JPH0673261A - Nonaqueous resin dispersion composition - Google Patents

Abstract

PURPOSE:To obtain a nonaqueous resin dispersion compsn. useful as a vehicle of a coating material for an exterior wall made of an inorg. material by copolymerizing vinyl acetate with an acrylic ester in a specific org. solvent in the presence of a specific acrylic copolymer as a dispersant. CONSTITUTION:This resin dispersion compsn. is produced by copolymerizing 10-50wt.% vinyl acetate, 50-90wt.% 1-12C alkyl (meth)acrylate, and 0-40wt.% comonomer other than the above monomers in an org. solvent mainly comprising an aliph. hydrocarbon and/or an alicyclic hydrocarbon in the presence of a dispersant obtd. by copolymerizing 70-90wt.% at least one monomer selected from the group consisting of n-, i-, and t-butyl acrylates, 10-30wt.% 6-18C alkyl (meth)acrylate, and 0-20wt.% comonomer other than the above monomers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-water-dispersible resin composition, and more particularly to a vehicle for a coating agent, particularly a vehicle for a coating agent on an outer wall of a building or structure such as a residence, which is mainly an inorganic base material such as concrete or mortar. When used as a coating agent, it becomes a coating agent that can be used even under coating conditions such as below −5 ° C., and the coating film obtained has high moisture permeability and is also waterproof and alkali resistant. Regarding a non-water-dispersible resin composition that becomes an excellent one,

More specifically, a dispersion stabilizer component (A) obtained by copolymerizing a specific methacrylic acid ester monomer as a main component in an organic solvent containing a specific hydrocarbon organic solvent as a main component.
The present invention relates to a non-aqueous dispersible resin composition, which is obtained by copolymerizing, as the dispersed particle component (B), a monomer having a specific composition containing vinyl acetate.

[0003]

2. Description of the Related Art Generally, a coating material for a structural material mainly made of an inorganic base material such as concrete or mortar, such as an outer wall of a building or structure such as a residence, is provided with beautiful appearance, waterproofness, stain resistance, It is required to be a film-forming material having various excellent properties such as resistance to discoloration or fading over time.

In response to such practical demands, as an outer wall coating agent for the above-mentioned buildings and structures, a coating agent having an acrylic resin aqueous emulsion having a waterproof function as a vehicle is widely adopted. There is. In general, for structural materials made of inorganic base materials such as concrete and mortar, water that has entered the interior in the cold season freezes and causes destruction of the inorganic base material.Therefore, prevent water from entering the inorganic base material. Is an important technical issue. From this point of view, an aqueous acrylate resin emulsion, which is particularly excellent in waterproofness, has come to be used as a vehicle for a coating agent for a structural material composed of an inorganic base material.

However, since coating agents using these aqueous emulsions as vehicles have insufficient film-forming properties (hereinafter sometimes referred to as low-temperature film-forming properties) below freezing, for example, at -5 ° C or less, they are cold regions. There are many problems with using it.

On the other hand, a coating agent using an organic solvent-soluble resin or an organic solvent-dispersed resin as a vehicle is also known.
In particular, those containing a large amount of aromatic hydrocarbons in the organic solvent have a problem in environmental hygiene due to volatilization of the organic solvent when the coating agent is used, and most of these coating films Although it has a high degree of waterproofness, it is often insufficient in terms of water vapor permeability.

Recently, with the spread of aluminum sashes, the number of rooms with high confidentiality is increasing. For this reason, in the cold season, the humidity in the room increases due to heating, etc., and the outside wall temperature decreases as the outside temperature decreases at night. As a result, the water vapor inside the outer wall does not diffuse to the outside and dew condensation easily occurs. At such a time, as described above, when a coating material having excellent waterproofness but small water vapor permeability is used, the coating film prevents the release of water vapor in the room that has penetrated into the inorganic base material. There is a possibility that such dew condensation is promoted and that the disadvantages such as deterioration of the inorganic base material due to freezing, generation of mold, blistering or peeling of the exterior coating agent, and the like are brought about.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies to solve the problems found in conventional coating agents, and as a result, in an organic solvent containing a specific hydrocarbon-based organic solvent as a main component, By copolymerizing a specific ratio of vinyl acetate and an acrylic monomer as a dispersed particle component in the presence of a dispersion stabilizer component formed by copolymerizing a specific methacrylic acid ester monomer as a main component. The resulting non-water-dispersible resin composition, when used as a vehicle for a coating agent, particularly for a building or structure such as a residence, as a vehicle for a coating agent for an outer wall mainly made of an inorganic base material such as concrete or mortar, below freezing point, for example, Seeing that it can be used as a coating agent even under coating conditions such as -5 ° C, and that the coating film obtained has high moisture permeability and is also highly waterproof and alkali resistant. However the present invention has been attained.

