JPH07113056A - Resin composition for coating compound and coating compound - Google Patents

Abstract

PURPOSE:To obtain the composition having excellent storage stability and improved stain resistance, curing properties, impact resistance, weathering resistance, etc., of coating film, comprising a mixture of a specific water non- dispersible resin and a solution type resin. CONSTITUTION:A water non-dispersible resin containing (A) an organic solvent- soluble vinyl-based polymer consisting essentially of an aliphatic hydrocarbon and (B) vinyl-based polymer particles insoluble in the organic solvent, obtained by polymerizing a polymerizable unsaturated compound in the organic solvent by using the component A as a dispersion stabilizer, is mixed with (C) a solution type resin composed of a vinyl-based polymer which is soluble in the organic solvent and contains a silyl group of the formula (R is alkyl, aryl, etc.; (k) is 1-3) to provide the composition. The water non-dispersible type resin is preferably obtained by synthesizing the component B in the organic solvent having dissolved the component A. gamma-(Meth)acryloyloxyethyltrimethoxysilane is preferable as the polymerizable unsaturated compound containing the group of the formula used for synthesizing the component C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition and a coating composition containing the resin composition.

[0002]

2. Description of the Related Art Paints used for mortar, slate, concrete, etc. for building exteriors are required to have high durability, that is, weather resistance, water resistance, moisture resistance, alkali resistance, acid resistance and the like. Copolymers containing acrylic acid esters and methacrylic acid esters as main components, so-called paints that use so-called solvent-type acrylic resin as a color-developing agent, are excellent in coating workability and have good durability, so they are suitable for building exteriors. It is used. However, when painting, a thinner containing a large amount of toluene and xylene as a main component is used.
There is a problem such as harmfulness to the environment. Further, when the coating material is used for repairing the exterior coating film, since toluene and xylene have a strong dissolving power, the coating film as the base is attacked to cause a lifting phenomenon and the like, which is difficult to use for repairing. On the other hand, there are paints that use acrylic emulsion resin with water as a medium to improve the repairability problem and harm to human body and environment, but for building exterior, durability, especially water resistance, moisture resistance Since it is inferior in nature, there is a practical problem.

[0003]

A non-aqueous dispersion type acrylic resin is a resin having an intermediate property between the above solvent type acrylic resin and acrylic emulsion resin. Since the non-aqueous dispersion type acrylic resin can use a solvent of an aliphatic hydrocarbon or a solvent containing an aliphatic hydrocarbon as a main component, it is less harmful to the human body and the environment as compared with a conventional solvent type acrylic resin. Since it does not contain a highly hydrophilic emulsifier, it has good durability. Although the non-aqueous dispersion type acrylic resin has such characteristics, its weather resistance is insufficient as compared with solvent-type acrylic urethane paints, fluororesins and the like, and improvement in characteristics is required.

On the other hand, silicone resin is excellent in heat resistance, weather resistance and the like, and attempts have been made to use a silicone-modified acrylic resin that takes advantage of its characteristics in paints. Japanese Examiner Sho 63
No. 443 discloses a method of hydrolyzing and condensing a solvent type acrylic resin having a silyl group using a curing catalyst. The coating film obtained by this method is excellent in chemical resistance and water resistance, but has a drawback that mechanical strength is not always sufficient and stain resistance and coating workability are poor. Further, JP-A-62-116605 discloses a method of producing a non-aqueous dispersion type acrylic resin by polymerizing an acrylic acid ester and a methacrylic acid ester in the presence of a polysiloxane resin. Although a non-aqueous dispersion can be obtained by this method, the film-forming property is insufficient. Furthermore, JP-A-64-75502 and JP-A-1-951
Japanese Unexamined Patent Publication No. 16 discloses a composition in which a curing catalyst is mixed with a non-aqueous dispersion liquid using an acrylic resin having a silyl group as a dispersion stabilizer. Although these compositions have excellent mechanical strength and chemical resistance of the coating film, they are not always sufficient in stain resistance and storage stability. Furthermore, JP-A-2-64
Japanese Unexamined Patent Publication No. 110 discloses a non-aqueous dispersion type composition using a vinyl polymer having a hydrolyzable silyl group in dispersed resin particles, which is inferior in stain resistance and coating film hardness. is there.

