JP2001254020A - Non-aqueous dispersible resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous dispersible resin composition excellent in preservation stability, having an extended pot life and excellent also in weather resistance, stain resistance and gloss properties. SOLUTION: The non-aqueous dispersible resin composition comprises an organic solvent (A), a specific silicate oligomer (B) soluble in the organic solvent (A), a resin-based dispersant (C) soluble in the organic solvent (A) and a polymer (D) insoluble in the organic solvent (A) obtained from a radically unsaturated monomer (d) soluble in the organic solvent (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous dispersion type resin composition, and more particularly to a non-aqueous dispersion type resin composition having excellent storage stability and low odor during construction, having a long pot life, and having weather resistance and resistance. The present invention relates to a non-aqueous dispersion type resin composition which forms a coating film having excellent stainability and glossiness.

[0002]

2. Description of the Related Art Conventionally, paints used for building exteriors have been required to have high durability, that is, weather resistance, water resistance, moisture resistance, alkali resistance, acid resistance, and the like. Among them, copolymers using acrylic acid ester and methacrylic acid ester as main components, so-called solvent-type acrylic resin, are used for architectural exteriors because of their excellent coating workability and good durability. ing.

[0003] However, since the paint uses a large amount of an organic solvent containing toluene or xylene as a main component at the time of actual coating, it is regarded as a problem from the viewpoint of safety to human body, air pollution, environmental problems, and the like. In particular, paints in which the amount of the harmful organic solvent used is reduced as much as possible have been desired.

[0004] Further, when the paint using the solvent-type acrylic resin is used as a repair of an exterior coating film, a lifting phenomenon or the like of an undercoat film occurs due to a strong dissolving power of toluene or xylene, and the repair is performed. It is difficult to use in terms of workability, and improvement is awaited.

[0005] On the other hand, as a paint which has improved the problem of repairability and harmfulness to the human body and the environment, a paint using an acrylic emulsion resin using water as a medium, and a silicone modification for imparting high functionality to the paint. There is also a paint using a water-based acrylic silicone emulsion-based resin which has been improved by this method, but it still has poor durability, especially water resistance and moisture resistance, and has many problems in practical use.

A non-aqueous dispersion type acrylic resin is a resin having an intermediate performance between the above-mentioned solvent type acrylic resin and water type acrylic emulsion type resin. Since a solvent containing an aromatic hydrocarbon as a main component is used, it is less harmful to the human body and the environment and less lifting phenomenon than a conventional solvent-based acrylic resin. In addition, since it does not contain an emulsifier having a strong hydrophilicity as in a paint using a water-based acrylic emulsion resin, the durability is good.

[0007] As described above, the non-aqueous dispersion type acrylic resin paint has such characteristics. However, in terms of weather resistance, it does not reach the solvent type acrylic urethane resin paint or the fluororesin paint, and has further characteristics. Improvement has been demanded.

As a countermeasure, for example, Japanese Patent Application Laid-Open
-75502, JP-A-7-138303, JP-A-2-64110, JP-A-7-97
Japanese Patent Publication No. 402 proposes a paint made of a silicone-modified resin by imparting a hydrolyzable silyl group to a resin dispersant or a core particle resin portion in a non-aqueous dispersion type resin composition. JP-A-8-127603 discloses that in the presence of a dispersant, at least two
There has been proposed a non-aqueous dispersion obtained by hydrolyzing a silicon compound having a hydrolyzable group bonded to a silicon atom, and subjecting a vinyl monomer to non-aqueous dispersion polymerization in the presence of an organic solvent.

[0009]

However, the present inventor has studied in detail that the non-aqueous dispersion resins disclosed in (1) to (4) have low odor, chemical resistance, flexibility and the like during construction. Although excellent, the dust resistance in the outdoors, exhaust gas, stain resistance to dirt due to raindrops, etc. is not sufficient, the above disclosed technology, although the weather resistance is somewhat excellent, storage stability is still not satisfactory, Further, there is a problem that a pot life cannot be obtained for a long time when a curing agent is compounded.

[0010] In addition, when used for building interior and exterior, the glossiness of the enamel coating film is required. However, in the techniques disclosed in the above (1), the glossiness is reduced upon enamelling, and the storage stability and pot life are also insufficient. And further improvement is desired. Under such circumstances, the present invention provides a non-aqueous dispersion type resin composition having a long pot life, storage stability, stain resistance, weather resistance, and glossiness, and a paint using the same. To provide.

[0011]

Means for Solving the Problems However, as a result of intensive studies to solve such problems, the present inventor has found that organic solvent (A) and the following general formula (1) soluble in organic solvent (A): (B), a resin-based dispersant (C) soluble in the organic solvent (A), and a radically unsaturated monomer (d) soluble in the organic solvent (A). The present inventors have found that the obtained non-aqueous dispersion type resin composition comprising the polymer (D) insoluble in the organic solvent (A) meets the above object, and completed the present invention.

[0012]

Embedded image (Here, R is either an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is an integer of 2 to 30.)

