JPH03239702A - Production of nonaqueous resin dispersion composition, and nonaqueous resin dispersion composition and containing material produced thereby - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for a repair coating agent excellent in stability, weathering resistance, water resistance, curability, etc., by polymerizing a specified monomer in a solution prepared by dissolving a polysiloxane resin having specified reactive organic groups in a aliphatic hydrocarbon solvent. CONSTITUTION:A monomer which can dissolve in a solvent based on aliphatic hydrocarbons (e.g. mineral terpene, a product of Showa-Shell Petroleum Co.) before being polymerized but cannot dissolve after being polymerized into a polymer (e.g. methyl methacrylate or ethyl acrylate) is polymerized in a solution prepared by dissolving a polysiloxane resin having 5-30wt.% hydrolyzable reactive organic groups in the molecule (e.g. methoxylated methylphenylpolysiloxane resin) in that solvent.

Description

[Detailed description of the invention] (Industrial application field) The present invention provides a method for producing a non-aqueous dispersible resin composition.

The present invention relates to a non-water-dispersible resin composition produced by the method and a paint containing the composition.

(Prior Art) Paints used for mortar, slate, concrete, etc. for building exteriors are required to have a high degree of durability, that is, water resistance, weather resistance, moisture resistance, and alkali resistance. Paints that use acrylic resin, a copolymer whose main component is acrylic ester or methacrylic ester, are used for building exteriors because they have excellent workability and good durability. ing. However, since a large amount of thinner containing toluene and xylene is used in single-packing, there is a problem that it is harmful to the human body and the environment. It was a cabinet. When this paint is used to repair exterior paint films, toluene and xylene, which have strong dissolving power, soak the underlying paint film and cause lifting phenomena, making it difficult to use for repair purposes.

Therefore, a paint using an acrylic emulsion resin using water as a medium has been proposed as a paint with improved repairability and toxicity to the human body and the environment.

This paint has a durability of 9% but poor water resistance and moisture resistance.
It is considered difficult to put it into practical use as a building exterior.

As a resin that combines the features of both the above-mentioned solvent-based acrylic resin and acrylic emulsion resin.

There are non-water dispersible acrylic resins. This non-water-dispersible acrylic resin uses an aliphatic hydrocarbon or a solution mainly composed of an aliphatic hydrocarbon as a solvent, so it is less harmful to the human body and the environment. -! Also, since it does not contain strong emulsifiers, it has very good durability.

However, their durability is insufficient compared to solvent-based acrylic urethane paints and fluororesin paints, and there is a need to improve their durability.

On the other hand, polysiloxane resin is a resin with excellent heat resistance and weather resistance, and attempts have been made to take advantage of its characteristics by acrylic modification and use as a paint resin. Tokuko Showa 6
No. 3-443 describes a method of curing a silyl group-containing acrylic resin under an acidic catalyst and/or a basic catalyst.

This method has the disadvantage of using large amounts of toluene and xylene, which are highly toxic like solvent-based acrylic resins. 1*,% Japanese Patent Publication No. 116605/1986 discloses that acrylic ester and/or methacrylic ester monomers are polymerized in the presence of an alkoxypolysiloxane resin,
A method of making a non-water dispersible acrylic resin is disclosed. According to this method, a non-water dispersible resin can be obtained, but 9
Dispersion stability is poor and weather resistance is also insufficient. Also.

JP-A-47-4084 discloses a method for producing a non-water-dispersible acrylic resin using a siloxane organic copolymer as a dispersant. However, the non-water dispersible acrylic resin obtained by this method has poor dispersion stability and curability.

(Problems to be Solved by the Invention) The present invention solves the drawbacks of the prior art as described above, and has excellent weather resistance and hardening properties9, and is less harmful to the human body and the environment9.
An object of the present invention is to provide a non-aqueous dispersible resin composition that has excellent dispersion stability and is useful as a repair paint, a method for producing the same, and a paint.

