JPH107979A - Nonaqueous dispersion type resin composition for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonaqueous dispersion type resin composition for coating materials, excellent in weatherability, staining resistance and applicability in cold districts and lowly odorous when applied by polymerizing a radical- polymerizable unsaturated monomer in the presence of a resin dispersant and a silicate oligomer in a specified organic solvent. SOLUTION: A radical-polymerizable unsaturated monomer is polymerized in the presence of a hydrolyzable-silyl-containing resin dispersant soluble in the organic solvent to be used and a silicate oligomer in an organic solvent in which the silicate oligomer is insoluble to obtain a nonaqueous dispersion type hydrolyzable-silyl-containing resin composition for coating materials. The polymerization is carried out by using such a reactant ratio that 5-200 pts.wt. silicate oligomer desirably represented by the formula (wherein R is H, a 1-4C alkyl or a phenyl; and (n) is 2-30), 3-80 pts.wt. resin dispersant containing 1-20wt.% hydrolyzable-silyl-containing vinyl monomer component, 3-600 pts.wt. organic solvent and 0.5-15 pts.wt. polymerization initiator are used per 100 pts.wt. radical-polymerizable unsaturated monomer.

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 for paints having excellent weather resistance and stain resistance, low odor during construction and excellent workability in cold regions.

[0002]

2. Description of the Related Art Conventionally, paints used for architectural 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. However, since the paint uses a large amount of an organic solvent containing toluene and xylene as a main component in actual coating, it has been regarded as a problem in terms of safety, poisoning, air pollution, and environmental problems for the human body. At the Central Pollution Control Council in June 1993, toluene and xylene, an organic solvent-based paint, were additionally specified as malodorous substances, and are subject to regulations under the Local Government Ordinance (the actual regulations are after the enactment of each local government) Since then, there has been a demand for a paint in which the amount of the harmful organic solvent used is reduced as much as possible. In addition, paints using the solvent-based acrylic resin, when used as a repair of exterior coatings, due to the strong solubility of toluene and xylene, causing lifting phenomena in the base coatings, etc. However, there is a point that it is difficult to use from the viewpoint of workability, and improvement is awaited.
On the other hand, as a paint with improved repairability problems and harm to the human body and the environment, a paint using an acrylic emulsion resin using water as a medium, and a silicone modification to impart high functionality to it There is also a paint using a water-based acrylic silicone emulsion resin, but it is still inferior in durability, especially water resistance and moisture resistance, and cannot be used solidified in cold areas where the temperature is 0 ° C or less. There are many problems.

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. Non-aqueous dispersion type acrylic resin, when used as a paint, uses a solvent containing aliphatic hydrocarbon as a main component, so less harmful to human body and environment than conventional solvent type acrylic resin. Also, the lifting phenomenon is small. 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. As described above, the non-aqueous dispersion type acrylic resin coating has such characteristics.However, in terms of weather resistance, it is not as good as a solvent type acrylic urethane resin coating or a fluororesin coating. It has been sought and developed.

For example, in order to improve the durability as a paint, Japanese Patent Application Laid-Open Nos. 64-75502 and 7-1 have been disclosed.
JP-A-38303, JP-A-2-64110 and JP-A-7-97402 disclose a hydrolyzable silyl group in a resin-based dispersant or a core particle resin portion in a non-aqueous dispersion type resin composition. Accordingly, a paint made of a resin modified with silicon is described.

[0005]

However, the present inventor has studied such a method in detail, and found that the non-aqueous dispersion type silicone acrylic resin paint has the following characteristics.
Although it is excellent in low odor during construction, hardening in cold district construction, chemical resistance, flexibility, storage stability, etc.
It was found that the stain resistance to exhaust gas, raindrops and the like was not sufficient, and that these properties, including chemical resistance, durability, and weather resistance, were not simultaneously provided with the stain resistance.

[0006]

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems. As a result, in an organic solvent which does not dissolve the silicate oligomer, a resin-based dispersant which dissolves in the organic solvent is used. And a silicate oligomer, particularly a silicate oligomer represented by the following formula 1, in which a radically unsaturated monomer is co-polymerized and the resin-based dispersant contains a hydrolyzable silyl group. The present inventors have found that a paint using a water-dispersed resin composition solves the above-mentioned problems, and completed the present invention.

