JPH107980A - 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 mixing a specified organic solvent with a specified resin dispersant, a polymer insoluble in the organic solvent and a silicate oligomer. SOLUTION: Hundred pts.wt. radical-polymerizable monomer is polymerized in the presence of 3-80 pts.wt. resin dispersant (B) containing 1-20wt.% hydrolyzable-silyl-containing vinyl monomer component and being soluble in A in an organic solvent (A) in which a silicate oligomer is insoluble to obtain a nonaqueous dispersion type resin composition (I) comprising a polymer (C) insoluble in A. Hundred pts.wt. B is mixed with 100-700 pts.wt. silicate oligomer (D) insoluble in A, desirably an oligomer represented by the formula (wherein R is H, a 1-4C alkyl or a phenyl; and (n) is 2-30) in A to obtain a nonaqueous dispersion (II). (I) and (II) are mixed with each other in such a mixing ratio that 5-200 pts.wt. D of (I) is present per 100 pts.wt. C of (I) to obtain the purpose resin composition.

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 to solve the above-mentioned problems. As a result, the present inventors have found that an organic solvent (A) that does not dissolve silicate oligomers and an organic solvent (A) A resin-based dispersant (B), a polymer (C) insoluble in the organic solvent (A), and a silicate oligomer (D) insoluble in the organic solvent (A); A paint using the non-aqueous dispersion type resin composition, wherein the agent (B) contains a hydrolyzable silyl group,
The present inventors have found that the above-mentioned problems have been solved and completed the present invention.

In the present invention, the silicate oligomer (D) is a silicate oligomer (D) represented by the following formula (1), and the polymer (C) insoluble in the organic solvent (A)
5 parts of silicate oligomer (D) per 100 parts by weight
To 200 parts by weight, and when 1 to 20% by weight of the weight component of the resin-based dispersant (B) is a hydrolyzable silyl group-containing vinyl monomer, the effect of the present invention can be remarkably exhibited. it can.

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.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The organic solvent (A) 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 and mineral thinner. , Petrolium spirit, white spirit, and mineral terpen. Of these, one or two are the main components, but pentane, hexane, heptane, octane, linear aliphatic hydrocarbons such as decane, cyclohexane, methyl It is also possible to add a cycloaliphatic hydrocarbon such as cyclohexane, ethylcyclohexane, or cycloheptane. In the present invention, the use of the organic solvent (A) containing such a petroleum-based mixed solvent as a main component reduces the odor. It is possible to achieve low-temperature construction in a cold region, as well as to achieve this. Incidentally, to the extent that the effects of the present invention are not impaired, esters such as ethyl acetate and butyl acetate,
It is possible to add ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, and aromatic hydrocarbons such as toluene and xylene. The weight ratio of the petroleum-based mixed solvent in the above is preferably 70% or more in view of the environment and the surface of the undercoat film repair.

The vinyl copolymer used as the resin-based dispersant (B) of the present invention must be dissolved in an organic solvent (A) which does not dissolve the silicate oligomer. Examples thereof include vinyl copolymers containing an acid ester or a methacrylic acid ester 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) ) One or two acrylates or methacrylates (E) having an alkyl group having 4 to 22 carbon atoms, such as acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. A vinyl copolymer obtained by copolymerizing the above as a main component is exemplified.

In the present invention, it is necessary that the resin-based dispersant (B) contains a hydrolyzable silyl group, and when the vinyl copolymer is polymerized, the unsaturated dihydric group containing a hydrolyzable silyl group is used. Compound (F) having a heavy bond, for example, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ-
(Meth) acryloxypropyltriethoxysilane, 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- A hydrolyzable silyl group can be contained by blending one or more of (meth) acryloxydodecyltrimethoxysilane and γ- (meth) acryloxyoctadecyltrimethoxysilane as copolymer components.

In the polymerization of such a vinyl copolymer,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, is as long as the solubility in the organic solvent (A) is not impaired.
Acrylate or methacrylate (G) having an alkyl group having 3 or less carbon atoms such as o-propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxypropyl (meth) acrylate,
Hydroxyl-containing compounds such as 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and 10-hydroxydecyl (meth) acrylate Acrylate or methacrylate (H), amino group,
An acrylic acid ester or methacrylic acid ester (J) containing an epoxy group, a halide group, a nitrile group, or an amide group can be added and copolymerized.