In the present invention, the silicate oligomer (B) represented by the general formula (1) soluble in the organic solvent (A) and the organic solvent (A) are soluble in the organic solvent (A). A non-aqueous dispersion type resin composition obtained by polymerizing a radically unsaturated monomer (d) in the presence of a resin dispersant (C);
Alternatively, after the radically unsaturated monomer (d) is polymerized in the organic solvent (A) in the presence of a resin-based dispersant (C) soluble in the organic solvent (A), (A) Soluble silicate oligomer (B) represented by the general formula (1)
Is preferably a non-aqueous dispersion type resin composition. In the present invention, it is preferable that an acid-modified alkyd resin (E) is further contained in view of improving pigment dispersibility, that is, glossiness as a coating film.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The organic solvent (A) used in the present invention is a petroleum-based mixed solvent or an organic solvent (A) containing an aliphatic hydrocarbon as a main component. Examples of such a petroleum-based mixed solvent include mineral spirit and mineral thinner. , Petroleum spirit, white spirit, mineral terpen, paraffin, isoparaffin, naphthene and the like. Among them, one or two kinds are main components, but linear fatty acids such as pentane, hexane, heptane, octane, decane, etc. Aromatic hydrocarbons, cyclohexane, methylcyclohexane, ethylcyclohexane, it is also possible to add a cycloaliphatic hydrocarbon such as cycloheptane, in the present invention,
By using such an organic solvent (A) containing a petroleum-based mixed solvent or an aliphatic hydrocarbon as a main component, it is possible to reduce odor and to prevent lifting at the time of repair. .

To the extent that the effects of the present invention are not impaired, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, toluene It is also possible to add aromatic hydrocarbons such as xylene and xylene. However, the weight ratio of the petroleum-based mixed solvent in the organic solvent (A) is 70% or more of the above environment and the surface of the undercoat film repair. It is preferable that

The silicate oligomer (B) used in the present invention is soluble in the organic solvent (A).
It has a structure represented by the general formula (1).
In the general formula (1), n is an integer of 2 to 30,
In particular, n = 4 to 8 is preferable, and components having n = 4 to 8 as a main component and n = 2 to 3 or n = 9 to 20 can be further contained.

The method for producing the silicate oligomer (B) is not particularly limited. For example, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane or tetraphenoxysilane are hydrolyzed and condensed. It can be obtained by: n can be adjusted by controlling the hydrolysis rate in this case.

The hydrolysis and condensation can be carried out by a known method. For example, the reaction is usually carried out at room temperature by adding a predetermined amount of water to the above tetraalkoxysilane and distilling off by-product alcohol in the presence of an acid catalyst. The reaction is carried out at about 100 ° C.
By this reaction, the alkoxysilane is hydrolyzed and further condensed to obtain a liquid silicate oligomer (B) represented by the general formula (1).

The silicate oligomer (B) thus obtained usually contains about 2 to 10% by weight of a monomer. When the monomer is contained, the storage stability of the coating agent composition is lacking, the viscosity increases during storage, and it becomes difficult to form a thin film. Therefore, the monomer content is 1% by weight or less,
The removal of the monomer is preferably carried out by flash distillation or vacuum distillation so that the content becomes preferably 0.3% by weight or less.

The resin-based dispersant (C) used in the present invention is a vinyl copolymer soluble in the organic solvent (A). Examples of the vinyl copolymer include (meth) acrylic acid esters and the like. And a vinyl copolymer of a radically unsaturated monomer (c) having as a main component. The content of the (meth) acrylate in the radically unsaturated monomer (c) is preferably from 70 to 100% by weight, more preferably from 80 to 100% by weight. If the content is less than 70% by weight, it becomes insoluble in the organic solvent (A), which is not preferable.

Specific examples of the (meth) acrylate include n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate. ) Acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. (Meth) acrylic acid esters having an alkyl group of the number 4 to 22;
More than one species is used.

In the polymerization of such a vinyl copolymer,
As long as the solubility in the organic solvent is not impaired, methyl (meth) acrylate, ethyl (meth) acrylate, n-
(Meth) acrylates having an alkyl group having 3 or less carbon atoms, such as propyl (meth) acrylate and iso-propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate,
8-hydroxyoctyl (meth) acrylate, 10-
A (meth) acrylic acid ester containing a hydroxyl group such as hydroxydecyl (meth) acrylate or a (meth) acrylic acid ester containing an epoxy group, a halide group, a nitrile group, or an amide group can be added and copolymerized.

Further, other radically unsaturated monomers (c) include styrene, vinyl toluene, (meth) acrylonitrile, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acryl chloride, vinyl acetate, and vinyl chloride. , Vinylidene chloride, vinyl pyridine, vinyl pyrrolidone, methyl vinyl ketone, acrylamide, acetoacetylated (meth) acrylate and the like can be used in combination.

In the present invention, the resin-based dispersant (C) is
It is preferable to contain a hydrolyzable silyl group in terms of weather resistance, stain resistance, chemical resistance, solvent resistance, etc., and when the vinyl copolymer is polymerized, the radically unsaturated monomer (c)
The hydrolyzable silyl group can be contained by blending and copolymerizing the hydrolyzable silyl group-containing monomer (c1) as a component.

The content of the hydrolyzable silyl group-containing monomer (c1) in the radically unsaturated monomer (c) is preferably 0.01 to 40% by weight, more preferably 0.1 to 40% by weight. -20% by weight. The content ratio is 0.0
If it is less than 1% by weight, the crosslinking property is poor, the weather resistance is poor, and
Exceeding the weight% is undesirable because the gelation becomes faster and unstable.

