JPH06128448A - Curable composition and paint - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent curability, pot-life, gloss and weather resistance and useful for paint, etc., by compounding a non-aqueous dispersion containing a specific vinyl polymer having a silyl group, etc., with a silicon compound. CONSTITUTION:The composition is produced by polymerizing a polymerizable unsaturated compound such as methyl (meth)acrylate in the presence of (A) a vinyl polymer having silyl group of formula (R1 is alkyl, aryl or aralkyl; X is halogen, alkoxy, etc.; (l) is 1-3), e.g. gamma-(meth)acryloxyethyl trimethoxysilane polymer in (B) a solvent such as aliphatic hydrocarbon dissolving the component A and compounding the obtained non-aqueous dispersion liquid containing vinyl polymer particles insoluble in the solvent with a silicon compound such as tetramethoxysilane as a curing agent. The compounding weight ratio of A/B is preferably 10/90 to 60/40.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition and a paint used as a paint or a sealing material.

[0002]

2. Description of the Related Art Paints used for mortar, slates, concrete, etc. for building exteriors are required to have high durability, that is, weather resistance, water resistance, moisture resistance, alkali resistance, acid resistance, etc. To be done. 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, since a thinner containing a large amount of toluene and xylene as a main component is used for coating, the human body,
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. In the non-aqueous dispersion type acrylic resin, since the solvent of the aliphatic hydrocarbon or the solvent of the aliphatic hydrocarbon main component can be used, the human body and the environment are less harmful than the conventional solvent type acrylic resin, Further, since it does not contain an emulsifier having a stronger hydrophilicity than the acrylic emulsion resin, 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. For example, JP-A-55-152745 discloses a method of hydrolyzing / condensing a solvent type acrylic resin having a silyl group in the presence of a basic catalyst. The coating film obtained by this method is excellent in chemical resistance and water resistance, but has the drawbacks that mechanical strength and gloss are not always sufficient and coating workability is poor. Further, since it is a solvent type, it has the same drawbacks as the solvent type acrylic resin. In addition, JP-A-1-
No. 95116, a non-aqueous dispersion liquid using a silyl group-containing acrylic resin as a dispersion stabilizer, an acidic compound,
A composition containing a curing catalyst such as a basic compound or a tin-containing compound is shown. This composition has good curability at low temperatures, and although the coating film has excellent mechanical strength, chemical resistance, and stain resistance, it does not have sufficient curability and gloss, and its weather resistance is slightly higher than that of fluororesin. Inferior. Furthermore, JP-A-62-1
Japanese Patent No. 16605 discloses a method for producing a non-aqueous dispersion type acrylic resin by polymerizing an acrylic acid ester and a methacrylic acid ester in the presence of an alkoxypolysiloxane resin. Although a non-aqueous dispersion can be obtained by this method, the dispersion stability is poor and the film-forming property is insufficient.

[0005]

The present invention has the general formula (I)
A vinyl polymer (A) having a silyl group represented by

[Chemical 3] (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 l is an integer of 1 to 3) (A) A non-aqueous dispersion containing vinyl polymer particles (B) insoluble in the solvent, which is obtained by polymerizing a polymerizable unsaturated compound in a dissolved solvent, is mixed with a silicon compound as a curing agent. The present invention relates to a curable composition and a coating composition.

In the present invention, a method for producing a vinyl polymer (A) having a silyl group represented by the general formula (I) is known. As the method, for example, 1) a method of copolymerizing a compound having a silyl group represented by the general formula (I) and a polymerizable unsaturated double bond with a polymerizable unsaturated compound, 2) a vinyl having a reactive functional group There is a method in which a silane compound having a functional group that reacts with the functional group and a silyl group represented by the general formula (I) is reacted with the polymer.

The former 1) is preferably a compound having a silyl group and a polymerizable unsaturated double bond represented by the general formula (I), for example, a polymerizable unsaturated group represented by the general formula (VIII). There is a compound.