Further, other polymerizable unsaturated compounds (K)
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.

The polymerization method of the resin-based dispersant (B) of the present invention is as follows:
Known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization and the like are possible, but solution polymerization that can directly proceed to the next polymerization step is most preferable, and such a solution polymerization method will be described below. However, the present invention is not limited to this. Regarding the weight ratio of various monomers (E) to (K) in the copolymerization, (F) is preferably 1 to 20% by weight, more preferably 5 to 15% by weight, and 1% by weight or less. In the case of (1), the curing speed is slow, and in the case of 20% by weight or more, the storage stability is short. The weight ratio of the other monomers is not particularly limited, but (G) to (K) is preferably 10% by weight or less.

The polymerization initiator (L) used in the polymerization includes, for example, isobutyl peroxide, lauryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, tert-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 (L) to be used is determined by the desired molecular weight of the resin-based dispersant (B), but is usually 0.1 to 100 parts by weight of the total of (E) to (K). The amount may be from 0.05 to 10.0 parts by weight.

The solution polymerization of the resin-based dispersant (B) is carried out in the above-mentioned organic solvent (A).
To 100 parts by weight of the total amount of the organic solvent (A)
0-600 parts by weight, preferably 80-600 parts by weight
It is polymerized at 150 parts by weight. The reaction temperature during the solution polymerization of the resin-based dispersant (B) 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 (B) is generally about 5,000 to 100,000, preferably about 5,000 in weight average molecular weight.
It is preferable to be in the range of about 50,000 to about 50,000. When the molecular weight is less than about 5,000, the dispersion particles are insufficiently stabilized, and aggregation and sedimentation tend to occur. On the other hand, when the molecular weight exceeds about 100,000, the viscosity becomes extremely high and handling may be difficult. Not preferred.

The radically polymerizable unsaturated monomer is polymerized in the organic solvent (A) in the presence of the resin-based dispersant (B) thus obtained, whereby the organic solvent (A) becomes insoluble. As a result, a non-aqueous dispersion type resin composition (I) comprising the polymer (C), that is, the core particle resin portion, and the resin dispersant (B) having an affinity for the organic solvent (A) is obtained.

The radically polymerizable unsaturated monomer which is a component of the resin portion of the core particles is appropriately selected from the components (E) to (K) which are components of the resin dispersant (B).
Species to 10 types are selected. The 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 monomer of the resin-based dispersant (B) component are suitably selected from among (E) and (G).
In the above, an acrylate or a methacrylate having an alkyl group having 1 to 8 carbon atoms is 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. The weight ratio of the radical polymerizable unsaturated monomers (E) to (L) can be any polymerization ratio, but preferably, (E) is 10 to 30% by weight,
(F) is 0 to 20% by weight, (G) is 50 to 80% by weight,
(H) and (J) are 0 to 10% by weight, and (K) is 10 to 30% by weight.
What is necessary is just to select suitably so that the sum of these (E) to (K) may be 100% by weight.

As the polymerization method for obtaining the non-aqueous dispersion type resin composition (I), known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization can be used. As in B), solution polymerization is most preferred. The polymerization initiator used in the polymerization may be of the same type as the polymerization initiator (L) used in the polymerization of the resin-based dispersant (B). The resin-based dispersant (B) is 3-80 parts by weight, the organic solvent (A) is 3-600 parts by weight, and the polymerization initiator (L) is 100 parts by weight of the radical polymerizable unsaturated monomer. The resin dispersant (B) is appropriately selected from the range of 0.5 to 15 parts by weight, and preferably contains 5 to 80 parts by weight of the resin dispersant (B) and 50 to 300 parts by weight of the organic solvent (A). ) 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, and the resin-based dispersant (B) exceeds 80 parts by weight or the organic solvent (A) (A)
When the amount exceeds 300 parts by weight, the sagging property and the drying property are inferior, 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 performed by a known method, the reaction temperature during the polymerization,
Usually, it is appropriate to use a temperature in the range of about 50 to 170 ° C., and the reaction is usually completed in about 1 to 18 hours.