[0005]

The present invention solves the above problems, and relates to a coating resin composition and a coating having excellent stain resistance and sufficient other properties. That is, the present invention relates to a vinyl polymer (A) which is soluble in an organic solvent containing an aliphatic hydrocarbon as a main component, and a polymerizable unsaturated polymer in the organic solvent using the vinyl polymer (A) as a dispersion stabilizer. A non-aqueous dispersion type resin containing vinyl polymer particles (B) insoluble in the organic solvent obtained by polymerizing a compound, and a silyl group soluble in the organic solvent and represented by the general formula (I) The present invention relates to a coating resin composition containing a mixture of a solution-type resin, which is a vinyl-based polymer (C), and a coating composition containing the coating resin composition.

[Chemical 2] (In the formula, R ₁ is an alkyl group, an aryl group or an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group or a hydroxy group, and k is an integer of 1 to 3.)

In the present invention, the vinyl polymer (A)
Is used as a dispersion stabilizer for a non-aqueous dispersion type resin, and a method for producing it is known. For example, a compound having a polymerizable unsaturated double bond such as (meth) acrylic acid ester can be polymerized by a known method. However, since the obtained vinyl polymer (A) needs to be dissolved in an organic solvent containing an aliphatic hydrocarbon as a main component, it is specifically used as a polymerizable unsaturated compound of (meth) acrylic acid ester. Is, for example, n-butyl (meth) acrylate,
t-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobornyl ( The main component is one or more kinds of alkyl groups such as (meth) acrylate and dicyclopentanyl (meth) acrylate having 4 or more carbon atoms, particularly (meth) acrylic acid esters having 4 to 30 carbon atoms. That is, it is preferably used as 50% by weight or more), and particularly preferably 60% by weight or more. In addition, (meth) acrylic acid ester means methacrylic acid ester or acrylic acid ester,
(Meth) acrylate means methacrylate or acrylate (the same applies hereinafter).

If the vinyl polymer (A) thus obtained is selected to be soluble in an organic solvent containing an aliphatic hydrocarbon as a main component, methyl (meth) acrylate,
Alkyl group of ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate (meth) acrylic acid ester having 3 or less carbon atoms, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxyl group-containing (meth) acrylic acid ester such as hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) An amino group-containing (meth) acrylic acid ester such as acrylate can be copolymerized. Furthermore, as other polymerizable unsaturated compounds, styrene, vinyltoluene, substituted styrenes such as α-methylstyrene, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide and the like can be used in combination.

Examples of the polymerization initiator used for the polymerization include isobutyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butylcumyl peroxide and benzoyl peroxide. Oxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, diisobutylperoxydicarbonate, 2-diethylhexylperoxydicarbonate, 2,5- Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexane) propane, 2,2-bis (t-butylperoxy) butane, t -Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-
Butyl peroxy-2-ethyl hexanoate, 1,
1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 2,2-bis (4,4 -Di-t-butylperoxycyclohexyl) propane and other organic peroxides, 2,2 '
-Azo compounds such as azobis (isobutyronitrile), dimethylazodiisobutyrate, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2-methylbutyronitrile) , And one or more kinds can be used. The amount used is determined depending on the intended molecular weight of the vinyl polymer (A), but is usually 0.1 to 0.1% with respect to the total amount of the polymerizable unsaturated compound.
10.0% by weight is preferred. If necessary, a molecular weight can be adjusted by using a chain transfer agent such as n-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane. You may.