[0009]

Means for Solving the Problems The present invention comprises the following (a-1) to (a) in an organic solvent containing an aliphatic hydrocarbon organic solvent and / or an alicyclic hydrocarbon organic solvent as a main component. -3),

(A-1) 70 to 90% by weight of at least one monomer selected from the group consisting of n-butyl methacrylate, i-butyl methacrylate and t-butyl methacrylate,

(A-2) A (meth) acrylic acid alkyl ester monomer having an alkyl group having 6 to 18 carbon atoms, which comprises (a-1)
Monomers other than 10 to 30% by weight, and

(A-3) 0 to 20% by weight of a comonomer other than the above (a-1) and (a-2),

In the presence of a dispersion stabilizer component (A) obtained by copolymerizing a monomer consisting of
1) to (b-3),

(B-1) 10 to 50% by weight of vinyl acetate,

(B-2) 50 to 90% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 18 carbon atoms, and

(B-3) 0 to 40% by weight of a comonomer other than the above (b-1) and (b-2),

A non-water-dispersible resin composition, characterized in that it is obtained by copolymerizing a monomer consisting of [a-1 to a-
The sum of 3) and the sum of (b-1) to (b-3) above are each 10
0% by weight].

The present invention will be described in detail below. The non-aqueous dispersible resin composition of the present invention contains a specific methacrylic acid ester-based monomer in an organic solvent containing an aliphatic hydrocarbon-based organic solvent and / or an alicyclic hydrocarbon-based organic solvent as a main component. It is obtained by copolymerizing a specific ratio of vinyl acetate as a dispersion particle component and an acrylic monomer in the presence of a dispersion stabilizer obtained by copolymerizing the main component amount.

Examples of the above-mentioned aliphatic hydrocarbon organic solvent and / or alicyclic hydrocarbon organic solvent which can be used in the present invention include, for example, n-hexane, i-hexane, n-heptane, n-octane, i-octane, n-decane, n-dodecane,
Cyclohexane, methylcyclohexane, cycloheptane, methylcycloheptane, "Loose", "Mineral Spirit EC", "Shellsol 72", "VM & P naphtha", "Shell TS 28 Solvent" [above, Shell company],

"Isopar C", "Isopar E",
"Isopar G", "Isopar H", "Isopar M", "Naphtha 3", "Naphtha 5", "Naphtha 6"
No. ”,“ Solvent No. 7 ”[above, manufactured by Exxon Chemical Co.],“ IP Solvent 1016 ”,“ IP Solvent 16 ”
20 "," IP Solvent 2028 "," IP Solvent 28 "
35 "[above, manufactured by Idemitsu Petrochemical Co., Ltd.]," Whitesol "[manufactured by Kyodo Oil Co., Ltd.]," Mitsubishi Mineral Tarpen ",
"Diamond Solvent" [above, Mitsubishi Oil Co., Ltd.
Made], "Pegasol AN-45", "Pegasol 3040"
[Above, manufactured by Mobile Oil Co., Ltd.] and the like can be mentioned. These hydrocarbon solvents can be used alone or in combination of two or more.

In the present invention, in addition to the aliphatic hydrocarbon-based organic solvent and the alicyclic hydrocarbon-based organic solvent, an organic compound other than the hydrocarbon-based organic solvent is used within a range that does not impair the excellent effects of the present invention. A solvent can be used together.

Examples of the organic solvent other than the aliphatic hydrocarbon-based organic solvent and the alicyclic hydrocarbon-based organic solvent include benzene, toluene, ethylbenzene, propylbenzene, t-butylbenzene, o-xylene and m. -Xylene, p-xylene, tetralin, decalin, "Solvesso
Aromatic hydrocarbon organic solvents such as "100", "Solvesso 150" [above, manufactured by Exxon Chemical Co.];

For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n
-Alcohol organic solvents such as butyl alcohol, i-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, i-octyl alcohol, 2-ethylhexyl alcohol; for example, acetone, methyl ethyl ketone, methyl-i-butyl ketone, methyl amyl ketone , Ketone organic solvents such as cyclohexanone; ester organic solvents such as methyl acetate, ethyl acetate, -n-butyl acetate, amyl acetate;

For example, methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, i-propyl cellosolve,
Cellosolve-based organic solvents such as n-butyl cellosolve, i-butyl cellosolve, i-amyl cellosolve, phenyl cellosolve, and benzyl cellosolve; methyl carbitol, ethyl carbitol, n-propyl carbitol, i-propyl carbitol, n-butyl carbitol , I-butyl carbitol, i-amyl carbitol, phenyl carbitol,
Carbitol-based organic solvents such as benzyl carbitol; and the like.

In the present invention, the expression "having the aliphatic hydrocarbon-based organic solvent and / or the alicyclic hydrocarbon-based organic solvent as a main component" means that those carbonic acids occupy in all the organic solvents used in the present invention. The proportion of hydrogen-based organic solvent is 50% by weight or more,
It is preferably 70 to 90% by weight or more. If the proportion of the hydrocarbon-based organic solvent is too small and less than the lower limit value,
The dispersed particle component (B) may not be stably formed in some cases, and the moisture permeability of the coating film of the coating composition using the obtained resin composition tends to decrease, which is not preferable.

As the organic solvent used in the present invention, it is preferable to use the cellosolve organic solvent in combination with the aliphatic hydrocarbon organic solvent and / or the alicyclic hydrocarbon organic solvent. As the cellosolve-based organic solvent, use of methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, i-propyl cellosolve, n-butyl cellosolve, i-butyl cellosolve is preferable, and use of methyl cellosolve is particularly preferable.