Embedded image (However, n is an integer of 2 to 30. R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) In the present invention, 100 parts by weight of the radically unsaturated monomer is used. On the other hand, when the silicate oligomer is a non-aqueous dispersion type resin composition comprising 5 to 200 parts by weight, and 1 to 20% by weight of the weight component of the resinous dispersant is a hydrolyzable silyl group-containing vinyl monomer. In this case, the effect of the present invention can be remarkably exhibited.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The organic solvent that does not dissolve the silicate oligomer used in the present invention is an organic solvent (A) containing a petroleum-based mixed solvent as a main component. Examples of such a petroleum-based mixed solvent include mineral spirit, mineral thinner, and the like.
Petrolium spirit, white spirit, mineral terpen, and one or more of these are the main components, but pentane, hexane, heptane, octane,
Linear aliphatic hydrocarbons such as decane, cyclohexane, methylcyclohexane, ethylcyclohexane, it is also possible to add cyclic aliphatic hydrocarbons such as cycloheptane, in the present invention, such a petroleum-based mixed solvent as a main component By using the organic solvent (A), it is possible to reduce odor and to achieve low-temperature construction in a cold region. 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, xylene and the like Although it is also possible to add aromatic hydrocarbons, the weight ratio of the petroleum-based mixed solvent in the organic solvent (A) should be 70% or more of the above environment and the surface of the undercoat film repair. Is preferred.

[0008] The vinyl copolymer used as the resin-based dispersant of the present invention must be dissolved in an organic solvent (A) that does not dissolve the silicate oligomer. Examples include vinyl copolymers containing methacrylic acid esters as a main component, and specifically, n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl Carbon such as (meth) acrylate Vinyl copolymer obtained by copolymerizing as a main component one or two or more acrylic acid ester or methacrylic acid ester (B) having an alkyl group of 4 to 22 and the like.

In the present invention, it is necessary that the resin-based dispersant contains a hydrolyzable silyl group, and the unsaturated double bond containing the hydrolyzable silyl group is formed during the polymerization of the vinyl copolymer. Compound (C) having, for example, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxy Propyltriethoxysilane, γ- (meth)
Acryloxypropylmethyldimethoxysilane, γ-
(Meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, 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- A hydrolyzable silyl group can be contained by blending one or more of (meth) acryloxyoctadecyltrimethoxysilane and the like as a copolymer component.

Further, at the time of polymerization of such a vinyl copolymer,
In a range that does not inhibit the solubility in the organic solvent,
Acrylate or methacrylate (D) having an alkyl group having 3 or less carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-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-hydroxydecyl Addition of a hydroxyl group-containing acrylate or methacrylate (E) such as (meth) acrylate or an amino, epoxy, halide, nitrile or amide group-containing acrylate or methacrylate (F) Can also be copolymerized.

Further, other polymerizable unsaturated compounds (G)
Styrene, vinyl toluene, (meth) acrylonitrile, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acryl chloride, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl pyridine, vinyl pyrrolidone, methyl vinyl ketone, acrylamide, acetoacetate An acetylated (meth) acrylate or the like can be used at the time of copolymerization.

Known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization can be used as the polymerization method for the resin-based dispersant of the present invention, but the process can be directly transferred to the next polymerization step. Solution polymerization is most preferable, and such a solution polymerization method will be described below, but is not limited thereto.
With respect to the weight ratio of various monomers (B) to (G) in the copolymerization, (C) is preferably set to 1 to 20% by weight,
The amount is preferably 5 to 15% by weight, and when it is 1% by weight or less, the curing speed becomes slow, and when it is 20% by weight or more, the storage stability becomes short. The weight ratio of the other monomers is not particularly limited, but (D) to (G) is preferably 10% by weight or less.