The polymerization of the vinyl polymer (A) of the present invention is
Known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization are possible, but solution polymerization that can be directly used in the next polymerization step is most preferable. This solution polymerization is
It is carried out in an organic solvent containing an aliphatic hydrocarbon as a main component (that is, containing 50% by weight or more). The organic solvent used in the present invention includes, of course, an organic solvent containing only an aliphatic hydrocarbon. Examples of the aliphatic hydrocarbons include linear aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, and cyclic aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane and cycloheptane. In addition, mineral spirits, mineral thinners, petroleum spirits, white spirits, which are mixed solvents mainly composed of aliphatic hydrocarbons,
Mineral terpen can also be used. In addition, add aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and alcohols such as methanol, ethanol, propanol and butanol. Although it is also possible, when an organic solvent other than these aliphatic hydrocarbons is added, it is preferably 30% by weight or less with respect to the total organic solvent.

The vinyl polymer (A) is obtained by the above method, and then the polymerizable unsaturated compound is polymerized in the dissolving organic solvent to obtain vinyl polymer particles (B) insoluble in the solvent. The vinyl-based polymer particles (B) obtained are
It is insoluble in organic solvents containing aliphatic hydrocarbons as the main component.
If the vinyl polymer particles (B) are dissolved in a solvent containing an aliphatic hydrocarbon as a main component, they do not become a non-aqueous dispersion type resin, and a useful coating resin having excellent effects as in the present invention. Can't get

Vinyl-based polymer particles (B) insoluble in an organic solvent containing an aliphatic hydrocarbon as a main component in the present invention
Can be obtained by polymerizing a polymerizable unsaturated compound by a known method in the same manner as the vinyl polymer (A). However, since the obtained vinyl polymer particles (B) are insoluble in an organic solvent, the polymerizable unsaturated compound as a starting material is
For example, methyl (meth) acrylate, ethyl (meth)
Alkyl group of acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate (meth) acrylic acid ester having 3 or less carbon atoms, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid ester such as N, N-dimethylaminoethyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Amino group-containing (meth) acrylic acid esters such as acrylate and N, N-dimethylaminopropyl (meth) acrylate are mainly used. It is preferable to copolymerize one or more of these polymerizable unsaturated compounds in an amount of 50% by weight or more, particularly 60% by weight or more, based on the total amount of polymerizable unsaturated compounds. Particularly, 60% by weight of a (meth) acrylic acid ester having 3 or less carbon atoms in all polymerizable unsaturated compounds.
It is preferable to copolymerize at least 70% by weight.

Further, within the range in which the component (B) becomes insoluble,
For example, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth). An alkyl group such as acrylate or dicyclopentanyl (meth) acrylate may be used together with a polymerizable unsaturated compound such as (meth) acrylic acid ester having 4 or more carbon atoms. Furthermore, substituted styrenes such as styrene, vinyltoluene and α-methylstyrene, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide and the like can be used in combination.

As the polymerization initiator used for the polymerization of the vinyl polymer particles (B), the same polymerization initiator as exemplified in the above description is used. The amount used is determined by the intended molecular weight of the vinyl polymer particles (B), but is usually 0.1 to 10.0 with respect to the total polymerizable unsaturated compound as the component (B). Weight percent is preferred.

Although the non-aqueous dispersion type resin is obtained as described above, the ratio of the organic solvent-soluble vinyl polymer (A) to the organic solvent-insoluble vinyl polymer particle (B) is the same. /
The latter (weight ratio) is preferably 10/90 to 60/40.
When it is less than 10/90, the dispersion stability tends to be poor, and when it exceeds 60/40, the drying property is poor and the coating workability may be a problem. During the polymerization, other additives such as dispersion stabilizers and rheology control agents may be used in combination.

The average particle size of the vinyl polymer particles (B) in the non-aqueous dispersion type resin is usually about 100 to 2000 nm.
It is preferably within the range. If the average particle size is less than 100 nm, the viscosity of the varnish tends to increase, and if the average particle size exceeds 2000 nm, the particles tend to swell or aggregate during storage. Further, in the present invention, the storage stability and the like can be further improved by chemically binding the vinyl polymer (A) and the vinyl polymer particles (B). As a method of binding, for example,
It can be carried out by polymerizing the polymerizable unsaturated compound in the presence of the vinyl polymer (A) having a polymerizable unsaturated double bond. The unsaturated double bond is introduced into the vinyl polymer (A) by using, for example, a carboxyl group-containing polymerizable unsaturated compound as a copolymerization component of the vinyl polymer (A), and using glycidyl (meta ) It can be carried out by reacting a polymerizable unsaturated compound containing an epoxy group such as acrylate and allyl glycidyl ether. Of course, it can also be carried out by allowing an epoxy group to be contained in the resin and reacting it with a carboxyl group-containing polymerizable unsaturated compound.