Next, the non-aqueous dispersion (II) is obtained by mixing and stirring the resin-based dispersant (B) and the silicate oligomer (D) in the organic solvent (A) which does not dissolve the silicate oligomer. . The mixing conditions of the resin-based dispersant (B) and the silicate oligomer (D) are not limited, but 100 to 700 parts of the silicate oligomer (D) are added to 100 parts of the resin-based dispersant (B). The appropriate stirring conditions are usually at a temperature of about 50 to 170 ° C. for about 1 to 8 hours.

The silicate oligomer (D) used in the present invention is not particularly limited, but it is preferable to use a specific silicate oligomer (n = 2 to 30) represented by the formula (1), and particularly, n = 4 to 8 Is preferred, but n =
Components having 4 to 8 as a main component and n = 2 to 3 or n = 9 to 20 can also be contained.

The silicate oligomer (D) can be produced by hydrolyzing tetraalkoxysilane or tetraphenoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane. . 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 (D) having two or more hydroxyl groups is obtained as a hydrolyzate by a condensation reaction.

The greatest feature of the present invention is that the obtained non-aqueous dispersion (II) and the above-mentioned non-aqueous dispersion type resin composition (I) are dissolved in an organic solvent (A) which does not dissolve the silicate oligomer.
And a non-aqueous dispersion type resin composition (III). Such a non-aqueous dispersion type resin composition (II
Regarding the compounding of I), 100 parts by weight of the polymer (C), that is, 100 parts by weight of the resin component of the non-aqueous dispersion type resin composition (I), are added to the silicate oligomer (N) in the non-aqueous dispersion (II). The amount of D) is preferably from 5 to 200 parts by weight, more preferably from 5 to 100 parts by weight, and if it is less than 5 parts by weight, the stain resistance is poor, and if it exceeds 200 parts by weight, the coating film becomes brittle. Thick coating becomes difficult. In addition, stirring here
The mixing conditions may be the same as in the preparation of the non-aqueous dispersion (II).

Thus, the non-aqueous dispersion type resin composition (III)
Is obtained, and the particle size of the particles dispersed therein is in the range of about 0.1 to 10 μm. When the particle size is smaller than this range, the viscosity of the varnish increases, while when the particle size is larger than this range, the particles swell or aggregate during storage, which is not preferable.

Non-aqueous dispersion type resin composition (III) of the present invention
In addition to pigment dispersants and leveling agents, pigments such as titanium white, phthalocyanine blue, carbon black, calcium carbonate, magnesium carbonate, barium sulfate, various silicas, glass fibers, iron oxide, fillers, hydrochloric acid, nitric acid, phosphoric acid , Inorganic acids such as boric acid, organic acids such as acetic acid, formic acid, maleic acid and phthalic acid; organic tin compounds such as dibutyltin laurate and dibutyltin octate; organic titanium compounds such as tetrabutyl titanate and tetrapropyl titanate; monoethyl phosphate By adding a curing catalyst such as a phosphoric acid ester such as monomethyl phosphate and an organic aluminum compound such as tris (acetylacetonato) aluminum and tris (ethylacetoacetonato) aluminum, the weather resistance and stain resistance can be reduced. Odorization and cold regions Excellent workability.Also uses petroleum-based hydrocarbon-based solvents and uses little toluene and xylene, making it a good paint and coating agent for the global environment and good for repair work. can do. Further, the non-aqueous dispersion type resin composition is blended with various paints, for example, a lacquer paint, an acrylic lacquer paint, a thermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxy paint, etc., to apply these paints. The adhesion and weather resistance of the film can also be improved. Further, the non-aqueous dispersion type resin composition can be used for various sealing agents.

