JP3210490B2 - Resin composition for sealer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an inorganic porous substrate, for example, a surface of a substrate such as mortar, concrete, slate plate, calcium silicate plate, ALC plate or the like, or a previously applied coating film (hereinafter referred to as an old coating film). A resin composition for a sealer suitable for adjusting the base of a surface that is chalked like a surface (sometimes referred to as a coating film), in particular, when applied to the surface of an inorganic porous substrate, impregnating properties, Excellent adhesion, water resistance and durability,
The present invention relates to a resin composition for a sealer that, when applied to a cement-based alkaline building material base, reinforces these surfaces, prevents leaching of alkali, and improves the durability of a top coat or the like.

[0002]

Problems to be solved by the prior art and the invention
Conventionally, as a method of coating an inorganic porous substrate, a method of applying a sealer having excellent adhesion and then applying various coating materials has been adopted in order to secure adhesion and durability. . In addition, as a resin for a sealer when coating on an inorganic porous substrate, a relatively low molecular weight moisture-curable urethane, a solvent-based resin dissolved in an aromatic hydrocarbon-based organic solvent such as toluene, or the like is used. But
The former is not toxic, and the latter has excellent penetration into the base material, but does not necessarily provide satisfactory surface reinforcement and alkali barrier effect to prevent leaching of alkali from the base material. In order to satisfy this, there is a need to increase the number of coatings, and further, there is a problem on environmental hygiene due to volatilization of the organic solvent at the time of coating. On the other hand, as a water-based sealer, those having a water-soluble resin as a main component have been variously studied, and those having a water-soluble resin as a main component have a water resistance and a water-dispersible resin as a main component. At present, there is no water-based sealer that has poor permeability and adhesion to a substrate and has long-term durability.

[0003] Accordingly, an object of the present invention is to provide an alkali barrier effect, by appropriate penetration into a substrate and surface reinforcement.
An object of the present invention is to provide a sealer resin composition having excellent adhesion. Another object of the present invention is to provide a resin composition for a sealer having less air pollution and environmental health problems, and still another object is to apply it to various old coating films, It is an object of the present invention to provide a resin composition for a sealer which does not attack the old coating film and does not cause bleeding or lifting phenomenon.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an organic solvent (A) mainly containing a fatty acid hydrocarbon-based solvent and / or an alicyclic hydrocarbon-based solvent contains: A resin for a sealer that achieves the above object by containing a copolymer (B) obtained by copolymerizing the following (i), (ii) and (iii) and a polymer (C) insoluble in the organic solvent. Composition (provided that the amount of the aliphatic hydrocarbon-based solvent and / or alicyclic hydrocarbon-based solvent with respect to 100 parts by weight of the copolymer (B) is 30 to 1200 parts by weight, and the polymer (C) is intended fluorine a monomer containing no resin (co) polymerized, and the amount is 20 to 150 parts by weight der of the copolymer (B) polymer relative to 100 parts by weight (C)
And does not include the above-mentioned fluororesin that gives the polymer (C).
Monomer is styrene and its derivatives,
Kill ester, alkyl methacrylate, cyclo
Hexyl acrylate, cyclohexyl metaacrylate
G, acrylic acid, methacrylic acid, maleic anhydride, N-
Vinylpyrrolidone, mono- or di-alkyl maleate
Esters, mono- or di-alkyl esters of fumaric acid
Mono- or di-alkyl itaconic acid,
Rilonitrile, methacrylonitrile, vinyl acetate, pro
Vinyl pionate, dimethylaminoethyl (meth) acryl
Rate, diethylaminoethyl (meth) acrylate,
Hydroxyethyl (meth) acrylate, hydroxyp
Propyl (meth) acrylate, vinyl pyridine, vinyl
Imidazole, ethoxyethyl (meth) acrylate,
Methoxyethyl (meth) acrylate, vinyl sulfone
Acid, p-vinylbenzenesulfonic acid, vinylamine, and
Or two or more selected from p-vinylnitrobenzene
That is all. ) Was obtained, and arrived at the present invention. (I) one or more alkyl acrylates and / or alkyl methacrylates having 6 to 18 carbon atoms in the alkyl group; 15 to 60% by weight; (ii) a vinyl monomer represented by the following [Chemical Formula 2];
~ 85% by weight