The coating resin composition of the present invention is soluble in the above-mentioned non-aqueous dispersion type resin and the above-mentioned organic solvent and has the general formula (I).
It is obtained by mixing a solution type resin, which is a vinyl polymer (C) having a silyl group represented by In the general formula (I), R ₁ is preferably an alkyl group having 1 to 18 carbon atoms, an aryl group such as a phenyl group or a naphthyl group, an aralkyl group such as a benzyl group, particularly preferably a methyl group or a phenyl group, and X is represented by X. Is preferably an alkoxy group having 1 to 8 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or a hydroxy group, and particularly preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group. The vinyl polymer (C) having a silyl group represented by the general formula (I) is produced by a known method, for example, a polymerizable unsaturated compound such as (meth) acrylic acid ester and a general formula (I). It is produced by polymerizing the polymerizable unsaturated compound having a silyl group shown by a known method. As the polymerizable unsaturated compound such as (meth) acrylic acid ester, those exemplified in the description of the vinyl polymer (A) are used. However, the resulting vinyl polymer (C) must be soluble in an organic solvent containing an aliphatic hydrocarbon as a main component.

As the polymerizable unsaturated compound having a silyl group represented by the general formula (I), for example, the polymerizable unsaturated compound represented by the general formula (II) is preferable.

[Chemical 3] (In the formula, R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
An alkyl group, an aryl group or an aralkyl group, R
₅ is a hydrogen atom or a methyl group, R ₆ is a divalent organic group, A is —COO— or a phenylene group, X
Is a halogen atom, an alkoxy group, an acyloxy group or a hydroxy group, a is 0 or an integer of 1 to 20, and k is an integer of 1 to 3) R ₂ , R ₃ and R ₅ are the same as those of R ₁ . Preferable ones are the same as those described above, X is also preferably the same, R ₆ is preferably an alkylene group having 1 to ₆ carbon atoms, and a is preferably 0 to 5.

Examples of the polymerizable unsaturated compound represented by the general formula (II) in the present invention include 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- (meth) acryloxydecyltrimethoxysilane, γ- (Meth) acryloxyoctadecyltrimethoxysilane,

[Chemical 4] Etc. In addition, "(meth) acryloxy" means "acryloxy" or "methacryloxy".
In addition, as the polymerizable unsaturated compound having a silyl group represented by the general formula (I), vinylsilane compounds such as trimethoxyvinylsilane, triethoxyvinylsilane, tris (ethylmethylketoxime) vinylsilane, and triacetoxyvinylsilane, or allyltrialkyl vinyl trisilane. Examples thereof include allylsilane compounds such as methoxysilane, allyltriethoxysilane and allyltrichlorosilane. These silyl group-containing polymerizable unsaturated compounds represented by the general formula (I) may be used either individually or in combination of two or more.

The polymerizable unsaturated compound having a silyl group as described above can be copolymerized with the polymerizable unsaturated compound exemplified as the raw material of the vinyl polymer (A). In this case, the polymerizable unsaturated compound having a silyl group is preferably blended in an amount of 5 to 40% by weight based on the total polymerizable unsaturated compound and polymerized. If it is less than 5% by weight, the weather resistance tends to be poor, while if it exceeds 40% by weight, it may thicken and gel. The polymerization method can be performed in the same manner as the method for producing the vinyl polymer (A). The resulting vinyl polymer (C) is a solution type resin that is soluble in a solvent containing an aliphatic hydrocarbon as a main component.