The hydrolyzable silyl group-containing monomer (c)
Examples of 1) include, for example, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyl Triethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethyl Ethoxysilane, γ
-(Meth) acryloxypropyltrichlorosilane, γ
-(Meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyldimethylchlorosilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ -(Meth) acryloxypropyltributoxysilane, γ- (meth) acryloxybutyltrimethoxysilane, γ- (meth) acryloxypentyltrimethoxysilane, γ- (meth) acryloxyhexyltrimethoxysilane, γ- ( (Meth) acryloxyhexyltriethoxysilane, γ- (meth) acryloxyoctyltrimethoxysilane, γ- (meth) acryloxydecyltrimethoxysilane, γ- (meth) acryloxydodecyltrimethoxysilane, γ- (meth) Acryloxyoctadecyltri Tokishishiran and the like, one or more may be used. Among them, γ- (meth) acryloxypropyltrimethoxysilane is particularly preferred.

In the present invention, it is particularly preferable that the resin dispersant (C) contains a hydrolyzable silyl group and an acid group and / or a base in terms of stability, gloss and weather resistance. During the polymerization of the copolymer, the above-mentioned hydrolyzable silyl group-containing monomer (c1), acid group-containing monomer (c2) and / or base-containing monomer are used as radically unsaturated monomer (c) components. It is obtained by blending (c3) and copolymerizing.

The content of the hydrolyzable silyl group-containing monomer (c1) in the radically unsaturated monomer (c) is preferably 0.01 to 40% by weight, more preferably 0.1 to 40% by weight. To 20% by weight of the acid group-containing monomer (c
The content of 2) is preferably from 0.1 to 3% by weight, more preferably from 0.3 to 1% by weight, and the content of the base-containing monomer (c3) is from 0.1 to 3% by weight. %, More preferably 0.3 to 1% by weight.

When the content of the hydrolyzable silyl group-containing monomer (c1) is less than 0.01% by weight, the crosslinking property is poor and the weather resistance is inferior. The content ratio of the acid group-containing monomer (c2) is 0.1%.
If it is less than 1% by weight, the effect of containing (c2) is difficult to obtain, and if it exceeds 3% by weight, resin stability is poor, which is not preferable, and the content of the base-containing monomer (c3) is 0.1%.
If the amount is less than 3% by weight, it is difficult to obtain the effect of containing (c3). If the amount is more than 3% by weight, the resin stability becomes poor.

Examples of the acid group-containing monomer (c2) include
For example, acrylic acid, methacrylic acid, maleic anhydride,
Maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, itaconic anhydride, itaconic acid, monoalkyl itaconate, citraconic anhydride, citraconic acid, crotonic acid, succinic acid, monoalkyl succinate,
(Meth) acryloyloxyethyl succinic acid and the like are used, and one kind or two or more kinds are used. Among them, acrylic acid, methacrylic acid and (meth) acryloyloxyethyl succinic acid are particularly preferred.

The base-containing monomer (c3) includes
For example, dimethylaminoethyl (meth) acrylate,
Diethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, N-vinylimidazole, 2- Methyl-N-vinylimidazole, dimethylallylamine, diallylamine, vinylpyrroline, vinylquinoline, vinylisoquinoline, N, N-dimethylaminoethylvinylether, 2- (N, N-dimethylamino) -4-vinylpyrimidine, trans-
1,2-dipyridylethylene, 3-cinnamoylpyridine, 2-methyl-5-cinnamoylpyridine, 4,6-
Diamino-2-vinyl-5-triazine and the like,
One or more kinds are used. Among them, diethylaminoethyl (meth) acrylate is particularly preferred.

In producing the resin-based dispersant (C), known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization can be used. Solution polymerization that can be directly transferred to the process is most preferable, and such a solution polymerization method will be described below.
It is not limited to this.

The polymerization initiator used in the polymerization includes:
For example, isobutyl peroxide, lauryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, Di-t-butyl peroxide, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutylperoxydicarbonate, di-2
Organic peroxides such as -ethylhexylperoxydicarbonate, t-butylperoxyisobutyrate and the like can also be mentioned, but azobisisobutyronitrile, dimethylazodiisobutyrate, 2,2-azobis (2,
4-dimethylvaleronitrile), 2,2-azobis (2
-Methylbutyronitrile) and the like, and one or more of these may be used. The amount of the polymerization initiator to be used is determined according to the intended molecular weight of the resin-based dispersant (C), and is usually based on 100 parts by weight of the radically unsaturated monomer (c) in total. 0.0
It may be 5 to 10 parts by weight.

The solution polymerization of the resin-based dispersant (C) is carried out in the above-mentioned organic solvent (A), and the total amount of the radically unsaturated monomer (c) is 100 parts by weight of the organic solvent (C). A) is preferably used in an amount of 30 to 600 parts by weight, more preferably 80 to 150 parts by weight. The reaction temperature during the solution polymerization of the resin-based dispersant (C) is usually 50 to 170 ° C.
It is appropriate to use a temperature within the range, and the reaction time is usually about 1 to 18 hours.