The amount of the cellosolve solvent used is preferably 1 to 30% by weight, and more preferably 5 to 20% by weight, based on the total organic solvent used in the present invention. When the amount used is at least the lower limit value, a coating agent using the obtained non-water-dispersible resin composition has appropriate thixotropy, and thus a thick coating film can be formed by one-time coating. Therefore, if the amount used is not more than the upper limit value, the effect of the stabilizer component (A) as a stabilizer does not decrease, and the drying property does not decrease at the time of forming a coating film. The membrane is preferable because it is not easily soiled or the water resistance is not lowered.

The dispersion stabilizer component (A) used in the present invention is n-
Butyl methacrylate, i-butyl methacrylate and t
-At least one monomer (a-1) selected from the group consisting of -butyl methacrylate is 70 to 90% by weight, preferably 70 to 90% by weight, based on all monomers constituting the dispersion stabilizer component (A). 75 ~ 85
It is obtained by copolymerization by weight%. If the amount of the monomer used exceeds the upper limit and is too large, the solubility of the obtained dispersion stabilizer component (A) in an organic solvent decreases and the dispersion stability decreases, which is not preferable. On the other hand, if the amount of the monomer used is less than the lower limit and is too small, the copolymer of the dispersion stabilizer component (A) becomes too soft, and thus coating with the obtained non-aqueous dispersible resin composition is performed. It is not preferable because the coating film of the agent has blocking property and is easily soiled.

The dispersion stabilizer component (A) used in the present invention
Is an alkyl group having 6 carbon atoms together with the above monomer (a-1).
To (18) alkyl (meth) acrylate monomers, which are obtained by copolymerizing a monomer (a-2) other than (a-1). If the number of carbon atoms in the monomer (a-2) (meth) acrylic acid alkyl ester monomer exceeds 18 and is too large, a coating agent coating film using the obtained non-aqueous dispersible resin composition is obtained. It is fragile and not desirable. On the other hand, if the carbon number is too small, less than 8, the solubility of the dispersion stabilizer component (A) in the organic solvent is lowered, and the dispersion stability is deteriorated, which is not preferable.

Examples of the above-mentioned monomer (a-2) include n-
Hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate,
C6-C18 linear or branched alkyl esters of acrylic acid such as lauryl acrylate and stearyl acrylate; for example, n-hexyl methacrylate, n-octyl methacrylate, i-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, Mention may be made of linear or branched alkyl esters of methacrylic acid having 6 to 18 carbon atoms such as stearyl methacrylate, and the use of 2-ethylhexyl acrylate is particularly preferred.

The amount of the above-mentioned monomer (a-2) used is 10 to 30% by weight, preferably 15 to 25% by weight, based on all the monomers constituting the dispersion stabilizer component (A). If the amount of the monomer used exceeds the upper limit and is too large, the copolymer of the dispersion stabilizer component (A) becomes too soft, and thus the coating agent using the obtained non-aqueous dispersible resin composition. It is not preferable because the coating film has a blocking property and is easily stained. On the other hand, if the amount of the monomer used is too small below the lower limit value, the solubility of the obtained dispersion stabilizer component (A) in an organic solvent will be low and the dispersion stability will be reduced, such being undesirable.

Further, the dispersion stabilizer component (A) used in the present invention
Is, together with the monomers (a-1) and (a-2), if necessary,
Comonomers (a-3) other than the above (a-1) and (a-2), the component (A)
The copolymer can be copolymerized in an amount of 0 to 20% by weight, preferably 0 to 10% by weight, based on all the monomers constituting the.

Examples of the above-mentioned monomer (a-3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, cyclohexyl acrylate and benzyl acrylate. Acrylic acid esters other than the above-mentioned monomer (a-2); for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate Monomer (a-1) such as
And methacrylic acid esters other than (a-2);

For example, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, n-butyrate, "vinyl versatate" (manufactured by Shell Co.); fragrances such as styrene, α-methylstyrene, vinyltoluene, etc. Group vinyl compounds; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; α, β-unsaturated mono- or di-carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, crotonic acid and itaconic acid;

Hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; for example, N, N-dimethylaminoethyl Examples thereof include aminoalkyl esters of (meth) acrylic acid such as acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate. Among these monomers, it is preferable to use acrylic acid esters other than the monomer (a-2) or methacrylic acid esters other than the monomers (a-1) and (a-2).

The dispersion stabilizer component (A) used in the present invention preferably has a weight average molecular weight of 100,000 to 300,000, particularly 150,000 to 250,000. When the molecular weight is not less than the lower limit, it is preferable because inconveniences such as deterioration of dispersion stability, water resistance, alkali resistance and the like do not occur, and when it is not more than the upper limit, the obtained non-aqueous dispersibility is obtained. It is preferable because practical problems such as the viscosity of the resin composition becoming too high do not occur.

The value of the weight average molecular weight in the present invention is the value obtained by measurement by gel permeation chromatography method (hereinafter sometimes abbreviated as GPC method).

The dispersion stabilizer component (A) used in the present invention is not particularly limited as long as it satisfies the above requirements, and a commercially available resin may be used, but usually, the dispersed particles described below are used. Prior to the polymerization of the component (B), in the same organic solvent as the organic solvent containing the aliphatic hydrocarbon-based organic solvent and / or alicyclic hydrocarbon-based organic solvent as a main component, the monomer (a -1) ~ (a-3) using a suitable polymerization initiator, and, if necessary, a chain transfer agent, in a nitrogen stream or at the reflux temperature of the organic solvent, to heat reaction for several hours while stirring Can be manufactured by. In this case, at least a part of these organic solvent, monomer, polymerization initiator and / or chain transfer agent may be sequentially added.