[0005]

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(Iii) Monomers other than the above (i) and (ii): 0 to 55% by weight [provided that the total of (i), (ii) and (iii) is 100% by weight. ]

Hereinafter, the resin composition for a sealer of the present invention will be described in detail. Examples of the aliphatic hydrocarbon-based solvent and / or alicyclic hydrocarbon-based solvent used in the present invention include n-hexane, i-hexane, n-heptane, and n-hexane.
Octane, i-octane, n-decane, n-dodecane,
Cyclohexane, methylcyclohexane, cycloheptane, methylcycloheptane, "Loose", "Mineral Spirit EC", "Shellsol 71", "VM & P naphtha", "Shell TS28 Solvent" (all from Shell), "Isopar C" , "Isoper E", "Isoper G", "Isoper H", "Isoper M",
"Naphtha No.3", "Naphtha No.5", "Naphtha No.6",
"Solvent 7" (Exceeded by Exxon Chemical Company),
“IP solvent 1016”, “IP solvent 162”
0 "," IP Solvent 2028 "," IP Solvent 2835 "(both manufactured by Idemitsu Petrochemical Co., Ltd.)," White Sol "(manufactured by Kyodo Petroleum Co., Ltd.)," Mitsubishi Mineral Tarpin "," Diamond Solvent "[ As mentioned above, "Mitsubishi Oil Co., Ltd.", "Pegazol AN-45", "Pegazol 3040" (all, manufactured by Mobil Sekiyu KK) and the like can be mentioned. Among these solvents, n-hexane,
The use of n-heptane, "loose" is preferred. These hydrocarbon solvents can be used alone or in combination of two or more.

In the present invention, an organic solvent other than the hydrocarbon solvent is used in addition to the aliphatic hydrocarbon solvent and the alicyclic hydrocarbon solvent as long as the excellent effects of the present invention are not impaired. can do. Examples of such an organic solvent include benzene, toluene, ethylbenzene, propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, “Solvesso 100” and “Solvesso 150”
Aromatic hydrocarbon-based organic solvents such as [manufactured by Exxon Chemical Co., Ltd.]; for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, n
-Hexyl alcohol, n-octyl alcohol, i-
Alcohol organic solvents such as octyl alcohol and 2-ethylhexyl alcohol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl-i-butyl ketone, methyl amyl ketone, and cyclohexanone; for example, methyl acetate, ethyl acetate, acetic acid-n- Ester-based organic solvents such as butyl and aluminum acetate; for example, methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, i
Cellosolve organic solvents such as -propyl cellosolve, n-butyl cellosolve, i-butyl cellosolve, i-amyl cellosolve, phenyl cellosolve, benzyl cellosolve; methyl carbitol, ethyl carbitol, n-propyl carbitol, i-propyl carbitol, n −
Carbitol organic solvents such as butyl carbitol, i-butyl carbitol, i-amyl carbitol, phenyl carbitol, benzyl carbitol; and the like. Among these solvents, toluene, o-xylene, m-xylene, p-xylene, “Solvesso 10
0 ", methyl alcohol and n-butyl alcohol are preferred.

In the present invention, the proportion of the aliphatic hydrocarbon solvent and / or the alicyclic hydrocarbon solvent in the total organic solvent used in the present invention is 50% by weight or more, preferably 70% by weight or more. is there. When the ratio of the hydrocarbon solvent is 50
When the content is not less than the lower limit, air permeability and environmental hygiene problems may occur when the content is less than the lower limit. When used as a resin composition for a sealer, it is not preferred because it may attack the old coating film and cause bleeding and lifting phenomena.

The copolymer (B) contained in the organic solvent (A) containing the aliphatic hydrocarbon solvent and / or the alicyclic hydrocarbon solvent as a main component of the present invention comprises: (i) an alkyl group At least one of alkyl acrylate and / or acryl methacrylate having 6 to 18 carbon atoms: 15 to 60% by weight (ii) a vinyl monomer represented by the following general formula: 85% by weight

[0011]

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(Iii) a monomer other than the above (i) and (ii); a monomer consisting of 0 to 55% by weight [provided that the total of the monomers (i), (ii) and (iii) To 100% by weight]. This copolymer (B) is substantially soluble in the organic solvent (A) containing the aliphatic hydrocarbon-based solvent and / or the alicyclic hydrocarbon-based solvent as a main component.