In producing the resin dispersant (C) containing a hydrolyzable silyl group of the present invention, the silicate oligomer (B) represented by the general formula (1) is used in the organic solvent (A). It is preferable to polymerize the radically unsaturated monomer (c) containing the hydrolyzable silyl group-containing monomer (c1) in the presence of).

In preparing the resinous dispersant (C) containing a hydrolyzable silyl group and an acid group and / or a base according to the present invention, the compound represented by the general formula (1) In the presence of the silicate oligomer (B) represented by the above formula, the above-mentioned hydrolyzable silyl group-containing monomer (c1), acid group-containing monomer (c2) and / or base-containing monomer (c3)
It is preferred to polymerize a radically unsaturated monomer (c) containing

The amount of the silicate oligomer (B) represented by the general formula (1) is 0.1 to 200 parts by weight based on 100 parts by weight of the total amount of the radically unsaturated monomer (c). And more preferably 10 to 10
0 parts by weight. If the used amount of the silicate oligomer (B) is less than 0.1 part by weight, the stability of the resin-based dispersant (C) becomes poor, and if it exceeds 200 parts by weight, it becomes brittle when formed into a coating film, making it difficult to apply a thick coating. Not preferred.

Further, the organic solvent (A) used in the present invention
Examples of the radically unsaturated monomer (d) soluble in water include the same as the above-mentioned radically unsaturated monomer (c), but when the monomer is monomeric, it is soluble in the organic solvent (A). There is no particular limitation on the radically unsaturated monomer (c) as long as it becomes insoluble as the polymerization proceeds and the polymerizability is excellent. Those having a smaller number of carbon atoms than the carbon number of the body are suitably selected, and in particular, those having an alkyl group having 1 to 8 carbon atoms (meth)
Acrylic esters are selected, but those having a large number of carbon atoms can be selected as long as the effects of the present invention are not impaired.

Further, as the radical unsaturated monomer (d), any of a hydrolyzable silyl group-containing monomer (d1), an acid group-containing monomer (d2) and a base-containing monomer (d3) Or 2
It is preferable from the viewpoints of weather resistance, pigment dispersibility, gloss, and resin stability to contain at least three kinds, preferably three kinds, and the hydrolyzable silyl group-containing monomer (d1) and the acid group-containing monomer ( d
2) As the base-containing monomer (d3), any of the above hydrolyzable silyl group-containing monomer (c1), acid group-containing monomer (c2), and base-containing monomer (c3) Similar ones are used.

The content of the hydrolyzable silyl group-containing monomer (d1) in the radically unsaturated monomer (d) is preferably 0.01 to 50% by weight, more preferably 0.5 to 50% by weight. To 20% by weight of the acid group-containing monomer (d
The content of 2) is preferably 0.02 to 15% by weight, more preferably 0.25 to 4% by weight, and the content of the base-containing monomer (d3) is 0.02 to 15% by weight. %, More preferably 0.25 to 3%.
% By weight.

If the content of the hydrolyzable silyl group-containing monomer (d1) is less than 0.01% by weight, weather resistance and stain resistance will be reduced. If it exceeds 50% by weight, resin stability will be reduced, which is not preferable. , The content ratio of the acid group-containing monomer (d2) is 0.0
If the content is less than 2% by weight, it is difficult to obtain the effect of containing (d2). If the content is more than 15% by weight, the stability of the resin is unfavorably reduced.
When the amount is less than 15% by weight, it is difficult to obtain the effect of containing (d3), and when the amount exceeds 15% by weight, the resin stability is undesirably reduced.

By polymerizing the radically unsaturated monomer (d), a polymer (D) insoluble in the organic solvent (A) is obtained. Thus, in the present invention, a non-aqueous dispersion resin comprising a polymer (D) obtained from an organic solvent (A), a silicate oligomer (B), a resin-based dispersant (C), and a radically unsaturated monomer (d) A composition is obtained.

The non-aqueous dispersion type resin composition comprises a core particle resin portion insoluble in the organic solvent (A) and a resinous dispersant having an affinity for the organic solvent (A). It is. Next, the non-aqueous dispersion type resin composition of the present invention will be described.

The non-aqueous dispersion type resin composition of the present invention comprises a polymer obtained from an organic solvent (A), a silicate oligomer (B), a resin dispersant (C), and a radically unsaturated monomer (d). The production method is not particularly limited as long as it comprises (D), but a particularly preferable method is represented by the general formula (1) which is soluble in the organic solvent (A) in the organic solvent (A). In the presence of a silicate oligomer (B) and a resin-based dispersant (C) soluble in the organic solvent (A),
A method comprising polymerizing a radically unsaturated monomer (d),
After polymerizing the radically unsaturated monomer (d) in the organic solvent (A) in the presence of the resin-based dispersant (C) soluble in the organic solvent (A), the organic solvent (A) ), And a method in which a silicate oligomer (B) represented by the general formula (1), which is soluble in (1), is blended.

In the above method, the silicate oligomer (B) coexisting in the polymerization of the radically unsaturated monomer (d) is present in the resin-based dispersant (C) produced in the presence of the silicate oligomer (B). The silicate oligomer (B) to be used can be used as it is together with the resin-based dispersant (C).

In addition to the coexistence of the silicate oligomer (B) during the polymerization of the radically unsaturated monomer (d), the polymerization of the radically unsaturated monomer (d) is followed by the further addition of the silicate oligomer (B). ) Can also be blended.