Examples of the above-mentioned polymerization initiator include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxy. Organic peroxides such as bevalate;
For example, 2,2'-azobis-i-butyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4-
Azo compounds such as methoxy-2,4-dimethylvaleronitrile; and the like can be used alone or in combination. The amount of the polymerization initiator used is the above monomers (a-1) to (a-3).
In general, about 0.01 to 1.0 part by weight, preferably about 0.02 to 0.5 part by weight, is used per 100 parts by weight of total.

Examples of the chain transfer agent include, for example,
Cyanoacetic acid; cyanoacetic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms; bromoacetic acid; bromoacetic acid esters having an alkyl group having 1 to 8 carbon atoms; fragrance such as anthracene, phenanthrene, fluorene, and 9-phenylfluorene Group compounds; p-nitroaniline, nitrobenzene,
Aromatic nitro compounds such as dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene;

Benzoquinone, 2,3,5,6-tetramethyl-p-
Benzoquinone derivatives such as benzoquinone; Borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,
Halogenated hydrocarbons such as 2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane, and 3-chloro-1-propene; aldehydes such as chloral and furaldehyde.

Alkylmercaptans having 1 to 18 carbon atoms;
Aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid; mercaptoacetic acid C1-C10 alkyl esters; C1-C12 hydroxyalkyl mercaptans; terpenes such as binene and terpinolene; be able to. When the chain transfer agent is used, the amount used is the sum of the monomers (a-1) to (a-3).
It is preferably about 0.005 to 3.0 parts by weight per 100 parts by weight.

The polymerization temperature is generally about 30 to 180 ° C.,
It is preferably in the range of about 60 to 150 ° C.

The non-water-dispersible resin composition of the present invention contains the above-mentioned specific methacrylic acid ester-based solvent in an organic solvent containing an aliphatic hydrocarbon-based organic solvent and / or an alicyclic hydrocarbon-based organic solvent as a main component. In the presence of a dispersion stabilizer (A) obtained by copolymerizing a monomer as a main component, vinyl acetate (b-1) as a dispersed particle component (B) constitutes the dispersed particle component (B). It is obtained by copolymerizing 10 to 50% by weight, preferably 15 to 40% by weight, of all the monomers.

If the amount of the monomer (b-1) used exceeds the upper limit and is too large, the coating composition using the resulting non-water-dispersible resin composition has insufficient alkali resistance. However, it is not preferred. On the other hand, if the amount of the monomer (b-1) used is too small and less than the lower limit, the moisture permeability of the coating composition using the obtained non-water-dispersible resin composition tends to decrease. It is not preferable.

The dispersed particle component (B) in the non-water-dispersible resin composition of the present invention comprises the above-mentioned vinyl acetate (b-1) and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms. It is obtained by copolymerizing the monomer (b-2).

The above-mentioned monomer component (b-2) is, for example,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate Acrylic acid ester monomers such as stearyl acrylate;

For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, i-octyl methacrylate, 2-ethylhexyl methacrylate, i-nonyl methacrylate. , N-dodecyl methacrylate, i-dodecyl methacrylate, stearyl methacrylate and other methacrylic acid ester monomers; and the like.

The amount of the monomer (b-2) used is 50 to 90% by weight, preferably 60 to 85% by weight, based on the total monomers constituting the dispersed particle component (B). If the amount of the monomer used exceeds the upper limit and is too large, the moisture permeability of the coating film of the coating composition using the resulting non-water-dispersible resin composition tends to decrease, which is not preferable. On the other hand, if the amount of the monomer used is too small below the lower limit, the water resistance and alkali resistance of the resulting coating film of the coating composition tend to decrease, which is not preferable.

Further, the dispersed particle component (B) in the non-water-dispersible resin composition of the present invention contains the above-mentioned monomers (b-1) and (b-2) and, if necessary, the above-mentioned (b-1). ) And (b-2) other than the comonomer (b-3) with respect to all monomers constituting the component (B) 0
It is possible to copolymerize 40% by weight, preferably 0 to 20% by weight.

Examples of the above-mentioned monomer (b-3) include (meth) acrylic acid esters other than the above-mentioned monomer (b-2) such as cyclohexyl acrylate, benzyl acrylate, cyclohexyl methacrylate and benzyl methacrylate; For example, vinyl esters other than the monomer (b-1) such as vinyl formate, vinyl propionate, n-butyrate, “vinyl versatate” (manufactured by Shell Co.); for example, acrylonitrile, methacrylonitrile, etc. Vinyl cyanide compound;

For example, α, β-unsaturated mono-acids such as acrylic acid, methacrylic acid, maleic acid, crotonic acid and itaconic acid.
-Or di-carboxylic acids; eg 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
Hydroxyalkyl ester of (meth) acrylic acid such as 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate (preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate) Kind;

For example, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N,
Aminoalkyl esters of (meth) acrylic acid such as N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate (preferably N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate); for example, acrylamide , Methacrylamide, N, N-dimethylacrylamide, N-methylacrylamide, Nn-butoxymethylacrylamide (preferably acrylamide, methacrylamide) or other amide group- or substituted amide group-containing monomer;

For example, epoxy group-containing monomers such as glycidyl methacrylate and glycidyl acrylate; for example, mercapto group-containing monomers such as vinyl mercaptan and allyl mercaptan; for example, (poly) ethylene glycol di (meth) acrylate and neopentyl. Glycol di
(Meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, divinylbenzene, etc. Two or more radically polymerizable unsaturated compounds in one molecule Examples thereof include a monomer having a group.

