness, flexibility, Wi impact resistance, and moisture resistance. properties, water resistance,
The secondary compactness after the salt spray resistance test was excellent in non-electrification, and the storage stability of the composition was also excellent in non-electrification.

Claims (1)

[Claims] (1) Monomers (1) to 6ψ are soluble but can be obtained from solvent-inbathable unsaturated 4,o-polynisglu, monomer 011) and monomer jV). In an aliphatic hydrocarbon solvent in which the polyester-modified vinyl copolymer is insoluble, (llrχ
, β-monoethylenically unsaturated Cal? a hydroxyalkyl ester monomer of
- Solvent-soluble vinyl resin dispersion stabilizer obtained by copolymerizing monoethylenically unsaturated monomers - #30~g
In the presence of θ, (α,β-monoethylenically unsaturated carcinamide N-alcogysimethylated monomer and Qψ(α other than l),
, β-monoethylenically unsaturated monomer, 50% to 93% double fluorescent compound, (alα, β-unsaturated dicarboxylic acid, (b) acid components other than (al) and (C) Mixture with 5 to 50% by weight of solvent-unbathable non-amorphous olopolyester obtained from polyhydric alcohol...-70 to 2O
A non-aqueous dispersion type resin composition of a polyvarnish modified vinyl polymer obtained by total graft polymerization with N-1f%. (The two solvent-soluble vinyl resin dispersion stabilizers are (a) α,
β-monoethylenic non-Ma 7Fo Cal? 11m of hydroxyargyl esgul 10 amount of acid...3~
/S city silkworm%, (b) General formula % formula % [In the formula, R is H or CH3, n represents an integer from O to /g] α,β-monoethylenically unsaturated monomer ・・
and (c) α, β-monoethylenically unsaturated monomers other than the above (a) and (b) 3 to 77 wt. - A non-aqueous dispersion type resin composition according to claim (1), which is a copolymer obtained from the following. (3) R ■ α,β-monoethylenically unsaturated monomer represented by the general formula CH2=C-C00CnH2,+, suethylhexyl (meth)acrylate, n-octyl (meth)
2. The non-aqueous dispersion resin composition according to claim 2, which is at least seven compounds selected from acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. (ri) The N-alkoxymethylated monomer of the above 1i11α,β-monoethylenically unsaturated carboxylic acid amide and the α,β-monoethylenically unsaturated monomer other than the above) are the former (15-25%, while the latter was '75-
A non-aqueous dispersion type resin composition according to claim 1, which is a monomer mixture in a proportion of 95% by weight. (b) A condensation reaction product obtained from 29 to 9 weight % of acid components other than (a) and 30 to 70 weight % of (C1 polyhydric alcohol) (non-aqueous dispersion type resin composition according to item C).