The polymerization initiator (H) used in the polymerization includes, for example, isobutyl peroxide, lauryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butyl cumide. Ruperoxide, 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-ethylhexyl peroxydicarbonate, t
-An organic peroxide such as butyl peroxyisobutyrate,
There are azo compounds such as azobisisobutyronitrile, dimethylazodiisobutyrate, 2,2-azobis (2,4-dimethylvaleronitrile) and 2,2-azobis (2-methylbutyronitrile). One or two or more can be used. The amount of (H) used is determined by the desired molecular weight of the resin-based dispersant, but is usually
With respect to 100 parts by weight of the total of (B) to (G), 0.0
The amount may be 5 to 10.0 parts by weight.

The solution polymerization of the resin-based dispersant is carried out in the above organic solvent (A), and the organic solvent (A) is used in an amount of 30 to 100 parts by weight based on the total of (B) to (G). Although it is used at 600 parts by weight, it is preferably polymerized at 80 to 150 parts by weight. The reaction temperature during the solution polymerization of the resin-based dispersant is usually suitably in the range of about 50 to 170 ° C, and the reaction is usually completed in about 1 to 18 hours.

In the present invention, the molecular weight of the copolymer used as the resin-based dispersant is usually about 50 by weight average molecular weight.
About 100 to 100,000, preferably about 5000 to 50
It is preferable to be in the range of about 000. If the molecular weight is less than about 5,000, the dispersion particles are insufficiently stabilized, and aggregation and sedimentation tend to occur.
If it exceeds 00000, the viscosity becomes extremely high and handling becomes difficult, which is not preferable.

The radical polymerizable unsaturated monomer is polymerized in the presence of the resin dispersant thus obtained in an organic solvent (A) in the presence of a silicate oligomer, whereby the organic solvent (A A non-aqueous dispersion type resin composition comprising a core particle resin portion insoluble in (1) and a resin dispersant having an affinity for the organic solvent (A) is obtained.

The radical polymerizable unsaturated monomer which is a constituent component of the resin portion of the core particle is appropriately selected from the group consisting of (B) to (G) which are constituent components of the resin-based dispersant.
Type is selected. The constituent components at this time are not particularly limited as long as they are soluble in the organic solvent (A) at the time of the monomer, become insoluble as the polymerization proceeds, and are excellent in polymerizability. Among them, those having a smaller number of carbon atoms than the carbon number of the monomer of the resin-based dispersant component are suitably selected. In particular, in (B) and (D), an alkyl group having 1 to 8 carbon atoms Or a methacrylic ester having the formula (1), but those having a large number of carbon atoms can be selected as long as the effects of the present invention are not impaired. The radical polymerizable unsaturated monomers (B) to (G) can be polymerized at an arbitrary weight ratio, but preferably 10 to 30% by weight of (B) and 10 to 30% by weight of (C). 0-20
%, (D) is 50 to 80% by weight, (E) and (F) are 0 to 10% by weight, (G) is 10 to 30% by weight, and the sum of (B) to (G) is What is necessary is just to select suitably so that it may become 100 weight%.

The most important feature of the present invention is that the above-mentioned radical polymerizable unsaturated monomer is co-polymerized in the presence of a silicate oligomer, and the silicate oligomer is not particularly limited. It is preferable to use silicate oligomers (n = 2 to 20), and particularly preferably n = 4 to 8, but n = 4 to 8 as a main component and further n = 2 to 3 or n = 9 to It may contain 20 components.

The method for producing the silicate oligomer is as follows:
For example, tetramethoxysilane, tetraethoxysilane,
It is obtained by hydrolyzing tetraalkoxysilane such as tetrapropoxysilane and tetrabutoxysilane or tetraphenoxysilane. n can be adjusted by controlling the hydrolysis rate in this case. In addition, the hydrolysis reaction itself can be performed by a known method. For example, while adding a predetermined amount of water to the tetraalkoxysilane to distill off alcohol by-produced in the presence of an acid catalyst, the hydrolysis reaction is usually performed at about room temperature to React at 100 ° C. By this reaction, the alkoxysilane is hydrolyzed, and a liquid silicate oligomer having two or more hydroxyl groups is obtained as a hydrolyzate by a condensation reaction.