The dispersed particle component (B) in the present invention has the solubility parameter (hereinafter, may be abbreviated as SP value) of 9.0 to 10.2.
It is preferred to copolymerize (b-3) with appropriate combinations. If the SP value is 9.0 or more, it is preferable because the moisture permeability of the coating composition using the obtained non-water-dispersible resin composition does not decrease, and if the SP value is 10.2 or less, it is obtained. It is not preferable because the water resistance and alkali resistance of the coating film of the coating agent do not deteriorate.

In the present invention, S of the dispersed particle component (B) is
The P value is a value calculated by the following calculation formula (1).

[0057]

[Equation 1]

(Where σ _i is SP of homopolymer of monomer i)
Value, and w _i represents the weight fraction of the monomer i).

The dispersed particle component (B) in the present invention has a glass transition point (hereinafter sometimes abbreviated as Tg) of 0.
It is preferable that the above-mentioned monomer components (b-1) to (b-3) are appropriately combined and copolymerized so that the temperature becomes -50 ° C, preferably 10-40 ° C. When Tg is at least the lower limit value, the coating film of the obtained non-water-dispersible resin composition does not cause inconveniences such as being hard and brittle, and is preferable, and when Tg is at most the upper limit value. If so, the coating agent using the composition is excellent in low-temperature film-forming property, and the resulting coating film does not cause inconvenience such as blocking property and easy stain.

In the present invention, Tg of the dispersed particle component (B) is a value calculated by the following calculation formula (2).

[0061]

[Equation 2]

[Where Tg _i is T of a homopolymer of monomer i]
g and w _i represent the weight fraction of the monomer i.
In addition, Tg and Tgi are expressed in absolute temperature (° K). ]

The non-water-dispersible resin composition of the present invention contains the above-mentioned specific methacrylic acid ester-based solvent in an organic solvent containing an aliphatic hydrocarbon-based organic solvent and / or an alicyclic hydrocarbon-based organic solvent as a main component. In the presence of the dispersion stabilizer (A) obtained by copolymerizing the monomer as the main component, the monomers (b-1) to (b-3) as the dispersed particle component (B) are appropriately mixed. It can be produced by using a polymerization initiator and, if necessary, a chain transfer agent, and copolymerizing by heating for several hours in a nitrogen stream or at the reflux temperature of the organic solvent with stirring. In this case, as the polymerization initiator, the chain transfer agent and the like, the same ones as used in the production of the dispersion stabilizer can be used, and the organic solvent, the monomer, the polymerization initiator and / or the chain transfer agent can be used. At least a portion of the agent may be added sequentially.

The amount ratio of the dispersion stabilizer component (A) and the dispersion particle component (B) contained in the non-water-dispersible resin composition of the present invention is determined by the dispersion stabilizer component (A) and the dispersion stabilizer component (A). The dispersion stabilizer is defined as 100% by weight of the total of the resin component comprising the particle component (B).
It is preferable that (A) is 15 to 50% by weight, particularly 20 to 40% by weight, and the dispersed particle component (B) is 50 to 85% by weight, especially 60 to 80% by weight.

When the proportion of the dispersion stabilizer (A) is at least the above lower limit value, the stability of the resulting non-aqueous dispersible resin composition is excellent, and the coating agent using the same is formed at low temperature. It is also preferable because it has excellent properties. On the other hand, when the ratio is less than or equal to the above upper limit value, the coating suitability and the drying property of the coating agent using the composition do not decrease, and the obtained coating film also has excellent moisture permeability. preferable.

The polymerization temperature is generally about 30 to 180 ° C.,
It is preferably in the range of about 60 to 150 ° C.

The non-water-dispersible resin composition of the present invention thus obtained generally contains the resin component consisting of the dispersion stabilizer component (A) and the dispersed particle component (B) in an amount of 20 to 70% by weight, preferably 40% by weight.
-60% by weight, the viscosity is generally about 100-20,
It should be 000 cps.

The weight average molecular weight of the resin component in the non-water-dispersible resin composition of the present invention is generally 5 to 250,000, preferably about 5 to 150,000. When the average molecular weight is not more than the upper limit, it is preferable because the coating film of the coating composition using the composition does not become hard and brittle, and when the average molecular weight is not less than the lower limit, the obtained coating composition is obtained. It is preferable because the coating film does not have a blocking property and is easily soiled, and the water resistance and alkali resistance of the coating film do not deteriorate.

The non-water-dispersible resin composition of the present invention may be used as it is, or if necessary, the non-water-dispersible resin composition may be colored with an organic or inorganic material such as titanium oxide, carbon black or phthalocyanine blue. Agent; for example,
Inorganic fillers such as calcium carbonate, silica, clay, talc, aluminum hydroxide, and glass powder; antiaging agents; preservatives / mold inhibitors; UV absorbers; antistatic agents; It can be used as an agent.