As the polymerization method for obtaining the non-aqueous dispersion type resin composition of the present invention, known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization can be used. As in C), solution polymerization is most preferred. The polymerization initiator used in the polymerization may be of the same type as the polymerization initiator used in the polymerization of the resin-based dispersant (C).

The compounding amount of the silicate oligomer (B) is determined based on the total amount of the radical unsaturated monomer (d) and the radical unsaturated monomer (c) constituting the resin dispersant (C). It is preferable to add 5 to 200 parts by weight as a total amount based on 100 parts by weight, more preferably 5 to 100 parts by weight. If the amount is less than 5 parts by weight, the weather resistance and stain resistance are poor, and if it exceeds 200 parts by weight, the coating becomes brittle and difficult to apply thickly.

The radically unsaturated monomer (d) 100
The polymerization initiator is selected from the range of 25 to 400 parts by weight, preferably 70 to 230 parts by weight, as the radically unsaturated monomer (c) constituting the resin-based dispersant (C) with respect to parts by weight. Is appropriately selected from the range of 0.5 to 30 parts by weight. The organic solvent (A) is blended so as to have a solid content of 30 to 80% by weight, preferably 40 to 65% by weight.

As the radically unsaturated monomer (c), 25
When the amount is less than 30 parts by weight or when the solid content is less than 30% by weight, the dispersion stability tends to be poor. If the content exceeds 80% by weight, the viscosity tends to be high, and the workability tends to deteriorate, which is not preferable.

In the polymerization, other additives such as a dispersion stabilizer and a rheology control agent may be used in combination. The polymerization can be carried out by a known method, and the reaction temperature at the time of polymerization is usually suitably in the range of about 50 to 170 ° C, and the reaction time is usually 1 to 1.
It is about 18 hours.

Thus, the non-aqueous dispersion type resin composition of the present invention in which the resin dispersant is bonded to the outer periphery of the core particle resin portion is obtained. However, in the present invention, the acid-modified alkyd resin (E ), And the method for containing the acid-modified alkyd resin (E) is not particularly limited, and the acid-modified alkyd resin (E) can be added at any stage. Among them, in the present invention,
When the radically unsaturated monomer (c) is polymerized during the production of the resin dispersant (C), the acid-modified alkyd resin (E)
Is preferably co-present and contained in the resin-based dispersant (C).

The content of the acid-modified alkyd resin (E) depends on the amount of the radically unsaturated monomer (c) constituting the resin dispersant (C) and the amount of the radically unsaturated monomer constituting the polymer (D). It is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and still more preferably 0.3 to 3% by weight, based on the monomer (d). If the content is less than 0.1% by weight, the effect of improving glossiness is difficult to obtain, and if it exceeds 10% by weight, the varnish is undesirably colored.

Examples of the acid-modified alkyd resin include acid-modified alkyd resins modified with maleic acid, succinic acid, fumaric acid, itaconic acid or anhydrides thereof.
Among them, a maleic anhydride-modified alkyd resin is preferably used.

The particle diameter of the particles of the non-aqueous dispersion type resin composition of the present invention is 0.1 to 10 μm, preferably 0.1 to 1 μm.
It is preferably in the range of m. If the particle size is smaller than this range, special consideration must be given to the production of varnish, and industrial profitability cannot be achieved. On the other hand, if the particle size is larger than this range, the particles swell or aggregate during storage, which is not preferable.

Thus, the non-aqueous resin composition of the present invention comprises an organic solvent (A), a specific silicate oligomer (B), a resin-based dispersant (C), and a radically unsaturated monomer (d). Since it is made of the obtained polymer (D), it has a long pot life, shows excellent effects of storage stability, weather resistance, stain resistance, and glossiness, and further, together with a pigment dispersant and a leveling agent, Titanium white, phthalocyanine blue, carbon black, calcium carbonate, magnesium carbonate, barium sulfate, various silicas, glass fibers, pigments such as iron oxide, fillers, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, boric acid, acetic acid, formic acid , Maleic acid, organic acids such as phthalic acid, organic tin compounds such as dibutyltin laurate, dibutyltin octiate, tetrabutyl titanate, tetrapropyl titanate, etc. By blending a curing agent or a curing catalyst such as an organic titanium compound, a phosphoric acid ester such as monoethyl phosphate and monomethyl phosphate, an organic aluminum compound such as tris (acetylacetonato) aluminum and tris (ethylacetoacetonato) aluminum. Excellent in weather resistance and pollution resistance, low odor during construction and workability in cold districts. Furthermore, it uses hydrocarbon solvents mainly composed of petroleum solvents and uses little toluene and xylene. This makes it possible to obtain a paint or coating agent that is good for the global environment and good at the time of repair work.

Also, the non-aqueous dispersion type resin composition is coated with various paints such as lacquer paint, acrylic lacquer paint,
Thermosetting acrylic paint, alkyd paint, melamine paint,
Blending with an epoxy paint or the like can also improve the adhesion and weather resistance of the coating film of these paints. Further, the non-aqueous dispersion type resin composition can be used for various sealing agents.

[0058]

The present invention will be specifically described below with reference to examples. In the examples, “%” and “parts” mean on a weight basis unless otherwise specified.