Hereinafter, the monomers (i), (ii) and (iii) constituting the soluble copolymer (B) will be described in detail. Examples of the monomer (i) include n-hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate,
Linear or branched alkyl esters of acrylic acid such as lauryl acrylate and stearyl acrylate having 6 to 18 carbon atoms; for example, n-hexyl methacrylate, n
Straight-chain or branched alkyl esters of methacrylic acid having 6 to 18 carbon atoms, such as -octyl methacrylate, i-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate; Of these monomers, use of 2-ethylhexyl acrylate and 2-erhexyl acrylate is preferred.

The amount of the monomer (i) to be used is 15 to 15 with respect to all the monomers constituting the soluble copolymer (B).
It is 60% by weight, preferably 15 to 50% by weight. If the amount of the monomer (i) used is less than the lower limit, the adhesion of the resin composition for a sealer containing the soluble copolymer (B) to the substrate is reduced. When the value is not less than the above value, excellent adhesion is obtained, and a film obtained from the resin composition has excellent alkali resistance, which is preferable. If the amount is more than the upper limit, the soluble copolymer (B) becomes too soft, and thus the blocking or overcoating agent on the sealer-coated surface to which the obtained resin composition for sealer is applied is water-based. Cissing of the coating agent may occur, which is not preferable.

As the monomer of the above (ii), in the general formula of the above formula, X is H, an alkyl group having 1 to 2 carbon atoms, Cl, OCOR ₂ , an aryl group having 6 to 8 carbon atoms. Can be used. Examples of such a monomer include an olefin monomer in which X is H and an alkyl group having 1 to 2 carbon atoms, for example, ethylene, propylene, n-butylene, i-butylene and the like; A vinyl chloride monomer, for example, vinyl chloride; a saturated fatty acid vinyl ester monomer in which X is OCOR ₂ and R ₂ is a linear or branched alkyl group having 1 to 12 carbon atoms, for example, vinyl acetate, propionic acid Vinyl, n-vinyl butyrate, trade name "vinyl versatate" (manufactured by Shell Co., Ltd.), etc .; an aromatic vinyl monomer in which X is an aryl group having 6 to 8 carbon atoms, for example, styrene, α-methylstyrene, vinyl Toluene, ethylvinylbenzene and the like can be mentioned. Of these monomers, the use of aromatic vinyl monomers is preferred, and the use of styrene and vinyl toluene is more preferred.

The amount of the monomer (ii) to be used is from 30 to 30% based on all the monomers constituting the soluble copolymer (B).
It is 85% by weight, preferably 45 to 75% by weight. If the amount of the monomer (ii) used is less than the lower limit, the alkali resistance and the surface barrier properties of the film obtained from the resin composition for a sealer containing the soluble copolymer (B) are reduced. It is not preferable because it lowers. Exceeding the upper limit is not preferred because the adhesiveness and permeability of the resin composition for a sealer to a substrate are reduced.

Examples of the monomer (iii) include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, Acrylates other than the monomer (i) such as benzyl acrylate; for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate;
Methacrylates other than the monomer (i) such as i-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate; for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, Maleic anhydride, fumaric acid, crotonic acid, citraconic acid, (preferably acrylic acid,
Carboxyl group-containing monomers such as methacrylic acid); for example, acrylamide, methacrylamide, N, N-dimethylacrylamide, N-methylacrylamide,
Amide or substituted amide group-containing monomers such as N-butoxymethylacrylamide (preferably acrylamide and methacrylamide); for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Propyl methacrylate, allyl alcohol, methallyl alcohol (preferably, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate) and other hydroxyl-containing monomers; for example, aminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate Amino group- or substituted amino group-containing monomers such as acrylate, N, N-diethylaminoethyl methacrylate (preferably, N, N-dimethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate);
For example, epoxy group-containing monomers such as glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, glycidyl methallyl ether, and glycidyl vinyl ether; for example, mercapto group-containing monomers such as vinyl mercaptan and allyl mercaptan; for example, (poly) ethylene glycol In one molecule of di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, divinyl benzene, etc. And a monomer having two or more radically polymerizable unsaturated groups; and in the present invention, one or more of these monomers may be appropriately selected and used. Can.