If desired, the non-water-dispersible resin composition of the present invention may contain a crosslinking agent such as an epoxy resin, an amino resin, an isocyanate compound or a metal chelate within a use range that does not impair the excellent effects of the present invention. However, it can also be crosslinked before use.

The coating agent containing the non-water-dispersible resin composition of the present invention may be diluted with an appropriate organic solvent, if necessary, and subjected to various methods such as dipping, spraying, coating and printing.
It can be applied to various substrates.

The base material to which the coating agent containing the non-water-dispersible resin composition of the present invention can be preferably applied is, for example, mortar, concrete, glass, ceramic,
An inorganic material such as a slate plate, rock, silica plate, ore, etc., and particularly an outer wall made of an inorganic base material of a building or structure such as residence can be mentioned.

Coating agents containing the non-water-dispersible resin composition of the present invention include, for example, aluminum plates, zinc plates,
Metal plates such as iron plates and stainless steel plates; for example, thermoplastic synthetic resins such as vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, styrene resin, acrylic resin, polyester resin, polycarbonate resin, ABS resin, AS resin, urethane resin, SBR, etc. It is preferably used for a base material such as a resin molding; for example, a thermosetting synthetic resin molding such as a phenol resin, a melamine resin, a urea resin, an epoxy resin, an unsaturated polyester resin or a polyimide resin; it can.

[0074]

EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Reference Examples. The methods of compounding the coating agent, preparing the coated plate, and testing various physical properties of the coating agent in Examples and Comparative Examples are shown below.

(1) Mixing of coating agent In a sand mill, 2 parts by weight of polyester dispersant organic solvent solution "Nissetsu KP-1156" [nonvolatile content: about 43% by weight; manufactured by Nippon Carbide Industry Co., Ltd.] and aliphatic carbonization After uniformly mixing 14 parts by weight of hydrogen-based organic solvent "Rousse" (manufactured by Shell Co.), titanium oxide "TCR-30" (manufactured by Tochem Products Co., Ltd.) 35 parts by weight, calcium carbonate "Sunlight # 1000"
[Takehara Chemical Co., Ltd.] Add 35 parts by weight and knead. After sufficiently kneading, 59 parts by weight of a non-water-dispersible resin composition (resin component content of about 50% by weight) and 5 parts by weight of "loose" were added to prepare a coating agent.

The coating composition obtained had a nonvolatile content of 67% by weight, a viscosity of 1500 to 6000 cps, and a pigment weight concentration (PWC) of 70% by weight.
Met.

(2) Preparation of Specimen (2-1) Preparation of Specimen for Coating Film Test The coating agent obtained in the above (1) has a viscosity of 1500 to 2000 cps by adding an appropriate amount of "rows". And apply it twice on a flexible plate with a brush at a thickness of about 150 g / m ₂ when wet.
It was dried at room temperature for a week and used as a test piece for various coating film tests.

(2-2) Preparation of Test Piece for Moisture Permeability Measurement The coating agent obtained in the above (1) was dried on a release paper to a dry thickness of 100 μm.
It was coated with a doctor blade so as to have a thickness of m, and dried at room temperature for 1 week to give a test piece.

(2-3) Preparation of Water Permeability Measurement Specimen The coating material obtained in (1) above was applied on a flexible plate with a doctor blade so that the dry thickness would be 100 μm,
It was dried at room temperature for 1 week to give a test piece.

(3) Low Temperature Film Formability Test The viscosity of the coating agent obtained in the above (1) is adjusted to 1500 to 2000 cps by adding an appropriate amount of "loose", and a doctor is added in an environment of -5 ° C. It was coated on a flexible plate with a blade to a dry thickness of 100 μm, 200 μm and 300 μm, left to dry at the same temperature for 1 week, and observed for cracks on the coated surface and evaluated according to the following criteria. .

○ ・ ・ ・ ・ No abnormality in all film thicknesses △ ・ ・ ・ ・ Cracks occurred in coatings of 200 μm and 300 μm × ・ ・ ・ ・ ・ ・ Cracks in all coatings Occurrence (4) Alkali resistance test The specimen prepared in (2-1) above was immersed in a 5 wt% sodium hydroxide aqueous solution for 2 days, and the presence or absence of change in the coating film such as blisters was observed. The evaluation was performed according to the standard.

○ ・ ・ ・ ・ ・ ・ No abnormalities △ ・ ・ ・ ・ ・ ・ Blistering occurs partially × ・ ・ ・ ・ ・ ・ Blistering occurs on the entire surface

(5) Blocking resistance test Using the test piece prepared in the above (2-1), the presence or absence of blocking property was observed by touching with a finger and evaluated according to the following criteria.

◯: No blocking property observed Δ: Some blocking property ×: Blocking property

(6) Contamination resistance test The test piece prepared in (2-1) above was exposed outdoors for 3 months,
The presence or absence of contamination on the coated surface was observed and evaluated according to the following criteria.