[0026]

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) Polymerization of resin-based dispersant (B) 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.
-20) 90 parts were charged. After heating to 90 ° C. under a nitrogen stream, 40 parts of butyl methacrylate, 35 parts of 2-ethylhexyl acrylate, and 10 parts of stearyl methacrylate
Parts, 5 parts of methyl methacrylate, and 10 parts of γ-methacryloxypropyltrimethoxysilane were added dropwise over 2 hours. After dropping, keep the temperature for 1 hour.
A solution prepared by dissolving 2 parts of azobisbutyronitrile in 30 parts of mineral terpene was dropped over 30 minutes. After completion of the dropwise addition, the temperature was raised to 100 ° C. to complete the polymerization reaction, and a resin-based dispersant (B-1) was obtained.

(2) Synthesis of Non-Aqueous Dispersion Type Resin Composition (I) A mineral turpentine 70 was placed in the same flask as in (1) above.
After the temperature of the mixture was raised to 100 ° C., 30 parts of the resin dispersant (B-1) polymerized in (1) was added. 10 under nitrogen stream
After the temperature was raised to 0 ° C., a solution prepared by dissolving 20 parts of styrene, 40 parts of methyl methacrylate, 20 parts of methyl acrylate, 20 parts of butyl acrylate, and 2 parts of 2,2-azobisbutyronitrile in 20 parts of a mineral terpene was used for 2 hours. The solution was dropped (b). 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 (I-1).

(3) Preparation of silicate oligomer (D) 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 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 (D-1).

(4) Preparation of Non-Aqueous Dispersion (II) In 120 parts of a mineral turpentine, 20 parts of the resin dispersant (B-1) polymerized in the above (1) and the silicate oligomer prepared in the above (3) ( D-1) 100 parts and 10
The mixture was stirred for 2 hours while keeping the temperature at 0 ° C.
1) was obtained. (5) Preparation of non-aqueous dispersion type resin composition (III) To 100 parts of non-aqueous dispersion type resin composition (I-1), add 50 parts of non-aqueous dispersion (II-1), and keep at 100 ° C. While 2
After stirring for an hour, a non-aqueous dispersion type resin composition (III-1) was obtained. Obtained non-aqueous dispersion type resin composition (III-1) 100
Parts, kneaded with 100 parts of titanium white tarpaque (manufactured by Ishihara Sangyo Co., Ltd.) as a pigment to obtain a paint, and after adjusting the viscosity using a mineral terpen with a Ford cup # 4 for 12 seconds (25 ° C.). Then, a solution prepared by dissolving 0.1 part of dibutyltin laurylate and 0.01 part of tris (acetylacetate) aluminum in 10 parts of mineral turpentine is added, stirred and mixed, so that the coating film becomes 45 μm to 55 μm (after drying). Then, a slate plate (JIS F5403 regulation) was spray-coated to obtain an evaluation test plate.

The evaluation test plate was left 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 until the retention of 60 ° specular gloss measured by Nippon Denshoku Co., Ltd. with a # -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 evaluation test plate was subjected to the following performance test (No. 2). -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) Polymerization of Resin Dispersant (B) Resin dispersant (B-1) polymerized by the same procedure as in Example 1.
I got (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition (I) Polymerization was carried out in the same manner as in Example 1 except that 20 parts of γ-methacryloxypropyltrimethoxysilane was further added dropwise (b). To obtain a non-aqueous dispersion type resin composition (I
-2) was obtained. (3) Preparation of silicate oligomer (D) In the same manner as in Example 1, silicate oligomer (D-1)
I got (4) Preparation of non-aqueous dispersion (II) A non-aqueous dispersion (II-1) was obtained in the same manner as in Example 1. (5) Preparation of non-aqueous dispersion type resin composition (III) In the preparation of Example 1, the non-aqueous dispersion type resin composition (I-
A non-aqueous dispersion type resin composition (III-) was prepared in the same manner except that the non-aqueous dispersion type resin composition (I-2) was used in place of 1).
2) was obtained, and the same evaluations as in Example 1 were performed.