[Chemical 4] (In the formula, R ₁₆ is a hydrogen atom or a methyl group, and R ₁₇ ,
R ₁₈ or R ₁₉ are each independently a hydrogen atom, an alkyl group,
Is an aryl group or an aralkyl group, R ₂₀ is a divalent organic group (preferably an alkylene group), and A is —COO.
-Or a phenylene group, X is a halogen atom, an alkoxy group, an acyloxy group or a hydroxy group, and a
Is an integer of 0 to 20, and l is an integer of 1 to 3)

Examples of the polymerizable unsaturated compound represented by the general formula (VIII) 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) acryloxydodecyltrimethoxysilane, γ- (meth) acryloxyoctadecyltrimethoxysilane, 1- (meth) acryloxypropyl-1,
1,3,3-tetramethyl-3-methoxydisiloxane, 1-
(Meth) acryloxypropyl-1,1,3,3,5,5-hexamethyl-5-methoxytrisiloxane, 1- (meth) acryloxypropyl-1,1-dimethyl-3,3,3-methoxydi Siloxane,

[Chemical 5] Etc. In addition, "(meth) acryloxy" means "acryloxy" or "methacryloxy".

Further, as a compound having a silyl group represented by the general formula (I) and a polymerizable unsaturated double bond,
Trimethoxyvinylsilane, triethoxyvinylsilane, tris (ethylmethylketoxime) vinylsilane,
Examples thereof include vinylsilane compounds such as triacetoxyvinylsilane and allylsilane compounds such as allyltrimethoxysilane, allyltriethoxysilane and allyltrichlorosilane. As the compound having a silyl group and a polymerizable unsaturated double bond represented by the general formula (I), one kind or two or more kinds can be used.

Further, the compound having a silyl group and a polymerizable unsaturated double bond represented by the general formula (I) in the present invention is copolymerized with a polymerizable unsaturated compound such as acrylic acid ester and methacrylic acid ester. The vinyl polymer (A) is used, but it needs to be dissolved in an organic solvent of an aliphatic hydrocarbon or an organic solvent containing an aliphatic hydrocarbon as a main component. Specific examples of the acrylic acid ester or methacrylic acid ester (hereinafter referred to as (meth) acrylic acid ester) include, for example, n-butyl (meth) acrylate,
tert-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) Acryle
(Meth) acrylic acid ester having an alkyl group having 4 or more carbon atoms, such as octyl, octyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. It is preferable to copolymerize one kind or two or more kinds as main components.

If the vinyl polymer (A) thus obtained is selected to be dissolved in an organic solvent of an aliphatic hydrocarbon or an organic solvent containing an aliphatic hydrocarbon as a main component, methyl (meth) acrylate is selected. , Ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-
Propyl (meth) acrylate alkyl group has 3 carbon atoms
The following (meth) acrylic acid ester, 2-hydroxyethyl (meth) acrylate, hydroxyl group-containing (meth) acrylic acid ester such as 2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth ) Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth)
It is also possible to copolymerize an amino group-containing (meth) acrylic acid ester such as an acrylate. The (meth) acrylate means acrylate or methacrylate.
Furthermore, as other polymerizable unsaturated compounds, styrene,
Substituted styrenes such as vinyltoluene and α-methylstyrene, vinyl chloride, vinylidene chloride, acrylonitrile,
Acrylamide and the like can be used together.

Regarding the ratio of the compound having a silyl group represented by the general formula (I) and the polymerizable unsaturated double bond in the present invention to be copolymerized with the polymerizable unsaturated compound of the (meth) acrylic acid ester, the former / The latter (weight ratio) is 5/9
5-40 / 60 is preferable. If it is less than 5/95, it is difficult to obtain a coating having good weather resistance, and if it exceeds 40/60, the vinyl polymer (A) is an organic solvent of an aliphatic hydrocarbon or an organic solvent containing an aliphatic hydrocarbon as a main component. Becomes insoluble in
The effect as a dispersant in the subsequent polymerization tends to disappear.

Examples of the polymerization initiator used in the polymerization include isobutylperoxide, lauroylperoxide, 3,5,5-trimethylhexanoylperoxide, octanoylperoxide, t-butylcumylperoxide and benzoylperoxide. -Oxide,
Dichlorobenzoylper oxide, dicumylper oxide, di-t-butylperoxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone oxide -Oxide, methylcyclohexanone peroxide, diisobutylperoxydicarbonate, 2-diethylhexylperoxydicarbonate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) ) Hexane, 1,1-bis (t-hexylpa-oxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t
-Butyl hydroper oxide, cumene hydroper
Oxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butylperoxy-2-
Ethyl hexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate Organic peroxides such as azobisisobutyronitrile, dimethylazodiisobutyrate
2,2-azobis (2.4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile)
And the like, and one or more kinds can be used. The amount used is determined by the intended molecular weight of the vinyl polymer (A), and is usually preferably 0.1 to 10.0% by weight based on the total amount of the polymerizable unsaturated compound.