In the present invention, it is important to use the non-aqueous dispersion type resin and the solution type resin which is the vinyl polymer (C) in combination, but the former and the latter are 97 in terms of solid content weight ratio.
It is preferable that they are mixed so as to be ⅓ to 60/40, particularly 97/3 to 70/30. Where this ratio is 97/3
If it exceeds, the curability tends to be inferior, while if it is less than 60/40, sagging or the like occurs, and workability tends to be inferior.
Further, it is preferable to adjust the vinyl polymer particles (B) in the non-aqueous dispersion type resin so as to have the silyl group represented by the general formula (I) because the curability is improved.
In that case, it is preferable to use the polymerizable unsaturated compound having a silyl group represented by the general formula (I) in an amount of 1 to 40% by weight based on all unsaturated compounds constituting the component (B). However, it is preferable that the vinyl polymer (A) does not contain the silyl group represented by the general formula (I) in terms of stain resistance and storage stability. The molecular weights of the components (A), (B) and (C) are not particularly limited, but the number average molecular weights of (A) and (B) are 5,000 to 50,000, and the number average molecular weight of (C) is number average. The molecular weight is preferably 1,000 to 40,000. The number average molecular weight as referred to herein is a value measured by gel permeation chromatography and converted into standard polystyrene.

The coating resin composition of the present invention further comprises, as a curing agent, an acidic compound, a basic compound or a tin-containing compound alone, a tin-containing compound and an acidic compound, or a mixture of a tin-containing compound and a basic compound. It can also be blended.
Examples of these compounds include acidic compounds, for example,
p-toluenesulfonic acid, acetic acid, (meth) acrylic acid,
Examples thereof include dibutyl phosphoric acid and dioctyl phosphoric acid, and examples of the basic compound include n-butylamine, t-butylamine, 2-ethylhexylamine, γ-aminopropyltriethoxysilane, trioctylamine, dibutylamine, hexylamine, and triethylamine. Examples of the tin-containing compound include dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dibutyltin dioctoate, and the like.

To the resin composition for paints of the present invention, pigments such as titanium white, carbon black and phthalocyanine blue, extender pigments such as calcium carbonate and barium sulfate, and a solvent may be added to prepare an enamel paint by a conventional method. it can. It is also possible to make a clear paint without adding the pigment. As a method for forming an enamel coating, for example, a known method such as roll, sand mill, disperser or the like can be used. Further, an enamel paint can be prepared by using a seed pen having good compatibility with the resin composition for paint of the present invention. Furthermore, in order to improve the performance as a paint, it is possible to add a pigment dispersant, a leveling agent, etc. at the time of making the paint or after making the paint.

[0023]

EXAMPLES Examples of the present invention will be described below. In the symbols indicating the types of resins, A is a solvent-soluble solution type resin,
N represents a non-aqueous dispersion type resin. Synthesis Example 1 (1) Synthesis of Resin (A-1) A flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 400 g of mineral terpen (manufactured by Showa Shell Sekiyu KK). After the temperature was raised to 95 ° C., the polymerizable unsaturated compound shown in Table 1 and the polymerization initiator were added dropwise over 2 hours.

[Table 1] After completion of dropping, the mixture was kept warm for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 20 g of mineral terpene was added dropwise over 30 minutes. After the completion of the dropping, the temperature was raised to 100 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight.

(2) Synthesis of non-aqueous dispersion type resin (N-1) The resin (A) synthesized in (1) was placed in the same flask as in (1).
-1) 400 g was collected, and 150 g of mineral turpentine was added. After the temperature was raised to 100 ° C., the polymerizable unsaturated compound shown in Table 2 and the polymerization initiator were added dropwise over 2 hours.

[Table 2] The liquid that was transparent before the dropping became cloudy as the polymerization proceeded, and became a non-aqueous dispersion liquid. After dripping, keep warm for 1 hour,
Further, a liquid prepared by dissolving 2 g of t-butylperoxy-2-ethylhexanoate in 50 g of mineral terpene was added dropwise, and the temperature was kept at 100 ° C. for 2 hours to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight. Resin viscosity 5400
A milky white non-aqueous dispersion resin having a centipoise, an average particle diameter of 780 nm and an acid value of 1 or less was obtained. This was named "N-1".