Example 3 (1) Polymerization of Resin Dispersant (B) Resin dispersant (B-1) was polymerized by the same operation as in Example 1.
I got (2) Synthesis of non-aqueous dispersion type resin composition (I) Polymerization was carried out in the same manner as in Example 1 to obtain a non-aqueous dispersion type resin composition (I-1). (3) Preparation of silicate oligomer (D) 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 (D-2). (4) Preparation of Non-Aqueous Dispersion (II) The same procedures as in Example 1 were carried out except that the silicate oligomer (D-2) obtained in (3) above was used instead of the silicate oligomer (D-1) in Example 1. In the same manner as in Example 1, a non-aqueous dispersion (II-2) was obtained. (5) Preparation of non-aqueous dispersion type resin composition (III) In the preparation of Example 1, a non-aqueous dispersion (II-2) was used in place of the non-aqueous dispersion (II-1). The mixture was mixed to obtain a non-aqueous dispersion type resin composition (III-3), and the same evaluation as in Example 1 was performed.

Example 4 (1) Polymerization of Resin Dispersant (B) The procedure was the same as in (a), except that γ-methacryloxypropylmethyldimethoxysilane was used instead of γ-methacryloxypropyltrimethoxysilane. Polymerization was carried out in the same manner as in Example 1 to obtain a resin-based dispersant (B-2). (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition (I) In the synthesis of Example 1, the resin-based dispersant (B) was added dropwise (b).
Polymerization was carried out in the same manner except that the above (B-2) was used instead of -1) to obtain a non-aqueous dispersion type resin composition (I-3). (3) Preparation of silicate oligomer (D) The silicate oligomer (D-1) was prepared in the same manner as in Example 1.
I got (4) Preparation of non-aqueous dispersion (II) In the preparation of Example 1, except that the resin-based dispersant (B-2) was used instead of the resin-based dispersant (B-1), A non-aqueous dispersion (II-3) was obtained. (5) Preparation of non-aqueous dispersion type resin composition (III) In the preparation of Example 1, a non-aqueous dispersion type (II-3) was used instead of the non-aqueous dispersion type (II-1). A non-aqueous dispersion type resin composition (III) was prepared in the same manner except that the non-aqueous dispersion type resin composition (I-3) was used in place of the resin composition (I-1).
-4), and the same evaluations as in Example 1 were performed.

Comparative Example 1 (1) Polymerization of Resin Dispersant (B) Polymerization was conducted in the same manner as in (a), except that 10 parts of 2-hydroxyethyl methacrylate was added instead of γ-methacryloxypropyltrimethoxysilane. Polymerization was carried out in the same manner as in Example 1 to obtain a resin-based dispersant (B-3). (2) Synthesis of non-aqueous dispersion type resin composition (I) Same as in the synthesis of Example 1, except that resin-based dispersant (B-3) was used instead of resin-based dispersant (B-1). To obtain a non-aqueous dispersion type resin composition (I-4). The same evaluation as in Example 1 was carried out by adding the pigment to the non-aqueous dispersion type resin composition (I-4) obtained above without mixing the non-aqueous dispersion (II) as a paint.

Comparative Example 2 (1) Polymerization of Resin Dispersant (B) Polymerization was carried out in the same manner as in Example 1 to produce a resin dispersant (B-1).
I got (2) Synthesis of non-aqueous dispersion type resin composition (I) In the synthesis of Example 1, polymerization was carried out by the same operation to obtain a non-aqueous dispersion type resin composition (I-1). The same evaluation as in Example 1 was performed by adding a pigment to the non-aqueous dispersion type resin composition (I-1) obtained above without mixing the non-aqueous dispersion (II) as a paint.

Comparative Example 3 (1) Polymerization of Resin Dispersant (B) Polymerization was conducted in the same manner as in (a), except that 10 parts of 2-hydroxyethyl methacrylate was added instead of γ-methacryloxypropyltrimethoxysilane. Polymerization was carried out in the same manner as in Example 1 to obtain a resin-based dispersant (B-3). (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition (I) In the synthesis of Example 1, the resin dispersant (B) was added dropwise (II).
Non-aqueous dispersion type resin composition polymerized by the same operation except that polymerization was performed using 20 parts of γ-methacryloxypropyltrimethoxysilane using a resin dispersant (B-3) instead of -1). (I-5) was obtained. The same evaluation as in Example 1 was carried out by adding the pigment to the non-aqueous dispersion type resin composition (I-5) obtained above without mixing the non-aqueous dispersion (II) as a paint.