The polymerization of these polymerizable unsaturated compounds of the present invention can be carried out by known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization, but can be directly used in the next polymerization step. Solution polymerization is most preferred. This solution polymerization is preferably performed in an organic solvent of an aliphatic hydrocarbon or an organic solvent containing an aliphatic hydrocarbon as a main component. Examples of the aliphatic hydrocarbons include linear aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane,
Examples thereof include cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane and cycloheptane. In addition, mineral spirits, which is a mixed solvent,
Mineral thinner, petroleum spirit, white spirit and mineral tape can also be used. Further, 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, methanol, ethanol, propanol, butanol and the like. It is also possible to add the alcohols. The range of adding the organic solvent other than the aliphatic hydrocarbon is preferably 30% by weight or less based on the total organic solvent.

Next, as a method for obtaining the vinyl polymer (A) having a silyl group represented by the general formula (I), the vinyl polymer having a reactive functional group of the above 2) is added to the vinyl polymer. A method of reacting a reactive functional group with a silane compound having a silyl group represented by the general formula (I) will be described. This method can be applied to vinyl polymers having functional groups such as carboxyl group, hydroxyl group, amide group and epoxy group, for example, in general formula (IX)

[Chemical 6] (In the formula, R ₂₁ 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 Z is a carboxyl group, a hydroxyl group, an amide group, an epoxy group or the like. It is a functional group that reacts with a functional group, and 1 is an integer of 1 to 3). Starting materials for vinyl polymers having a functional group such as a carboxyl group, a hydroxyl group, an amide group and an epoxy group are compounds having a functional group such as a carboxyl group, a hydroxyl group, an amide group and an epoxy group and a polymerizable unsaturated double bond. And a vinyl polymer is obtained by copolymerizing these with (meth) acrylic acid ester. Examples of the compound having these functional groups and a polymerizable unsaturated double bond include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
, (Meth) acrylamide, glycidyl (meth) acrylate and the like. The ratio of copolymerizing a compound having a polymerizable unsaturated double bond with a functional group such as a carboxyl group, a hydroxyl group, an amide group, an epoxy group and a (meth) acrylic acid ester is 10/90 to 50 for the former / latter. / 5
0 is preferred. If it is less than 10/90, it is difficult to obtain a coating film having good durability because the amount of silyl groups added is small. When it exceeds 50/50, it becomes insoluble in an organic solvent of an aliphatic hydrocarbon or an organic solvent containing an aliphatic hydrocarbon as a main component, and the effect as a dispersant tends to be lost. Examples of the compound represented by the general formula (IX) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and γ. -Glycidoxypropylmethyldiethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane and the like.

The reaction method is, for example, a method in which the vinyl polymer having the above functional group is dissolved in an organic solvent, then the compound represented by the general formula (IX) is added, and the mixture is heated to 80 ° C. or higher and stirred. is there. The ratio of the compound represented by the general formula (IX) to the vinyl polymer having a functional group is 0.5 / 1.0 to 1.0 in terms of the former functional group / the latter functional group molar ratio.
/1.0 is preferable. If it is less than 0.5 / 1.0, it is difficult to obtain a coating film with good durability because the amount of silyl groups added is small. If it exceeds 1.0 / 1.0, unreacted organic silane compound remains in the resin, so that the storage stability of the coating tends to be poor.

The polymerizable unsaturated compound is then polymerized in a solvent in which the vinyl polymer (A) having a silyl group represented by the general formula (I) obtained by each of the above methods is dissolved, A non-aqueous dispersion containing the vinyl polymer particles (B) insoluble in the solvent is obtained. If the vinyl-based polymer particles (B) are dissolved in an organic solvent of an aliphatic hydrocarbon or a solvent containing an aliphatic hydrocarbon as a main component, the non-aqueous dispersion type resin is not obtained but a solution type resin is obtained. No useful curable composition of the invention is obtained.