As a polymerization method for obtaining the non-aqueous dispersion type resin composition, known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization and the like are possible. Solution polymerization is most preferred. The polymerization initiator used in the polymerization may be of the same type as the polymerization initiator (H) used in the polymerization of the resin-based dispersant. The amount of the silicate oligomer is preferably 5 to 200 parts by weight, more preferably 5 to 100 parts by weight, and preferably less than 5 parts by weight, based on 100 parts by weight of the radical polymerizable unsaturated monomer. If it exceeds 200 parts by weight, the coating film becomes brittle and it becomes difficult to apply a thick coating. The resin-based dispersant is used in an amount of 3 to 100 parts by weight of the radical polymerizable unsaturated monomer.
80 parts by weight, 3 to 600 parts by weight of the organic solvent (A) and 0.5 to 15 parts by weight of the polymerization initiator (H), and preferably 5 to 80 parts by weight of the resin dispersant. When the organic solvent (A) is 50 to 300 parts by weight and the resin dispersant is less than 5 parts by weight or the organic solvent (A) is less than 50 parts by weight, the dispersion stability tends to be poor. If the resin dispersant exceeds 80 parts by weight or the organic solvent (A) is 30
If it exceeds 0 parts by weight, the sagging and drying properties are poor,
Painting workability tends to be a problem. 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.
It is appropriate to use a temperature in the range of about 0 to 170 ° C., and the reaction is usually completed in about 1 to 18 hours.

Thus, a particle of a non-aqueous dispersion resin in which a resin-based dispersant is bonded to the outer periphery of the core particle resin portion is obtained, and the particle diameter of these particles is in the range of about 0.1 to 10 μm. . If the particle diameter is smaller than this range, special consideration is required for the production of varnish, and industrial profitability cannot be obtained,
On the other hand, if the particle diameter is larger than this range, the particles swell or aggregate during storage, which is not preferable.

In the non-aqueous dispersion type resin composition of the present invention, titanium white, phthalocyanine blue, carbon black, calcium carbonate, magnesium carbonate, barium sulfate, various silicas, glass fibers, iron oxide are used together with a pigment dispersant and a leveling agent. Such as pigments, fillers, hydrochloric acid, nitric acid, phosphoric acid,
Inorganic acids such as boric acid, acetic acid, formic acid, maleic acid, organic acids such as phthalic acid, organic tin compounds such as dibutyltin laurate, dibutyltin octate, and organic titanium compounds such as tetrabutyl titanate and tetrapropyl titanate;
By adding a curing catalyst such as phosphoric acid esters such as monoethyl phosphate and monomethyl phosphate, and organoaluminum compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetonato) aluminum, weather resistance and stain resistance, construction It is excellent in the global environment because it has low odor and excellent workability in cold areas, and uses little hydrocarbon and toluene as solvent. Good paints and coatings can be obtained during construction. In addition, various paints to the non-aqueous dispersion type resin composition,
For example, by blending with a lacquer-based paint, an acrylic lacquer-based paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy paint, or the like, the adhesion and weather resistance of the coating film of these paints can also be improved. Further, the non-aqueous dispersion type resin composition can be used for various sealing agents.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below.
In the following description, "parts" means parts by weight. Example 1 (1) Preparation of silicate oligomer 76 parts of tetramethoxysilane and 4 parts of methanol were added to a flask equipped with a stirrer, a condenser for reflux and a thermometer and mixed, and then 7 parts of 0.05% hydrochloric acid was added. The hydrolysis was carried out at an internal temperature of 65 ° C. for 2 hours. 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 hydrolyzate. The polymerization degree was 2 to 9, and the number of hydroxyl groups was 10 or more. 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) Polymerization of resin-based dispersant A mineral turpent ("Cactus" manufactured by Japan Energy Co., Ltd.) was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer.
90 parts were charged. After heating to 90 ° C. under a nitrogen stream, 40 parts of butyl methacrylate, 35 parts of 2-ethylhexyl acrylate, 10 parts of stearyl methacrylate, 5 parts of methyl methacrylate, and 10 parts of γ-methacryloxypropyltrimethoxysilane are added dropwise over 2 hours ( I) did. After completion of the dropwise addition, the temperature was maintained for 1 hour, and a liquid in which 2 parts of 2,2-azobisbutyronitrile was dissolved in 30 parts of a mineral turpent was dropped over 30 minutes. After dropping, 100
° C. to complete the polymerization reaction, the resin dispersant (D-
1) was obtained.