Synthesis Example 2 (3) Synthesis of Resin (A-2) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
400 g of mineral terpene was added. After heating to 95 ° C,
The polymerizable unsaturated compound shown in Table 3 and the polymerization initiator were added dropwise over 2 hours.

[Table 3] After completion of dropping, the mixture was kept warm for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 20 g of mineral terpene was added dropwise over 30 minutes. After the completion of the dropping, the temperature was raised to 100 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight.

(4) Synthesis of Non-Aqueous Dispersion Resin (N-2) The resin (A) synthesized in (3) was placed in the same flask as in (3).
-2) 400 g was collected, and 160 g of mineral terpen was added. After the temperature was raised to 100 ° C., the polymerizable unsaturated compound shown in Table 4 and the polymerization initiator were added dropwise over 2 hours.

[Table 4] The liquid that was transparent before the dropping became cloudy as the polymerization proceeded, and became a non-aqueous dispersion liquid. After dripping, keep warm for 1 hour,
Further, a liquid prepared by dissolving 2 g of t-butylperoxy-2-ethylhexanoate in 50 g of mineral terpene was added dropwise, and the temperature was kept at 100 ° C. for 2 hours to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight. Resin viscosity 480
A milky white non-aqueous dispersion type resin having 0 centipoise, an average particle size of 770 nm and an acid value of 1 or less was obtained. This was named "N-2".

Synthesis Example 3 (5) Synthesis of Resin (A-3) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
400 g of mineral terpene was added. After heating to 95 ° C,
The polymerizable unsaturated compound shown in Table 5 and the polymerization initiator were added dropwise over 2 hours.

[Table 5] After completion of the dropping, the temperature was kept for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 50 g of mineral terpene was added dropwise over 30 minutes. After the completion of the dropping, the temperature was raised to 100 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight.

(6) Synthesis of Non-Aqueous Dispersion Resin (N-3) The resin (A) synthesized in (5) was placed in the same flask as in (5).
-3) 400 g was collected, and 150 g of mineral turpentine was added. After the temperature was raised to 100 ° C., the polymerizable unsaturated compound shown in Table 6 and the polymerization initiator were added dropwise over 2 hours.

[Table 6] The liquid that was transparent before the dropping became cloudy as the polymerization proceeded, and became a non-aqueous dispersion liquid. After dripping, keep warm for 1 hour,
Further, a solution prepared by dissolving 2 g of t-butylperoxy-2-ethylhexanoate in 50 g of mineral terpene was additionally dropped, and the temperature was kept at 100 ° C. for 2 hours to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight. A milky white non-aqueous dispersion type resin having a resin viscosity of 5000 centipoise, an average particle size of 760 nm and an acid value of 1 or less was obtained. This was named "N-3".

Synthesis Example 4 (7) Synthesis of Resin (A-4) A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 400 g of mineral terpene. After heating to 95 ° C,
The polymerizable unsaturated compound shown in Table 7 and the polymerization initiator were added dropwise over 2 hours.

[Table 7] After completion of dropping, the mixture was kept warm for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 20 g of mineral terpene was added dropwise over 30 minutes. After the completion of the dropping, the temperature was raised to 100 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight.

(8) Synthesis of Non-Aqueous Dispersion Resin (N-4) The resin (A) synthesized in (7) was placed in the same flask as in (7).
-4) 400 g was collected, and 150 g of mineral turpentine was added. After the temperature was raised to 100 ° C., the polymerizable unsaturated compound shown in Table 8 and the polymerization initiator were added dropwise over 2 hours.

[Table 8] The liquid that was transparent before the dropping became cloudy as the polymerization proceeded, and became a non-aqueous dispersion liquid. After dripping, keep warm for 1 hour,
Further, a solution prepared by dissolving 2 g of t-butylperoxy-2-ethylhexanoate in 50 g of mineral terpene was additionally dropped, and the temperature was kept at 100 ° C. for 2 hours to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight. A milky white non-aqueous dispersion type resin having a resin viscosity of 8500 centipoise, an average particle size of 740 nm and an acid value of 1 or less was obtained. This was named "N-4".