The polymerizable unsaturated compound as a starting material for the vinyl polymer particles (B) insoluble in the organic solvent of the aliphatic hydrocarbon or the organic solvent containing the aliphatic hydrocarbon as the main component in the present invention is For example, a methyl (meth) acrylate, an ethyl (meth) acrylate, an iso-propyl (meth) acrylate, an n-propyl (meth) acrylate having an alkyl group having 3 or less carbon atoms (meth) acryl Acid ester, 2-hydroxyethyl (meth) acrylate
Hydroxyl group-containing (meth) acrylic acid ester such as 2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Examples thereof include amino group-containing (meth) acrylic acid esters such as N, N-dimethylaminopropyl (meth) acrylate.

As other polymerizable unsaturated compounds, polymerizable unsaturated compounds represented by the general formula (VIII), styrene, vinyltoluene, substituted styrenes such as α-methylstyrene, vinyl chloride, vinylidene chloride and acrylonitrile. , Acrylamide, etc. can also be used together. Further, within a range of a non-aqueous dispersion type resin, for example, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth ) Acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. A polymerizable unsaturated compound such as (meth) acrylic acid ester may 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 of the vinyl polymer (A) is used. This amount used is determined by the intended molecular weight of the vinyl polymer (B), and is usually 0.1 to 10.0% by weight.
Is preferred.

In the non-aqueous dispersion obtained as described above, the ratio of the organic solvent-soluble vinyl polymer (A) to the organic solvent-insoluble vinyl polymer particles (B) is the same as the former / the latter ( The weight ratio is preferably 10/90 to 60/40. 1
If it is less than 0/90, the dispersion stability tends to be poor,
If it exceeds 60/40, the drying property tends to be poor and the coating workability becomes a problem. At the time of polymerization, additives such as a dispersion stabilizer and a rheology control agent may be used in combination.

The particle diameter of the vinyl polymer particles (B) in the obtained non-aqueous dispersion is usually preferably in the range of about 100 to 1500 nm. If the particle size is less than 100 nm,
If the viscosity of the varnish becomes high and the particle size exceeds 1500 nm, the particles may swell or aggregate during storage. In the present invention, by chemically bonding the vinyl polymer (A) and the vinyl polymer particles (B) described above,
Storage stability and the like can be further improved. As a method of binding, for example, the polymerizable unsaturated compound as the component (B) is polymerized 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 thus obtained non-aqueous dispersion has good storage stability because the vinyl polymer (A) and the vinyl polymer particles (B) are chemically bonded.

The curable composition of the present invention exerts a remarkable effect as a coating material and a coating film by adding a silicon compound as a curing agent to the above non-aqueous dispersion liquid. In particular, as a curing agent, the following general formula (II), general formula (III), general formula (IV), general formula (V), general formula (VI)
Alternatively, it is preferable to add a silicon compound represented by the general formula (VII) because the effect is excellent.

[Chemical 7] (In the formula, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R
₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently an alkyl group, an aryl group or an aralkyl group, Y is an organic group, and m is an integer of 2 to 4. , N is 0 to 20
Is an integer)

The curing agent particularly imparts excellent curability at low temperature to the composition. That is, the silyl group represented by the general formula (I) in the vinyl polymer (A) is hydrolyzed by moisture in the system to give a silanol group (Si-OH).
And then a silanol group and general formula (II), general formula (III), general formula (IV), general formula (V), general formula (VI)
Alternatively, the silicon compound represented by the general formula (VII) reacts at a low temperature to cause crosslinking (low temperature curing). Needless to say, the silanol groups in the vinyl polymer (A) or the silanol groups react with the silyl groups represented by the general formula (I).

As the curing agent for the silicon compound represented by the general formula (II), for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, decyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-dimethylaminopropyldiethoxymethylsilane, 3-
[2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, 3-morpholinopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane,
Examples thereof include 3-isocyanatopropyltriethoxysilane and methyltrichlorosilane.

Examples of the curing agent for the silicon compound represented by the general formula (III) include tetraacetoxysilane, methyltriacetoxysilane, triacetoxyvinylsilane, dimethyldiacetoxysilane, 3-mercaptopropyltriacetoxysilane, and 3-amino. Examples thereof include propyltriacetoxysilane and 3-glycidoxypropyltriacetoxysilane.