(Means for Solving the Problems) The present invention solves the above problems by using, as a dispersant, a polysiloxane resin in which a specific amount of hydrolyzably reactive organic groups is distributed in nine molecules.

That is, 1 the present invention is a solution in which a polysiloxane resin having 5 to 30% by weight of hydrolyzable reactive organic groups in one molecule is dissolved in a solvent containing an aliphatic hydrocarbon as a main component. A method for producing a non-water-dispersible resin composition, which comprises polymerizing a monomer that dissolves before polymerization but does not dissolve after one polymerization, and a non-water-dispersible resin composition produced by the method. and a paint containing the composition.

In the method of the present invention, a polysiloxane resin having 5 to 30 by weight of hydrolyzable reactive organic groups in the molecule is used as a dispersant. here.

The hydrolyzable reactive organic group has 9, e.g. 1 to 1 carbon atom.
6 flukoxy group, a'/ /l/ having 1 to 6 carbon atoms
, a toxy group, an oximo group having 1 to 14 carbon atoms, etc., and an alkoxy group such as a methoxy group is preferable from the viewpoint of curability. As the polysiloxane resin having such an organic group, one composed of generally known inert monovalent hydrocarbon groups is preferable. The -valent hydrocarbon group is, for example, 9.

Alkyl groups such as methyl group, ethyl group, propyl group, inglovir group, butyl group, inobutyl group, aluminum group, hexful group, cycloalkyl group such as 7 clobe/tyl group, cyclohexyl group, aryl group such as phenyl group, Examples include aralkyl groups such as benzyl groups and alkaryl groups such as tolyl groups.

In accordance with the present invention, the content of hydrolyzable reactive organic groups is required to be 5 to 30% by weight. If the amount is more than 30 weight, the reactivity becomes too high and the stability of the resin deteriorates, and if it is less than 5 weight, the curability is poor.

As the polysiloxane resin that produces a stable non-aqueous dispersible resin composition, a methylphenyl polysiloxane resin having a methyl group and a phenyl group as the -valent hydrocarbon group is used, and the polysiloxane resin has a molecular weight of about 500 to 20,000°, particularly 700 to 15,000°.
Those having an average molecular weight within the range of are preferred. Those having an alkyl group with a large number of carbon atoms tend to deteriorate the curability of the coating film, and those with an average molecular weight of about 500
When the amount is less than 1, the acrylic resins that are dispersed in one form aggregate together.

If the molecular weight exceeds about 20,000 because precipitation is likely to occur, the solubility in a solvent will decrease and the dispersion stability will deteriorate. What is the average molecule i in the present invention?

This is a measurement value using the GPC method.

Such a reactive organic group-containing polysiloxane resin is produced by condensing trifunctional silane and difunctional silane containing silane as a main component of gold by a known method. Examples of such seven raw materials include methyltrimethoxysilane, methyltriethoxysilane, and methyltributoxysilane.

Trifunctional silanes such as ethyltritoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane/, phthyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrisilanol, methyltrisilanol, dimethyldimethoxysilane/ , dimethyljethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, methylphenyldimethoxysilane, diphenyljethoxysilane and the like.

A specific example of the reactive organic group-containing polysiloxane resin is an alkoxy group-containing methylphenyl polysiloxane resin KR9218 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Average molecular weight within 1,000. methoxy equivalent weight 210 (methoxy group content 15%)), KR217 (manufactured by Shin-Etsu Chemical Co., Ltd., average molecular weight approximately 800, methoxy group content 25), and others from Talk Silicone ■ and Nippon Unicar ■. Commercially available polysiloxane resins containing reactive organic groups can be used.

In the present invention, the polysiloxane resin described above is used as a dispersant, dissolved in a solvent containing an aliphatic hydrocarbon as a main component, and monomers are polymerized in the solution. Here, the aliphatic hydrocarbon solvents that can be used include linear hydrocarbons such as pentane, hexane, heptane, and octane, cyclic hydrocarbons such as cyclohexane, methylcyclohexane, and cycloheptane, and mixed solvents. Examples include mineral turpentine (manufactured by Showa Shell Sekiyu) and Isopar (manufactured by Etsuso). Along with these aliphatic hydrocarbons, aromatic hydrocarbons such as toluene/xylene, ethyl acetate,
Esters such as butyl acetate.