(3) Synthesis of Non-Aqueous Dispersion Type Resin Composition A mineral turpent 70 was placed in the same flask as in (2) above.
After the temperature was raised to 100 ° C., 30 parts of the resin-based dispersant (D-1) polymerized in (2) was added. 10 under nitrogen stream
After the temperature was raised to 0 ° C., 20 parts of styrene, 40 parts of methyl methacrylate, 20 parts of methyl acrylate, 20 parts of butyl acrylate, 40 parts of the silicate oligomer (S-1) obtained in the above (1), 2,2-azobisbutyl Lonitrile 2
Was dissolved dropwise over 2 hours (II). After the completion of the dropwise addition, the temperature was maintained at 100 ° C. for 6 hours to complete the polymerization reaction and obtain a cloudy non-aqueous dispersion type resin composition (N-1).

The obtained non-aqueous dispersion type resin composition (N-1)
To 100 parts, 300 parts of titanium white tarpaque (manufactured by Ishihara Sangyo Co., Ltd.) was kneaded as a pigment to prepare a paint, and a mineral turpent was used in a Ford cup # 4 for 12 seconds (25 seconds).
° C), and a solution prepared by dissolving 0.1 part of dibutyltin laurylate and 0.01 part of tris (acetylacetate) aluminum in 10 parts of a mineral turpentine is added, followed by stirring and mixing. 45 μm to 55 μ
m (after drying) so that a slate plate (JISF54
03 rules), and used as an evaluation test plate.

The evaluation test plate was allowed to stand for one week under the curing room conditions defined by JIS, and the following performance test (No. 1) was performed.・ Water resistance: Investigation was performed based on the state of the coated surface after immersion in tap water at 20 ° C. for 240 hours. -Alkali resistance: Examined by the state of the coated surface after 72 hours in a 5% aqueous NaOH solution (20 ° C). -Acid resistance: Investigated by the state of the coated surface after 72 hours in a 5% aqueous HCl solution (20 ° C).・ Solvent resistance: Xylene is placed on a part of the coating surface, 20 ℃
The coated surface is circumferentially coated with gauze impregnated with xylene
The state of the coated surface after rubbing 0 times was examined.

Weather resistance: The state of the coated surface is examined over time using a sunshine weather meter, and until the retention of 60 ° specular gloss measured by Nippon Denshoku Co., Ltd., Σ-90, becomes 80% or less. (Hr) was examined.・ Repeated test of hot and cold: Immerse in water of 20 ° C for 18 hours, then repeat the operation of -40 ° C for 3 hours and then 60 ° C for 3 hours for 10 cycles. It was examined whether or not abnormal occurrence such as was observed.・ Stain resistance: After three months of outdoor exposure (Ibaraki City, Osaka Prefecture) at a 45 ° southward inclination, evaluation of an evaluation test plate with attached dirt and a blank without outdoor exposure The color difference ΔE from the test plate was measured with に て -90 manufactured by Nippon Denshoku Co., Ltd. to check the stain state of the coated surface.

After standing at 20 ° C. for 45 minutes immediately after coating, the following performance test (No. 2) was performed on the evaluation test plate. -Low-temperature construction stability: After leaving at -5 ° C for 16 hours,
The resin composition on the coated surface was examined for abnormalities such as freezing and cracks and blisters. Odor sensitivity test: The odor of toluene and xylene emitted from the coated surface was examined.

Example 2 (1) Preparation of Silicate Oligomer The silicate oligomer (S-1) was prepared in the same manner as in Example 1.
I got (2) Polymerization of resin-based dispersant Resin-based dispersant (D-1) polymerized by the same operation as in Example 1.
I got (3) Synthesis of Non-Aqueous Dispersion Type Resin Composition Polymerization was carried out in the same manner as in Example 1 except that, in the synthesis of Example 1, 20 parts of γ-methacryloxypropyltrimethoxysilane was further added and polymerized. Non-aqueous dispersion type resin composition (N
-2), and the same evaluations as in Example 1 were performed.