Examples of the curing agent for the silicon compound represented by the general formula (IV) include methyltris (dimethylamino).
Examples thereof include silane, methyltris (diethylamino) silane, bis (dimethylamino) dimethylsilane, and ethyltris (dimethylamino) silane.

Examples of the curing agent for the silicon compound represented by the general formula (V) include methyltris (N, N-dimethylaminoxy) silane, methyltris (N, N-diethylaminoxy) silane, and bis (N, N-). Examples thereof include diethylaminoxy) dimethoxysilane and ethyltris (N, N-diethylaminoxy) silane.

Examples of the curing agent for the silicon compound represented by the general formula (VI) include methyltris (ethylmethylketoxime) silane, ethyltris (ethylmethylketoxime) silane, and tris (ethylmethylketoxime).
Vinyl silane, methyl tris (dimethyl ketoxime)
Examples thereof include silane and methyltris (diethylketoxime) silane.

As the curing agent for the silicon compound represented by the general formula (VI), for example,

[Chemical 8]

[Chemical 9] In addition, general formula (II), general formula (III), general formula (IV),
In addition to the silicon compound represented by the general formula (V) or the general formula (VI), a tetramethoxysilane or tetraethoxysilane oligomer (eg, dimer, trimer, tetramer, pentamer) as a curing agent. Etc.) and silanol group-containing phenyl-substituted cyclic organopolysiloxanes can be used.

The curable composition of the present invention is made into an enamel paint by a conventional method by adding a pigment such as titanium white, carbon black or phthalocyanine blue, an extender pigment such as calcium carbonate or barium sulfate, and a solvent. You 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 a roll, a sand mill and a disperser can be used. Further, an enamel paint can be prepared by using a seed pen having good compatibility with the curable composition obtained by 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.

[0032]

EXAMPLES Examples of the present invention will be described below. Hereinafter, "%" means "% by weight" unless otherwise specified. 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 taper (manufactured by Showa Shell Sekiyu KK). After the temperature was raised to 90 ° C., the following polymerizable unsaturated compound was added to 2
It dripped over time.

[Table 1] 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 tape 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 tapene was further added to adjust the heating residue to 50%.

(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) 450 g was collected and 350 g of mineral tape was added. After the temperature was raised to 100 ° C., the following polymerizable unsaturated compound was 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, t-butylperoxy-2-ethylhexanoe-
A solution prepared by dissolving 50 g of mineral tape in 50 g of mineral tape was additionally added dropwise, and the temperature was kept at 100 ° C. for 2 hours to complete the polymerization reaction. After cooling, add more mineral tape and heat remaining 5
It was adjusted to be 0%. A milky white non-aqueous dispersion type resin having a resin viscosity of 5700 centipoise, an average particle size of 770 nm and an acid value of 1 or less was obtained. This was named "N-1".

Synthetic Example 2 (Synthesis of Non-Aqueous Dispersion Resin N-2) 430 g of the resin (A-1) synthesized in Synthetic Example 1 was sampled in the same flask as in Synthetic Example 1, and the mineral tape pen 330 was used.
g was added. After the temperature was raised to 100 ° C., the following polymerizable unsaturated compound was added dropwise over 2 hours.

[Table 3] Other operations were performed in the same manner as in Synthesis Example 1 to obtain a milky white non-aqueous dispersion type resin having a resin viscosity of 6100 centipoise, an average particle diameter of 810 nm, and an acid value of 1 or less. This was named "N-2".

Comparative Synthesis Example 1 (1) Synthesis of Resin (A-2) The same operation as in (1) of Synthesis Example 1 was carried out except that the composition of the polymerizable unsaturated compound to be dropped was changed to the following composition. Minute 5
0% of acrylic resin (A-2) was obtained.

[Table 4]

(2) Synthesis of non-aqueous dispersion type resin (N-3) As in Example 1, except that 460 g of a resin soluble in the mineral tapen synthesized in (1) was charged. The same operation was performed to obtain a milky white non-aqueous dispersion type resin having a heating residue of 50%, a resin viscosity of 7500 centipoise, an average particle diameter of 790 nm, and an acid value of 1 or less. This was named "N-3".