Ketones such as methyl ethyl ketone and methyl imbutyl ketone, and alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol can also be used in combination.

Generally, a solvent containing an aliphatic hydrocarbon as a main component and a mixture of aromatic hydrocarbons, esters, ketones, or alcohols within a range that does not disturb the dispersion of the non-water-dispersible resin is used.

As the monomer to be polymerized in the presence of the reactive organic group-containing polysiloxane resin dissolved in the above-mentioned solvent containing an aliphatic hydrocarbon as a main component, any radically polymerizable double bond-containing compound 1 such as acrylic Examples include acid esters, methacrylic esters, and/or radically polymerizable unsaturated double bond-containing compounds copolymerizable with these. Specific examples of such monomers include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and cyclohexyl acrylate. and the corresponding methacrylic esters, 2-hydroxyethyl acrylate,
Hydroxyl group-containing acrylic esters such as hydroxypropyl acrylate, corresponding hydroxyl group-containing methacrylic esters, and dimethylaminoethyl acrylate.

Amino group-containing acrylic esters such as diethylaminoethyl acrylate, and corresponding amino group-containing methacrylic esters and acrylic acid.

Methacrylic! ! ! , Malay/acid, fumaric acid and other acids.

Styrene, substituted styrenes such as α-methylstyrene, r
-Methacryloxypropyltrimethoxysilane, vinyl) Radically polymerizable compounds containing alkoxy 7-rane groups such as IJ methoxysilane, acrylonitrile, vinyl acetate,
Fumaric acid dibutyl ester.

Examples include fumaric acid monobutyl ester.

These monomers can be used alone or in combination of two or more. Among them, when a radically polymerizable compound containing an alkoxysilane group is used, the 9 polymer and the dispersant bond,
It is preferable because it can improve the stability of the resin and the transparency of the coating film when made into a clear paint.

The ratio of the dispersant to the monomer to be polymerized is preferably 10/90 to 60/40 (former/latter (weight ratio)). If it is less than 10,790, it is difficult to obtain a heavy film with good weather resistance. Spread. If it exceeds 60/40, the drying properties of the coating film, which is a characteristic of 9-dispersion resins, tend to deteriorate.

Bipolymerization is usually carried out in the presence of a monopolymerization initiator.

A suitable polymerization initiator is benzoyl peroxide.

Dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, Z5-di(bero-dibenzoate) hexyne-3,1,3-bis(tert-butylberoxyisopropyl)benzene, lauroyl peroxide,
Peracetic acid @ tert-butyl, 2,5-dimethyl-25-di(tert-butylperoxy)hexyne-3,2,5
-dimethyl-25-di(tert-phthylberoxy)
hexane, perbenzoin, tert-butyl, tert
There are organic peroxides such as -butyl peroxy 2-hexanoate, methyl ethyl ketonovel oxide, and methyl cyclohexanone peroxide, and azo compounds such as azobisisobutyronitrile, and one or more of these can be used. The amount of the polymerization initiator to be used depends on the desired molecular weight of the dipolymer, but it is preferably used in an amount of 0.1 to 4.0% by weight based on the monomer.

When the non-water-dispersible resin composition of the present invention is used as a coating material, a known curing catalyst may be used in combination to promote the complete condensation of two reactive organic groups. for example.

Examples include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, tin oleate, tin stearate, tin palmitate, and zinc octylate. The blending amount of these components is preferably 0,001 to 10% by weight based on the resin.

The non-aqueous dispersible resin composition obtained by the method of the present invention is
Although it is useful as a clear paint, it can also be made into an enamel paint by adding colored pigments such as titanium white and carbon black, extender pigments such as barium sulfate and barium carbonate, and a solvent. As a method for producing an enamel paint, known methods can be applied.9 For example, a roll, a mill, a disperser, etc. can be used. It was a cabinet. Pigment dispersant.