Example 1 (1) Production of silicate oligomer (B) 76 parts of tetramethoxysilane and 4 parts of methanol were added to a flask equipped with a stirrer, a reflux condenser and a thermometer, and mixed. % Hydrochloric acid was added, and the mixture was hydrolyzed for 2 hours at an internal temperature of 65 ° C. Next, the condenser was replaced with an extraction tube, the temperature was raised until the internal temperature reached 150 ° C, extracted with methanol, and further heated at 150 ° C for 4 hours to obtain a hydrolyzed condensate. The polymerization degree was 2-9. Further, the tetramethoxysilane oligomer was boiled in a jacket heated to 150 ° C., and the vaporized monomer was discharged out of the system together with the inert gas to obtain a silicate oligomer (S-1).

(2) Production of Resin Dispersant (C) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
104 parts of mineral terpene ("Cactus", manufactured by Japan Energy Co., Ltd.), 59 parts of n-butyl methacrylate, 40 parts of isobutyl methacrylate, 0.5 part of γ-methacryloxypropyltrimethoxysilane, 0.5 part of 2-methacryloyloxyethyl succinic acid 0.5 Parts, 0.4 parts of diethylaminoethyl methacrylate and 20 parts of the above silicate oligomer (S-1) were charged, and the mixture was heated to 87 ° C., and 2 parts of 2,2-azobisbutyronitrile was further added. After the addition was completed, the temperature was raised to 90 ° C. and kept for 6 hours.
0.3 parts of azobisbutyronitrile was added and the mixture was kept warm for 2 hours to complete the polymerization reaction to obtain a resin-based dispersant (C-1).

(3) Production of Non-Aqueous Dispersion-Type Resin Composition Into the same flask as in (2) above, 1 mineral turpentine was placed.
Parts, after adding the resin-based dispersant (C-1) polymerized in (2) in such an amount that the radically unsaturated monomer constituting the resin-based dispersant (C-1) becomes 60 parts. The temperature was raised to 90 ° C., and styrene 2.5 parts, methyl methacrylate 17 parts, ethyl acrylate 17 parts, n-butyl methacrylate 1.5 parts
Parts, 1 part of isobutyl methacrylate, 0.9 part of γ-methacryloxypropyltrimethoxysilane, 0.25 part of 2-methacryloyloxyethylsuccinic acid, and 0.2 part of diethylaminoethyl methacrylate.
0.8 parts of azobisbutyronitrile and 6 parts of mineral terpene were added dropwise over 2.5 hours. After dropping, 90 ° C
After keeping the temperature for 4 hours to complete the polymerization reaction,
8 parts of the above silicate oligomer (S-1) was added, and the cloudy non-aqueous dispersion type resin composition (N-1) (solid content 59%) was added.
% And a viscosity at 25 ° C of 27300 mPa · s).

The obtained non-aqueous dispersion type resin composition (N-1)
Was evaluated for storage stability and pot life time as follows. (Storage stability) Put the above non-aqueous dispersion type resin composition (N-1) in a sealed container, leave at 20 ° C., evaluate the sedimentation stability of the particles, and gel or float the varnish (particle sedimentation). The number of months before wake up was measured.

(Pot life time) In a 100 ml container, 10 parts of the non-aqueous dispersion type resin composition (N-1) and 2-ethylhexyl acid phosphate (“AP
-8 ") 0.004 parts, dibutyltin tin 0.016
And 1 part of a curing agent consisting of 0.98 parts of a mineral turpentine, and after mixing, the time (hour) until skinning occurred on the surface was measured.

Further, the obtained non-aqueous dispersion type resin composition (N
-1) 70 parts of varnish for mill base (resin similar to resin-based dispersant (C-1)) 30 parts, titanium oxide 47
Parts and 20 parts of a mineral turpent were mixed and dispersed by a high-speed mill, and further mixed and dispersed to obtain a paint. The paint 1
To 100 parts, 10 parts of a curing agent composed of 0.04 part of 2-ethylhexyl acid phosphate (“AP-8” manufactured by Daihachi Chemical Co., Ltd.), 0.16 part of dibutyltin tin, and 9.8 parts of a mineral terpene were blended. After stirring and mixing, the mixture was coated on a glass plate using an applicator so that the thickness after drying was 60 μm, and dried for 24 hours to form a coating film.
The following evaluation was performed about this coating film.

(Weather resistance) The state of the coated surface was examined over time using a sunshine weather meter.
According to No. 90, the retention of 60 ° specular gloss after 3000 hours was measured. The evaluation criteria are as follows. ○: 80% or more △: 50 to less than 80% ×: less than 50%

(Stain resistance) After 6 months of outdoor exposure (Ibaraki City, Osaka Prefecture) at a 45 ° southward inclination, an evaluation test plate with attached dirt and a blank without outdoor exposure were used. The lightness difference ΔL from the evaluation test plate was determined by Nippon Denshoku Σ-90.
And the stain condition of the coated surface was examined. The evaluation criteria are as follows. ○ ・ ・ ・ less than 4 △ ・ ・ ・ less than 4-10 × ・ ・ ・ 10 or more

(Glossy) 6
The 0 ° specular gloss and the 20 ° specular gloss were measured. The evaluation criteria are as follows. In the case of 60 ° specular gloss ◎ ・ ・ ・ 80% or more ○ ・ ・ ・ 75 to less than 80% △ ・ ・ ・ 50 to less than 75% × ・ ・ ・ less than 50% In the case of 20 ° specular gloss ◎ ・ ・ ・ 65% Above ○: less than 60 to 65% △: less than 40 to 60% ×: less than 40%

Examples 2 to 6 (1) Production of silicate oligomer In the same manner as in Example 1, silicate oligomer (S-1)
I got (2) Production of Resin Dispersant (C) In Example 1, resin dispersants (C-2 to 4) were obtained in the same manner except that the composition was as shown in Table 1.