Comparative Synthesis Example 2 Synthesis of Resin (A-3) The same operation as in (1) of Synthesis Example 1 was carried out except that the polymerizable unsaturated compound to be dropped was changed to the following composition, and the heating residue was 5
0% of acrylic resin (A-3) was obtained.

[Table 5]

Examples 1 to 6 and Comparative Examples 1 to 6 The non-aqueous dispersion type resins prepared in Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1 and 2 were blended as shown in Table 1 to give white enamel paints.
However, the white-type pen in Table 1 means the resin (A-1) of Synthesis Example 1 as a color-developing agent and titanium white typeque R-9 as a pigment.
30 (made by Ishihara Sangyo Co., Ltd.) is used and refers to a seed pen made by kneading. Using a mineral taper as a thinner,
The paint was prepared by adjusting the viscosity so that it would be 12 seconds (25 ° C) in the cup # 4 (PWC (Pigment Weight Cont
ent) = 40%), and spray coating was performed on a plate (JIS F5403 standard) so that the coating film had a thickness of 25 to 35 μm (after drying). It was left for 2 weeks in a curing room defined by JIS and used as an evaluation test plate. The evaluation results are shown in Tables 6 and 7.

[0039]

[Table 6]

[0040]

[Table 7] Abbreviation of curing agent A: 3-aminopropyltetraethoxysilane B: tetraacetoxysilane C: methyltris (N, N-dimethylamino) silane D: N, N-diethylaminoxytrimethoxysilane E: methyltris (ethylmethylketoxime) Silane F: silanol group-containing organopolysiloxane ("KR-211" manufactured by Shin-Etsu Chemical Co., Ltd.) G: monobutyl phosphate H: dibutyltin dilaurate

The test evaluation method is shown below. (1) Paint storage stability (pot life): At 40 ° C., the number of days until the viscosity increased to a pudding-like state was examined. (2) Gloss: 20 degree specular reflectance and 60 degree specular reflectance were measured. (3) Yield stress (difficulty in sagging): Determined by the Cone & Plate method. (4) Residual viscosity (lightness of brush): Cone & Plate
Obtained by law. (5) Curability: Curing was performed under the conditions of a temperature of 23 ± 2 ° C. and a humidity of 75 ± 10% for the above time, and was determined from the gel fraction by the Soxhlet-extraction method *.

[Equation 1] * Extraction conditions: Extraction was performed for 8 hours using a mixed solution of acetone / methanol (1/1 weight ratio). (6) Impact resistance: Measured by a method defined by JIS 1421 method. (7) Alkali resistance: After being immersed in a saturated slaked lime aqueous solution for 1 month, the appearance was visually evaluated. (8) Water resistance: After being immersed in tap water for 1 month, the appearance was visually judged. (9) Moisture resistance: It was placed in a blister ring box at 50 ° C. and a relative humidity of 98% for 1 month, and the appearance was visually evaluated. (10) Accelerated weather resistance: Using a Sunshine Weathero 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]

[0042]

INDUSTRIAL APPLICABILITY The curable composition and coating composition of the present invention have particularly good curability and long pot life by blending a non-aqueous dispersion type resin containing a specific silyl group and a silicon compound as a curing agent. In addition, the coating film is excellent in gloss and weather resistance, and is also excellent in moisture resistance, water resistance, alkali resistance and impact resistance.

 ─────────────────────────────────────────────────── ─── 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 (4)

[Claims] 1. A vinyl polymer (A) having a silyl group represented by the general formula (I): (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 l is an integer of 1 to 3) (A) A non-aqueous dispersion containing vinyl polymer particles (B) insoluble in the solvent, which is obtained by polymerizing a polymerizable unsaturated compound in a dissolved solvent, is mixed with a silicon compound as a curing agent. A curable composition comprising: 2. The curable composition according to claim 1, wherein the solvent is an organic solvent of an aliphatic hydrocarbon or an organic solvent containing an aliphatic hydrocarbon as a main component. 3. A curing agent comprising a silicon compound represented by the general formula (II):
General formula (III), general formula (IV), general formula (V), general formula (V
I) or general formula (VII) (In the formula, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R
₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently an alkyl group, an aryl group or an aralkyl group, Y is an organic group, and m is an integer of 2 to 4. , N is 0 to 20
It is a compound shown by these. The curable composition according to claim 1. 4. A coating material containing the curable composition according to claim 1.