Various additives such as leveling agents can also be added during or after forming the coating.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Among the nine examples, "part" and "part" indicate "part by weight" and "part by weight", respectively, unless otherwise specified.

Example 1 Production of a non-water dispersible resin composition In a flask equipped with a stirrer, a reflux condenser and a thermometer, 300 parts of mineral turpentine (manufactured by Showa Shell Sekiyu Co., Ltd.) and KR9218 (Shin-Etsu Co., Ltd.) as a methoxy group-containing methylphenyl polysiloxane resin were added. Manufactured by Kagaku Kogyo Co., Ltd., methoxy equivalent: 210
．． Methoxy group content: 15%, average molecular weight: 1000%) 8
I prepared 0 copies. After raising the temperature to 100°C, a mixture of 160 parts of methyl methacrylate, 160 parts of ethyl acrylate, and 1 part of azobisisobutyronitrile was added dropwise over a period of 3 hours, and the temperature was kept for 1 hour even after the completion of 9 drops. A solution prepared by dissolving 2 parts of butyl peroxy 2-ethylhexanoate in 50 parts of mineral turpentine was added dropwise, and the mixture was kept warm for 3 hours to complete 9 polymerizations. The heating residue was adjusted to 50%, the viscosity was 5000c/tepoise, and the average particle size was 70%.
A milky white dispersion of 0 nm was obtained. Even if left at room temperature for 3 months.

No sedimentation of particles was observed.

Example 2 Production of a non-aqueous dispersible resin composition Using the same dispersant as in Example 1, two drops of monomer were polymerized using 140 parts of methyl methacrylate and 14 parts of ethyl acrylate.
Polymerization was carried out in the same manner except that 40 parts of silane and 40 parts of γ-methacryloxypropyltrimethoxysilane were used. Heating residue 5o
qIb, viscosity 8000 centipoise, average particle size 600
A milky white dispersion of nm was obtained. No sedimentation of particles was observed even after being left at room temperature for 3 months.

Example 3 Production of non-water-dispersible resin composition Methoxy group-containing methylphenylpolysiloxane resin KR217 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a dispersant.

Polymerization was carried out in the same manner as in Example 1, except that methoxy group content 25% and average molecular weight 5OO) were used. Heating residue: 50 or so, viscosity: 7000 centimeters/chipoise, average particle size: 650
A milky white dispersion of nm was obtained.

No sedimentation of particles was observed even after being left at room temperature for 3 months.

Comparative Example 1 (1) Synthesis of acrylic resin dispersant Using the same apparatus as in Example 1, 60 parts of mineral turpentine was charged, and after raising the temperature to 100°C, acrylic resin dispersant was used. ! 2
-40 parts of ethylhexyl, 80 parts of isobutyl methacrylate
3 parts, 60 parts of styrene, 20 parts of 2-hydroxyethyl methacrylate and 0.4 parts of azobisisobutyronitrile.
It was added dropwise over a period of time, and after keeping it warm for 1 hour, a solution prepared by dissolving 1 part of tert-butylperoxy 2-ethylhexanoate in 50 parts of mineral turpentine was added dropwise, and it was kept at 120°C for 2 hours to complete one polymerization. . The viscosity of the resin adjusted to have a heating residue of 50% was Z (Gardner method).

(2) 200 parts of the dispersant prepared in (1) above and 50 s of mineral turpentine were placed in a synthetic flask made of non-aqueous dispersible resin, and the temperature was raised to 100°C.
80 parts of methyl methacrylate, 40 parts of styrene, 28 parts of ethyl acrylate, 2 parts of methacrylic acid, methacrylic M2-
30 parts of hydroxyethyl and 0.4 parts of azobisisobutyronitrile were added dropwise over 3 hours, and the same procedure as in (1) above was carried out.

A milky white dispersion having a heating residue of 50%, a viscosity of 5000 centivoids, and an average particle size of 600 nm was obtained. No sedimentation of particles was observed even after being left at room temperature for 3 months.