Synthesis Example 5 (9) Synthesis of Resin (A-5) 400 g of mineral terpene was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. After heating to 95 ° C,
The polymerizable unsaturated compound in Table 9 and the polymerization initiator were added dropwise over 2 hours.

[Table 9] After completion of the dropping, the temperature was kept for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 50 g of mineral terpene was added dropwise over 30 minutes. After the completion of the dropping, the temperature was raised to 100 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight.

(10) Synthesis of non-aqueous dispersion type resin (N-5) The resin (A) synthesized in (9) was placed in the same flask as in (9).
-5) 300 g was collected and 250 g of mineral terpen was added. After the temperature was raised to 100 ° C., the polymerizable unsaturated compound shown in Table 10 and the polymerization initiator were added dropwise over 2 hours.

[Table 10] The liquid that was transparent before the dropping became cloudy as the polymerization proceeded, and became a non-aqueous dispersion liquid. After dripping, keep warm for 1 hour,
Further, a solution prepared by dissolving 2 g of t-butylperoxy-2-ethylhexanoate in 30 g of mineral terpene was additionally dropped, and the temperature was kept at 100 ° C. for 2 hours to complete the polymerization reaction. After cooling, mineral terpen was further added to adjust the heating residue to 50% by weight. A milky white non-aqueous dispersion type resin having a resin viscosity of 4500 centipoise, an average particle size of 750 nm and an acid value of 1 or less was obtained. This was named "N-5".

Synthesis Example 6 (11) Synthesis of Resin (A-6) 400 g of mineral terpene was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. After heating to 90 ℃,
The polymerizable unsaturated compound shown in Table 11 and the polymerization initiator were added dropwise over 2 hours.

[Table 11] After completion of dropping, the mixture was kept warm for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 20 g of mineral terpene was added dropwise over 30 minutes. After the completion of the dropping, the temperature was raised to 100 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, additional xylene was added and the heating residue was 5
It was adjusted to be 0% by weight. This one is "A-6"
I named it.

Comparative Synthesis Example 1 (12) Synthesis of Resin (A-7) 400 g of mineral terpene was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer. After heating to 95 ° C,
The polymerizable unsaturated compound shown in Table 12 and the polymerization initiator were added dropwise over 2 hours.

[Table 12] After completion of the dropping, the temperature was kept for 1 hour, and a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 50 g of xylene was added dropwise over 30 minutes. After completion of dropping, 1
The temperature was raised to 00 ° C. and the temperature was kept for 1 hour to complete the polymerization reaction. After cooling, xylene was further added to adjust the heating residue to 50% by weight. This was named "A-7".

(13) Synthesis of Non-Aqueous Dispersion Resin (N-7) 400 g of the resin (A-7) synthesized in (12) was collected in the same flask as in (12), and 200 g of heptane was added. After the temperature was raised to 100 ° C., the polymerizable unsaturated compound shown in Table 13 and the polymerization initiator were added dropwise over 2 hours.

[Table 13] The liquid that was transparent before the dropping became cloudy as the polymerization proceeded, and became a non-aqueous dispersion liquid. After dripping, keep warm for 1 hour,
Furthermore, a solution of 2 g of t-butylperoxy-2-ethylhexanoate dissolved in 20 g of heptane was added dropwise, and 10
Incubation at 0 ° C was continued for 2 hours to complete the polymerization reaction. After cooling, heptane was further added to adjust the heating residue to 50%. A milky white non-aqueous dispersion type resin having a resin viscosity of 7500 centipoise, an average particle size of 960 nm and an acid value of 1 or less was obtained. This was named "N-7".

Comparative Synthesis Example 2 (14) Synthesis of Resin (A-8) Same as (1) of Synthesis Example 1 except that the composition of the polymerizable unsaturated compound and the polymerization initiator to be dropped are changed to those shown in Table 14. The operation was performed to obtain an acrylic resin with a heating residue of 50% by weight.
This was named "A-8".