○: Dirt is hardly noticeable △: ・ Slightly conspicuous ×: ・ Conspicuous stain

(6) Moisture Permeability Test The test pieces prepared in the item (2-2) above were measured according to JIS Z 0208. The moisture permeability value is preferably 150 g / m ₂ · 24 hrs or more.

(7) Water Permeability Test The test pieces prepared in (2-3) above were measured according to JIS A 6910. The water permeability value is preferably 0.5 ml or less.

Synthesis of dispersion stabilizer:

Reference Example 1 A reactor equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 50 parts by weight of "loose", and then another container was charged with 50% by weight of n-butyl methacrylate (nBMA). , I
-Prepare 400 parts by weight of a monomer mixture consisting of 30% by weight of butyl methacrylate (iBMA) and 20% by weight of 2-ethylhexyl acrylate (EHA). Charge 200 parts by weight of this to the reactor, and nitrogen inside the reactor. After replacement, raise the temperature to 100 ° C,
2,2'-Azobis-i-butylnitrile (AIBN) (0.1 part by weight) was added and the mixture was kept at the same temperature for 30 minutes. Furthermore, a mixture of 200 parts by weight of the remaining monomer mixture, 50 parts by weight of "loose" and 0.5 part by weight of AIBN was sequentially added dropwise over 2 hours, and then A
After 3 parts by weight of IBN was added and kept at the same temperature for 3 hours, 500 parts by weight of "loose" was added and cooled to obtain a dispersion stabilizer solution.

Table 1 shows the composition of the monomers used, the nonvolatile content and viscosity of the obtained dispersion stabilizer solution, and the weight average molecular weight of the dispersion stabilizer.

Reference Examples 2 to 3 In Reference Example 1, nBMA and iBM of the monomer mixture used
A dispersion stabilizer solution was obtained in the same manner as in Reference Example 1 except that the composition ratio of A and EHA was changed. Table 1 shows the composition of the used monomers, the nonvolatile content and viscosity of the obtained dispersion stabilizer solution, and the weight average molecular weight of the dispersion stabilizer.

Reference Example 4 In Reference Example 1, 30% by weight of iBMA in the monomer mixture was used.
Instead of using t-butyl methacrylate (tBMA) 30
A dispersion stabilizer solution was obtained in the same manner as in Reference Example 1 except that the weight% was used. Table 1 shows the composition of the used monomers, the nonvolatile content and viscosity of the obtained dispersion stabilizer solution, and the weight average molecular weight of the dispersion stabilizer.

Reference Examples 5-6 In Reference Example 1, 20% by weight of EHA in the monomer mixture was used.
Instead of using 2-ethylhexyl methacrylate (EHMA) 20% by weight or lauryl methacrylate (LM
A) A dispersion stabilizer solution was obtained in the same manner as in Reference Example 1 except that 20% by weight was used. Table 1 shows the composition of the used monomers, the nonvolatile content and viscosity of the obtained dispersion stabilizer solution, and the weight average molecular weight of the dispersion stabilizer.

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[Table 1]

Synthesis of non-aqueous dispersion type resin composition:

Example 1 A reactor similar to that used in Reference Example 1 was charged with 50 wt.
Parts by weight, 50 parts by weight of methyl cellosolve and 300 parts by weight of the dispersion stabilizer solution obtained in Reference Example 1 were charged, and then, in a separate container, vinyl acetate (VA) was used as a monomer for the dispersed particle component.
c) 400 parts by weight of a monomer mixture consisting of 30% by weight, 40% by weight of ethyl acrylate (EA) and 30% by weight of methyl methacrylate (MMA) was prepared, and 200 parts by weight of this was charged into a reactor to obtain nitrogen. After replacement, raise the temperature to 100 ℃ and
1 part by weight was added and kept at the same temperature for 60 minutes. 200 parts by weight of the remaining monomer mixture, 220 parts by weight of "loose" and
A mixture consisting of 3 parts by weight of AIBN was sequentially added dropwise over 2 hours, then 3 parts by weight of benzoyl peroxide (BPO) was added, and the mixture was kept at the same temperature for 3 hours to obtain a non-aqueous dispersible resin composition.

A coating agent was prepared using the obtained non-water-dispersible resin composition and various physical properties of the coating agent were tested.

Type of dispersion stabilizer solution used, content of dispersion stabilizer component in all resin components, composition of monomer for dispersed particle component, solubility parameter value of dispersed particle component and dispersion in all resin components The content of the particle component is shown in Table 2, the nonvolatile content of the obtained non-water-dispersible resin composition, the viscosity and the weight average molecular weight of the resin component, and the results of various physical properties of the coating agent are shown in Table 3.

Examples 2-3 and Comparative Examples 1-2 Non-aqueous dispersibility was the same as in Reference Example 1 except that the composition ratio of VAc, EA and MMA of the monomer mixture used in Example 1 was changed. A resin composition was obtained. A coating agent was prepared using the obtained non-water-dispersible resin composition, and various coating agent physical property tests were conducted.

Type of dispersion stabilizer solution used, content of dispersion stabilizer component in all resin components, composition of monomer for dispersed particle component, solubility parameter value of dispersed particle component and dispersion in all resin components The content of the particle component is shown in Table 2, the nonvolatile content of the obtained non-water-dispersible resin composition, the viscosity and the weight average molecular weight of the resin component, and the results of various physical properties of the coating agent are shown in Table 3.