Comparative Example 2 Synthesis of dispersant Tetrabutoxysilane monomer was reacted with water under an acid catalyst to undergo hydrolysis and condensation reaction, and then diluted with n-butyl alcohol to obtain butoxypolysiloxane with an average molecular weight of 20.000. fc (Atoxy group content 40 or more)
.

240 parts of the above-mentioned dispersant (1) and 300 parts of mineral turpentine were charged into a synthetic flask for a non-water-dispersible resin composition, and the temperature was raised to 90°C.

35 parts of styrene, 73 parts of methyl methacrylate, 73 ml of methyl acrylate, 76 parts of methyl acrylate.

Acrylic a! A mixture of 46 parts of 2-hydroxyethyl and 1.2 parts of 1-butylperoxy (2-ethylhexanony) was added dropwise over 3 hours. Thereafter, operations were carried out in the same manner as in Example 1 to obtain a colored dispersion having a heating residue of 50 seconds, a viscosity of 10.000 centipoise, and an average particle size of 800 nm. However, this dispersion had poor stability, and the resin turned into cake after one month at room temperature.

Evaluation of coating film performance Titanium white R-930 (manufactured by Hara Sangyo Co., Ltd.) 33.3 per 100 parts of the resin obtained in Examples 1 to 3 and Comparative Examples 1 to 2
and 20 parts of mineral turpentine were kneaded to prepare a white coating group.

To the paints of Examples 1 to 3 and Comparative Example 2, 0.1 part of dibutyltin dilaurate was added to 100 parts of the resin. Polyisocyanate (Coronate EH, manufactured by Nippon Polysilethane Co., Ltd.) was added to the paint of Comparative Example 1 (OH group/NCO
(Molar ratio = 1/1) and diluted with mineral turpentine to a volume of 18 seconds using a Ford cup ◆4. Paint film thickness is 2
A treated steel plate (Bonderite ◆144, manufactured by Nippon Test Panel Co., Ltd.) was spray-painted to a thickness of 5 to 35 μm. The test was carried out in a curing room (23°C, relative humidity 709G) for 2 hours.
I did this after leaving it for a week. The evaluation results are shown in Table 1.

Among them, evaluation was performed using the following method.

(a) Gloss 60°# according to JIS K 5400! , the surface reflectance was measured.

(b3 Pencil hardness Measured by pencil hardness scratch method after 2 days and 14 days according to JIS K 5400.

(C1 water resistance After being immersed in tap water for one week, the appearance was visually judged.

(di After being immersed in an alkali-resistant saturated calcium hydroxide aqueous solution for one week, the appearance was visually judged.

(e) Use an accelerated weather resistance sunshine weather meter to meet JIS-5.
The gloss was measured under the conditions of 400°C and the gloss retention rate after 2000 hours of irradiation was determined.

From the results shown in Table 1, it is clear that the paint of the present invention is more stable and has significantly improved weather resistance than the conventional paint shown in Comparative Example.

(Effect of the invention)

Claims (1)

[Scope of Claims] 1. In a solution in which a polysiloxane resin having 5 to 30% by weight of hydrolyzable reactive organic groups in the molecule is dissolved in a solvent mainly composed of aliphatic hydrocarbons, On the other hand, a method for producing a non-water-dispersible resin composition, which comprises polymerizing a monomer that dissolves before polymerization but does not dissolve in the polymer after polymerization. 2. The method for producing a non-water-dispersible resin composition according to claim 1, wherein the polysiloxane resin is obtained by condensing raw materials containing trifunctional silane and difunctional silane as main components. 3. The method for producing a non-aqueous dispersible resin composition according to claim 1 or 2, wherein the polysiloxane resin is a methylphenyl polysiloxane resin. 4. A non-aqueous dispersible resin composition produced by the method according to claim 1, 2 or 3. 5. A coating material comprising the non-water-dispersible resin composition according to claim 4. 6. The paint according to claim 5, further comprising a curing catalyst.