Example 3 (1) Preparation of silicate oligomer In a flask equipped with a stirrer, a reflux condenser and a thermometer, 76 parts of tetramethoxysilane and 24 parts of methanol were placed.
Then, 7 parts of 0.05% 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 3 hours to obtain a hydrolyzate. The polymerization degree was 2 to 6, and the number of hydroxyl groups was 10 or more. 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-2). (2) Polymerization of resin-based dispersant Resin-based dispersant (D-1) polymerized by the same operation as in Example 1.
I got (3) Synthesis of Non-Aqueous Dispersion Type Resin Composition In the synthesis of Example 1, the silicate oligomer (S-2) obtained in the above (1) was replaced with the silicate oligomer (S-1) in the dropwise addition (II). Polymerization was carried out in the same manner as in Example 1, except that a non-aqueous dispersion type resin composition (N-3) was obtained. The same evaluation as in Example 1 was performed.

Comparative Example 1 (1) Polymerization of Resin Dispersant Example 1 was repeated except that, instead of γ-methacryloxypropyltrimethoxysilane, 10 parts of 2-hydroxyethyl methacrylate was added and polymerized. Polymerization was carried out in the same manner as in the above to obtain a resin-based dispersant (D-2). (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition In the synthesis of Example 1, the resin dispersant (D) was added dropwise (II).
Polymerization is carried out by the same operation except that a resin dispersant (D-2) is added instead of -1) and the silicate oligomer (SO-1) is not added, and the non-aqueous dispersion type resin composition (N'-1) is obtained. And the same evaluation as in Example 1 was performed.

Comparative Example 2 (1) Polymerization of Resin Dispersant Resin dispersant (D-1) polymerized by the same operation as in Example 1.
I got (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition In the synthesis of Example 1, polymerization was carried out by the same operation except that silicate oligomer (SO-1) was not added by dropping (II), and non-aqueous dispersion type was obtained. A resin composition (N'-2) was obtained, and was evaluated in the same manner as in Example 1.

Comparative Example 3 (1) Polymerization of Resin Dispersant Example 1 was repeated except that in place of dropping (I), 10 parts of 2-hydroxyethyl methacrylate was added instead of γ-methacryloxypropyltrimethoxysilane. Polymerization was carried out in the same manner as in the above to obtain a resin-based dispersant (D-2). (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition In the synthesis of Examples, the resin-based dispersant (D-
Polymerization was carried out by the same procedure except that resin dispersant (D-2) was added in place of 1) and polymerization was carried out using 20 parts of γ-methacryloxypropyltrimethoxysilane in place of silicate oligomer (S-1). Non-aqueous dispersion type resin composition (N '
-3), and the same evaluations as in Example 1 were performed.

Comparative Example 4 (1) Polymerization of Resin Dispersant Resin dispersant (D-1) polymerized by the same operation as in Example 1.
I got (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition In the synthesis of Example 1, polymerization was carried out using 20 parts of γ-methacryloxypropyltrimethoxysilane instead of silicate oligomer (S-1) in dropping (II). Polymerization was performed in the same manner as above to obtain a non-aqueous dispersion type resin composition (N'-4), and the same evaluation as in Example 1 was performed.

The evaluation results of the examples and comparative examples are shown in Tables 1 to 3. Table 1 shows the evaluation results of water resistance, alkali resistance, acid resistance, and solvent resistance. Table 2 shows the evaluation results of weather resistance, hot / cold repetition test, and stain resistance. The evaluation results of the odor and odor sensitivity tests were shown. The weather resistance was evaluated as good when it was 3000 hours or more, and the stain resistance was evaluated as good when ΔE was 1.0 or less.