Examples 4 to 5 In Example 1, 30% by weight of VAc, 40% by weight of EA and MM
Instead of using a monomer mixture consisting of 30% by weight of A,
VAc 30% by weight, n-butyl acrylate (nBA) 30% by weight
And 40% by weight of MMA or 20% by weight of VAc, 30% by weight of EA, 40% by weight of MMA and 10% by weight of acrylonitrile (AN)
A non-water-dispersible resin composition was obtained in the same manner as in Example 1 except that the monomer mixture consisting of A coating agent was prepared using the obtained non-water-dispersible resin composition, and various coating agent physical property tests were conducted.

Type of dispersion stabilizer solution used, content of dispersion stabilizer component in all resin components, composition of monomer for dispersed particle component, solubility parameter value of dispersed particle component and dispersion in all resin components The content of the particle component is shown in Table 2, the nonvolatile content of the obtained non-water-dispersible resin composition, the viscosity and the weight average molecular weight of the resin component, and the results of various physical properties of the coating agent are shown in Table 3.

Examples 6 to 7 Instead of using 300 parts by weight of the dispersion stabilizer solution and 400 parts by weight of the monomer mixture in Example 1, 260 parts by weight of the dispersion stabilizer solution and a single amount of the dispersion stabilizer solution were used. Example 1 except that the amount of the monomer mixture was 416 parts by weight, or the amount of the dispersion stabilizer solution charged was 520 parts by weight and the amount of the monomer mixture was 312 parts by weight, and the amount of "loose" used was changed accordingly. A non-water-dispersible resin composition was obtained in the same manner as in. A coating agent was prepared using the obtained non-water-dispersible resin composition, and various coating agent physical property tests were conducted.

Type of dispersion stabilizer solution used, content of dispersion stabilizer component in all resin components, composition of monomer for dispersed particle component, solubility parameter value of dispersed particle component and dispersion in all resin components The content of the particle component is shown in Table 2, the nonvolatile content of the obtained non-water-dispersible resin composition, the viscosity and the weight average molecular weight of the resin component, and the results of various physical properties of the coating agent are shown in Table 3.

Examples 8 to 10 and Comparative Examples 5 to 6 The procedure of Example 1 was repeated except that the dispersion stabilizer solutions of Reference Examples 2 to 6 were used instead of the dispersion stabilizer solution of Reference Example 1. A non-water-dispersible resin composition was obtained in the same manner as in Example 1. A coating agent was prepared using the obtained non-water-dispersible resin composition, and various coating agent physical property tests were conducted.

Type of dispersion stabilizer solution used, content of dispersion stabilizer component in all resin components, composition of monomer for dispersed particle component, solubility parameter value of dispersed particle component and dispersion in all resin components The content of the particle component is shown in Table 2, the nonvolatile content of the obtained non-water-dispersible resin composition, the viscosity and the weight average molecular weight of the resin component, and the results of various physical properties of the coating agent are shown in Table 3.

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[Table 2]

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[Table 3]

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INDUSTRIAL APPLICABILITY The present invention provides a dispersion stabilizer component obtained by copolymerizing a specific methacrylic acid ester monomer as a main component in an organic solvent containing a specific hydrocarbon organic solvent as a main component.
The present invention relates to a non-aqueous dispersible resin composition, which is obtained by copolymerizing a monomer having a specific composition containing vinyl acetate as the dispersed particle component (B) in the presence of (A).

The non-water-dispersible resin composition of the present invention is suitable for use as a vehicle for a coating agent for outer walls mainly made of an inorganic base material such as concrete or mortar, especially for buildings and structures such as residences. The obtained coating agent can be used even under coating conditions such as below freezing, for example, -5 ° C, and the obtained coating film of coating agent has high moisture permeability and is also excellent in waterproofness and alkali resistance. Form a film.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08F 220/18 MLQ 7242-4J C09D 131/04 PFV 6904-4J 133/08 PFY 7921-4J // C09D 5 / 00 PNZ 6904-4J

Claims (1)

[Claims] 1. In an organic solvent containing an aliphatic hydrocarbon organic solvent and / or an alicyclic hydrocarbon organic solvent as a main component,
70 to 90 weight of at least one monomer selected from the group consisting of the following (a-1) to (a-3), (a-1) n-butyl methacrylate, i-butyl methacrylate and t-butyl methacrylate %, (A-2) a (meth) acrylic acid alkyl ester monomer having an alkyl group with 6 to 18 carbon atoms, other than (a-1)
Dispersion stability obtained by copolymerizing a monomer consisting of 10 to 30% by weight, and (a-3) 0 to 20% by weight of a comonomer other than (a-1) and (a-2) above. Agent component
In the presence of (A), the following (b-1) ~ (b-
3), (b-1) 10 to 50% by weight of vinyl acetate, (b-2) 50 to 90% by weight of a (meth) acrylic acid alkyl ester monomer having an alkyl group with 1 to 18 carbon atoms, and (b) b-3) A non-water-dispersible resin composition characterized by being obtained by copolymerizing a monomer consisting of 0 to 40% by weight of a comonomer other than (b-1) and (b-2) above. object. [However, the total of (a-1) to (a-3) and the total of (b-1) to (b-3) are 100% by weight, respectively. ]