[Table 14]

Comparative Synthesis Example 3 (15) Synthesis of Resin (A-9) Same as (1) in Synthesis Example 1 except that the composition of the polymerizable unsaturated compound and the polymerization initiator to be dropped are changed to those in Table 15. The operation was performed to obtain an acrylic resin with a heating residue of 50% by weight.
This was named "A-9".

[Table 15]

In the following, "part" means "part by weight". Examples 1 to 7 and Comparative Examples 1 to 4 First, the resins (N-1) and (N-) obtained in Synthesis Examples 1 to 5 were used.
2), a resin composition obtained by mixing 135 parts of each of (N-3), (N-4), and (N-5) with 15 parts of resin (A-6), and Comparative Synthesis Example 1 Resin (N
The change in viscosity and the change in average particle size of (7) and (A-8) at 40 ° C. were measured. The results are shown in Table 16.

[Table 16]

Next, Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 3
The resin prepared in 1 above was kneaded with 75 parts of a white-type pen in the composition shown in Table 17 to obtain a white enamel paint. The white-type pen was prepared by using 15 parts of the resin (A-6) of Synthesis Example 6 as a color-developing agent and 50 parts of titanium white typec CR-95 (manufactured by Ishihara Sangyo Co., Ltd.) as a pigment, and kneading with 10 parts of mineral terpen. did.
Using a mineral terpene as a thinner, adjust the viscosity with a Ford cup # 4 for 15 seconds (25 ° C), and spray onto a slate plate (JIS F5403 standard) so that the coating film is 25 to 35 μm (after drying). Painted. J
It was left for 2 weeks in a curing room defined by IS and used as an evaluation test plate. The evaluation results are shown in Tables 17 and 18.

[0040]

[Table 17]

[0041]

[Table 18]

The test evaluation method is shown below. (1) Yield stress (difficulty in sagging): Determined by the Cone & Plate method. (2) Residual viscosity (lightness of brush): Determined by Cone & Plate method. (3) Curability: Cured under the conditions of temperature 23 ± 2 ° C. and humidity 75 ± 10% for the above time, and determined from gel fraction by Soxhlet extraction method ^* .

[Equation 1] * Extraction conditions: Extraction was performed for 8 hours using a mixed solution of acetone / methanol (1/1 weight ratio). (4) Contamination resistance: After being sprinkled with carbon and left for 12 hours for cleaning, the color difference between the contaminated part and the non-contaminated part was measured. (5) Impact resistance: Measured by a method defined by JIS 1421 method. (6) Accelerated weather resistance: Using a Sunshine Weather Meter (manufactured by Suga Test Instruments Co., Ltd.), the gloss was measured under the conditions of JIS 5400 to obtain the gloss retention rate.

[Equation 2]

[0043]

EFFECT OF THE INVENTION The resin composition for coating material of the present invention can be a coating material having excellent storage stability and excellent stain resistance, curability, impact resistance and weather resistance of the coating film.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Hironaka 3-8-40 Kitadamiya, Tokushima City, Tokushima Prefecture Hitachi Chemical Polymer Co., Ltd. Tokushima Factory

Claims (3)

[Claims] 1. A vinyl polymer (A) soluble in an organic solvent containing an aliphatic hydrocarbon as a main component, and a polymerizable unsaturated polymer in the organic solvent using the vinyl polymer (A) as a dispersion stabilizer. A non-aqueous dispersion type resin containing vinyl polymer particles (B) insoluble in the organic solvent, which is obtained by polymerizing a compound,
A resin composition for coating material, which comprises a mixture of a solution type resin which is soluble in the organic solvent and which is a vinyl polymer (C) having a silyl group represented by the general formula (I). [Chemical 1] (In the formula, R ₁ is an alkyl group, an aryl group or an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group or a hydroxy group, and k is an integer of 1 to 3.) 2. The resin composition for coating according to claim 1, wherein the weight ratio of the non-aqueous dispersion type resin to the solution type resin is 97/3 to 60/40 in the former / the latter. 3. A paint comprising the resin composition for paint according to claim 1 or 2.