Comparative Example 4 (1) Polymerization of Resin Dispersant (B) Polymerization was conducted in the same manner as in Example 1 to obtain a resin dispersant (B-1).
I got (2) Synthesis of Non-Aqueous Dispersion Type Resin Composition (I) The same operation as in the synthesis of Example 1 except that polymerization was carried out dropwise (b) using 20 parts of γ-methacryloxypropyltrimethoxysilane. To obtain a non-aqueous dispersion type resin composition (I-2). The same evaluation as in Example 1 was performed by adding a pigment to the non-aqueous dispersion type resin composition (I-2) obtained above without mixing the non-aqueous dispersion (II) as a paint.

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.

[0041]

[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

[0042]

[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 5.2 ４ 4 2000 peels 4.8

[0043]

[Table 3]

[0044]

The present invention provides an organic solvent that does not dissolve silicate oligomers, a resin-based dispersant that is soluble in the organic solvent, a polymer that is insoluble in the organic solvent, and a silicate oligomer that is insoluble in the organic solvent. And the resin-based dispersant is a non-aqueous dispersion type resin composition characterized by containing a hydrolyzable silyl group, so that when used for coating applications, the coating composition has stain resistance and weather resistance. The present invention can provide a resin composition for a paint that can provide a film with a high solid content and that can be applied in a cold region where it cannot be applied with a low odor or an aqueous emulsion during application.

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[Procedure amendment]

[Submission date] September 11, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

As the polymerization method for obtaining the non-aqueous dispersion type resin composition (I), known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization can be used. As in B), dispersion polymerization is most preferred. The polymerization initiator used in the polymerization may be of the same type as the polymerization initiator (L) used in the polymerization of the resin-based dispersant (B). The resin-based dispersant (B) is 3-80 parts by weight, the organic solvent (A) is 3-600 parts by weight, and the polymerization initiator (L) is 100 parts by weight of the radical polymerizable unsaturated monomer. Suitably selected from the range of 0.5 to 15 parts by weight,
Preferably, the resin-based dispersant (B) is 5 to 80 parts by weight, the organic solvent (A) is 50 to 300 parts by weight, and the resin-based dispersant (B) is less than 5 parts by weight or the organic solvent (A) Is 50
When the amount is less than 10 parts by weight, the dispersion stability tends to be poor, and when the amount of the resin dispersant (B) exceeds 80 parts by weight or the amount of the organic solvent (A) exceeds 300 parts by weight, the sagging property is poor. And drying properties are poor, and 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] 0032

[Correction method] Change

[Correction contents]

After standing at 20 ° C. for 45 minutes immediately after coating, the evaluation test plate was subjected to the following performance test (No. 2).・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 (6)

[Claims] 1. An organic solvent (A) that does not dissolve a silicate oligomer, a resin dispersant (B) that is soluble in the organic solvent (A), and a polymer (C) that is insoluble in the organic solvent (A) When,
Silicate oligomer (D) insoluble in the organic solvent (A)
Wherein the resin-based dispersant (B) contains a hydrolyzable silyl group. 2. The silicate oligomer (D) is represented by the following formula 1.
The non-aqueous dispersion type resin composition for paint according to claim 1, which is represented by: 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. A polymer (C) 1 insoluble in an organic solvent (A)
5 parts by weight of the silicate oligomer (D)
3. The non-aqueous dispersion type resin composition for paint according to claim 1, wherein the amount is 200 parts by weight. 4. The resin component dispersant (B) having a weight component of 1 to 2
The non-aqueous dispersion type resin composition for paint according to claim 1, wherein 0% by weight is a hydrolyzable silyl group-containing vinyl monomer. 5. A non-aqueous dispersion comprising a polymer (C) obtained by polymerizing a radically unsaturated monomer in an organic solvent (A) in the presence of a resin-based dispersant (B). The non-aqueous dispersion type resin for paint according to claim 1, wherein the resin composition (I) and a non-aqueous dispersion (II) containing a silicate oligomer (D) as a main component are mixed. Composition. 6. The non-aqueous dispersion (II) is prepared by mixing (A)
The non-aqueous dispersion type resin composition for coating material according to claim 4, comprising a resin, a resin-based dispersant (B) and a silicate oligomer (D).