[0037]

[Table 1] Water resistance, alkali resistance, acid resistance, solvent resistance Example 1 No abnormality No abnormality No abnormality No abnormality No abnormality 〃 2 No abnormality No abnormality No abnormality No abnormality 〃 3 No abnormality No abnormality No abnormality No abnormality ４ 4 No abnormality No abnormality No abnormalities No abnormalities Comparative Example 1 Whitening blisters Whitening blisters Whitening blisters Swelling 〃2 Whitening blisters Whitening blisters Whitening blisters Swelling 〃3 No abnormalities No abnormalities Swelling No abnormalities No abnormalities No abnormalities No abnormalities Swelling

[0038]

[Table 2] Weathering resistance Hot and cold cycling Stain resistance (Hr) repetition test ΔE Example 1 3000 <No abnormalities 0.8〃2 3000 <No abnormalities 0.8 33000 <No abnormalities 0.8〃43000 < No abnormality 0.9 Comparative Example 1 500 cracks 6.9 〃 2 1000 cracks 6.3 ３ 3 1500 1500 peels 4.3 ４ 4 2000 peels 3.6

[0039]

[Table 3]

[0040]

According to the present invention, a non-aqueous dispersion type resin composition is produced by polymerizing an unsaturated monomer in an organic solvent in the presence of a hydrolyzable silyl group-containing resin dispersant and a silicate oligomer. Therefore, when used in paint applications, it can provide a coating film with high stain resistance and weather resistance, and can be applied in cold areas where it can be applied with low odor during application and water-based emulsion. A resin composition for use.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 11, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

As a polymerization method for obtaining the non-aqueous dispersion type resin composition, known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization and the like are possible. Most preferred is dispersion polymerization . The polymerization initiator used in the polymerization may be of the same type as the polymerization initiator (H) used in the polymerization of the resin-based dispersant. The amount of the silicate oligomer is preferably 5 to 200 parts by weight, more preferably 5 to 100 parts by weight, and preferably less than 5 parts by weight, based on 100 parts by weight of the radical polymerizable unsaturated monomer. If it exceeds 200 parts by weight, the coating film becomes brittle and it becomes difficult to apply a thick coating. The resin-based dispersant is used in an amount of 3 parts by weight per 100 parts by weight of the radical polymerizable unsaturated monomer.
To 80 parts by weight, the organic solvent (A) is from 3 to 600 parts by weight, and the polymerization initiator (H) is appropriately selected from the range of from 0.5 to 15 parts by weight. Preferably, the resinous dispersant is from 5 to 80 parts by weight. Department,
When the organic solvent (A) is 50 to 300 parts by weight and the resin-based dispersant is less than 5 parts by weight or the organic solvent (A) is less than 50 parts by weight, the dispersion stability tends to be poor, If the resin dispersant exceeds 80 parts by weight or the organic solvent (A)
When the amount exceeds 00 parts by weight, the sagging property and the drying property are poor, and the coating workability tends to be a problem. 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 is usually completed in about 1 to 18 hours. .

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

After standing at 20 ° C. for 45 minutes immediately after coating, the following performance test (No. 2) was performed on the evaluation test plate.・Low temperature stability・ ・ ・ ・After leaving at -5 ℃ for 16 hours ,
The fat composition was examined for abnormalities such as freezing . Odor sensitivity test: The odor emitted from the painted surface was examined.

Claims (4)

[Claims] 1. An organic solvent which does not dissolve a silicate oligomer, wherein a radically unsaturated monomer is polymerized in the presence of a resin-based dispersant and a silicate oligomer which are soluble in the organic solvent. A non-aqueous dispersion type resin composition for paint, wherein the dispersant contains a hydrolyzable silyl group. 2. The non-aqueous dispersion type resin composition for a paint according to claim 1, wherein the silicate oligomer is represented by the following chemical formula 1. Embedded image (However, n is an integer of 2 to 30. R is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) 3. The non-aqueous dispersion type resin composition for a paint according to claim 1, wherein the silicate oligomer is 5 to 200 parts by weight based on 100 parts by weight of the radical unsaturated monomer. . 4. The non-aqueous dispersion type for paint according to claim 1, wherein 1 to 20% by weight of the weight component of the resin-based dispersant is a vinyl monomer having a hydrolyzable silyl group. Resin composition.