[Table 1] Resin-based dispersant (C) radically unsaturated monomer (c) silicate oligomer (B) (parts) (parts) C-1 nBMA iBMA MPTMS HOMS DEAEM S-1 (59) ( 40) (0.5) (0.5) (0.4) (20) C-2 nBMA iBMA MPTMS HOMS DEAEM S-1 (57) (39.5) (3.0) (0.5) (0.4) (20) C-3 nBMA iBMA MPTMS HOMS --- S-1 (57) (39.5) (3.0) (0.5) (20) C-4 nBMA iBMA MPTMS --- DEAEM S-1 (57) (39.5) (3.0) (0.4) (20)

Note) nBMA: n-butyl methacrylate iBMA: isobutyl methacrylate MPTMS: γ-methacryloxypropyltrimethoxysilane HOMS: 2-methacryloyloxyethyl succinic acid DEAEM: diethylaminoethyl methacrylate

(3) Production of non-aqueous dispersion type resin composition The same procedure as in Example 1 was carried out except that the composition shown in Table 2 was used, to obtain non-aqueous dispersion type resin compositions (N-2 to 6). Was.

[Table 2] Resin-based components Radical unsaturated unsaturated silicate powder (C) Monomer (c) Orodimer (parts) (parts) (B) (solids) (parts) Example 1 C-1 ST MMA EA nBMA iBMA MPTMS HOMS DEAEM S-1 (60) (2.5) (17) (17) (1.5) (1) (0.9) (0.25) (0.2) (8) Example 2 C-2 ST MMA EA nBMA iBMA MPTMS HOMS DEAEM S-1 (60) (2.5) (17) (17) (1.5) (1) (0.3) (0.25) (0.2) (18) Example 3 C-2 ST MMA EA nBMA iBMA MPTMS HOMS- -S-1 (60) (2.5) (17) (17) (1.5) (1) (0.3) (0.25) (18) Example 4 C-2 ST MMA EA nBMA iBMA MPTMS --- DEAEM S- 1 (60) (2.5) (17) (17) (1.5) (1) (0.3) (0.2) (18) Example 5 C-3 ST MMA EA nBMA iBMA MPTMS HOMS DEAEM S-1 (60) (2.5) (17) (17) (1.5) (1) (0.3) (0.25) (0.2) (18) Example 6 C-4 ST MMA EA nBMA iBMA MPTMS HOMS DEAEM S-1 (60) (2.5) (17) ) (17) (1.5) (1) (0.3) (0.25) (0.2) (18)

Note) ST: styrene MMA: methyl methacrylate EA: ethyl acrylate nBMA: n-butyl methacrylate iBMA: isobutyl methacrylate MPTMS: γ-methacryloxypropyltrimethoxysilane HOMS: 2-methacryloyloxyethyl succinate DEAEM: diethylaminoethyl methacrylate

Example 7 (1) Production of a silicate oligomer A silicate oligomer (S-1) was prepared in the same manner as in Example 1.
I got (2) Production of Resin Dispersant (C) Resin dispersant (C-1) was obtained in the same manner as in Example 1. (3) Production of non-aqueous dispersion type resin composition In Example 1, silicate oligomer (S-1) 8
A non-aqueous dispersion type resin composition (N-7) was obtained in the same manner except that the polymerization reaction was carried out in the presence of parts, and the same evaluation as in Example 1 was performed.

Example 8 (1) Production of silicate oligomer The silicate oligomer (S-1) was prepared in the same manner as in Example 1.
I got (2) Production of Resin Dispersant (C) A resin dispersant (C-5) was prepared in the same manner as in Example 1 except that 1 part of a maleic anhydride-modified alkyd resin (modified amount: 10%) was further added. I got (3) Production of Non-Aqueous Dispersion Resin Composition The same procedure as in Example 1 was carried out except that the resin dispersant (C-1) was replaced with the resin dispersant (C-5). A composition (N-8) was obtained, and was evaluated in the same manner as in Example 1.

Example 9 In Example 1, the non-aqueous dispersion type resin composition (N-1) 1
The same procedure was repeated except that 1 part of a maleic anhydride-modified alkyd resin (modified amount: 10%) was added to and mixed with 00 parts.
A non-aqueous dispersion type resin composition (N-9) was obtained, and the same evaluation as in Example 1 was performed.

Comparative Example 1 The procedure of Example 1 was repeated except that the silicate oligomer (S-1) was not used during the production of the resin dispersant (C) and the production of the non-aqueous dispersion type resin composition. And a resin composition, and the same evaluation as in Example 1 was performed.

Comparative Example 2 (1) Production of silicate oligomer The same silicate oligomer (S-1) as in Example 1 was further hydrolyzed to prepare a silicate oligomer (S-2) containing 100% of hydroxyl groups. . In Example 1, during the production of the resin-based dispersant (C) and the production of the non-aqueous dispersion type resin composition, the silicate oligomer (S-1)
Example 1 was repeated except that the silicate oligomer (S-2) was used in place of the above, to obtain a non-aqueous dispersion type resin composition.
The same evaluation was performed. Table 3 shows the evaluation results of the examples and the comparative examples.

[Table 3] Storage stability Hot life time Weatherability Stain resistance Glossiness (months) (hours) 60 ° 20 ° Example 1 6 months or more 4 ○ ○ ◎ ◎ 〃 26 months or more 4 ○ ○ ○ ○ 〃 36 months or more 3.5 ○ ○ ◎ ◎ 〃 46 months or more 4 ○ ○ ○ ○ ５ 5 6 months or more 3.5 ○ ○ ◎ ◎ ６ 66 months or more 4 ○ ○ ○ ○ 〃 76 4 months or more 4 ○ ○ ○ ○ 〃 86 6 months or more 4 ○ ○ ◎ ◎ ９ 96 months or more 4 ○ ○ ◎ ◎ Comparative Example 1 A non-aqueous dispersion type resin composition could not be obtained. 2 3 months 2 ○ ○ △ △

[0080]

The non-aqueous dispersion type resin composition of the present invention comprises an organic solvent (A), a specific silicate oligomer (B), a resin dispersant (C), and a radical unsaturated monomer (d). It has excellent storage stability, has a long pot life, and shows excellent effects on weather resistance, stain resistance, and gloss when formed into a coating film because it is composed of the polymer (D) obtained from It is very useful as a resin composition for paints.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C09D 167/00 C09D 167/00 F term (reference) 4J002 AA011 BG051 BG071 BQ001 CP022 CP171 HA08 4J011 AA05 JA06 JB25 PA69 PA99 PB30 PC02 4J026 AB44 BA27 BA43 BB02 DA05 FA04 GA06 4J038 DD122 DD242 DL021 DL022 FA041 FA042 FA051 FA052 FA061 FA062 FA081 FA082 FA101 FA102 FA111 FA112 FA121 FA122 FA151 FA152 FA161 FA162 FA181 FA182 FA211 FA212 JA03 GA06 JA03 JA03 JA03 JA03 MA07 NA03 NA04 NA05 NA19 NA26 PA19 PB05

Claims (12)

[Claims] 1. An organic solvent (A), a silicate oligomer (B) represented by the following general formula (1) soluble in the organic solvent (A), and a resin-based dispersant soluble in the organic solvent (A) (C) and a polymer (D) insoluble in the organic solvent (A) obtained from the radically unsaturated monomer (d) soluble in the organic solvent (A). A water-dispersed resin composition. Embedded image (Here, R is either an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is an integer of 2 to 30.) 2. A silicate oligomer (B) represented by the general formula (1) soluble in the organic solvent (A) and a resin dispersion soluble in the organic solvent (A) in the organic solvent (A). The non-aqueous dispersion type resin composition according to claim 1, wherein the radically unsaturated monomer (d) is polymerized in the presence of the agent (C). 3. After polymerizing a radically unsaturated monomer (d) in an organic solvent (A) in the presence of a resin-based dispersant (C) soluble in the organic solvent (A), 2. A composition comprising a silicate oligomer (B) represented by the general formula (1), which is soluble in the organic solvent (A).
The non-aqueous dispersion type resin composition according to the above. 4. The non-aqueous dispersion type resin composition according to claim 1, wherein the resin dispersant (C) contains a hydrolyzable silyl group. 5. The method according to claim 1, wherein the resin dispersant (C) is an organic solvent (A).
In the presence of the silicate oligomer (B),
The non-aqueous dispersion type resin composition according to claim 4, which is obtained by polymerizing a radically unsaturated monomer (c) containing a hydrolyzable silyl group-containing monomer (c1). 6. The non-aqueous dispersion type resin composition according to claim 1, wherein the resin dispersant (C) contains a hydrolyzable silyl group and an acid group and / or a base. . 7. The method according to claim 1, wherein the resin-based dispersant (C) is an organic solvent (A).
In the presence of the silicate oligomer (B),
It is obtained by polymerizing a radically unsaturated monomer (c) containing a hydrolyzable silyl group-containing monomer (c1), an acid group-containing monomer (c2) and / or a base-containing monomer (c3). The non-aqueous dispersion type resin composition according to claim 6, characterized in that: 8. As the radically unsaturated monomer (d),
8. The composition according to claim 1, comprising at least two of a hydrolyzable silyl group-containing monomer (d1), an acid group-containing monomer (d2), and a base-containing monomer (d3). Or a non-aqueous dispersion type resin composition as described above. 9. The non-aqueous dispersion type resin composition according to claim 1, further comprising an acid-modified alkyd resin (E). 10. The non-aqueous dispersion type resin composition according to claim 1, wherein the acid-modified alkyd resin (E) is contained in a resin-based dispersant (C). 11. A paint comprising the non-aqueous dispersion type resin composition according to any one of claims 1 to 10. 12. The coating according to claim 11, further comprising a curing agent or a curing catalyst.