The amount of the monomer (iii) used is based on the total amount of the monomers constituting the soluble copolymer (B).
It is 0 to 55% by weight, preferably 0 to 40%. If the amount of the monomer (iii) exceeds the upper limit, the alkali resistance of the film obtained from the resin composition for a sealer containing the soluble copolymer (B) is undesirably reduced. It is preferable to copolymerize the monomer (iii) with the used amount in the above range, since dispersibility and storage stability are improved when a pigment or the like is blended with the resin composition for a sealer.

The soluble copolymer (B) used in the present invention preferably has a weight average molecular weight of 20,000 to 300,000, more preferably 30,000 to 200,000, and most preferably 50,000 to 150,000. When the molecular weight exceeds 300,000, the viscosity of the resin composition for a sealer containing the soluble copolymer (B) tends to increase, and the permeability as a sealer to an inorganic porous substrate may decrease. There is not preferred. When the molecular weight is less than 20,000, the alkali resistance of the resin composition for a sealer containing the soluble copolymer (B) tends to decrease, and the resin composition is not suitable for use as a sealer in a cement-based alkaline building material. Is not preferred. The value of the weight average molecular weight in the present invention is measured by a gel permeation chromatography method (hereinafter, sometimes abbreviated as GPC method).

The soluble copolymer (B) has a glass transition point (Tg) of preferably from 0 to 80 ° C.
More preferably, the temperature is 20 to 70 ° C. When the glass transition point (Tg) exceeds the upper limit, when the resin composition of the present invention is used at room temperature, the permeability and adhesion of the resin composition to an inorganic porous substrate are preferably reduced. In addition, if the amount is less than the lower limit, blocking occurs on the sealer-coated surface to which the obtained resin composition for a sealer has been applied, and the reinforcing property of the base material surface is undesirably reduced.

Here, Tg is one of the important characteristics of the polymer (polymeric substance) as described above. E. FIG. It is described in "Mechanical Properties of Polymers" by Nielsen, translated by Nojiharu Onoki. The Tg of the copolymer is 26
As described on pages 27 to 27, it is determined by the following equation.

1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂
+ ····· + W _n / Tg _n where, in the above formula, Tg, indicating that each Tg _n and W _n below. Tg: Glass transition temperature Tg n expressed in absolute temperature of the copolymer: Glass expressed in absolute temperature of the homopolymer of the _n component transition temperature W _n: weight fraction of copolymer of n components W ₁ + W ₂ +
... + W _n = 1

The amount of the aliphatic hydrocarbon solvent and / or the alicyclic hydrocarbon solvent per 100 parts by weight of the copolymer (B) obtained by copolymerizing the above (i), (ii) and (iii) is as follows: 30
To 1200 parts by weight, preferably 45 to 450 parts by weight.

Further, the resin composition for a sealer of the present invention comprises:
In an organic solvent (A) containing an aliphatic hydrocarbon-based solvent and / or an alicyclic hydrocarbon-based solvent as a main component, a polymer (C) insoluble in the organic solvent together with a soluble copolymer (B). and those containing the copolymer in the organic solvent (a) a resin component composed of (B) and polymer (C), generally 20 to 70% by weight, preferably contains 40 to 60 wt% And the viscosity is generally about 100 cps to 20,000 cp.
s is good.

[0025] Examples of monomers which provide the above-mentioned organic solvent (A) not soluble polymer (C), although the monomer is soluble in the solvent, the nature of solubility precipitates decreases to become polymer Having a monomer. Such monomers include styrene and its derivatives, alkyl acrylates, alkyl methacrylates, maleic anhydride, N-vinylpyrrolidone, mono- or di-maleic acid.
Alkyl esters, fumaric acid mono- - or di - alkyl esters, itaconic acid mono - or di - alkyl esters, acrylic nitrile, methacrylic nitrile, vinyl acetate, vinyl propionate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth A) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, vinylpyridine, vinylimidazole, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, vinylsulfonic acid, p-vinylbenzenesulfonic acid, vinylamine, Examples include p-vinylnitrobenzene and other monomers. Among these monomers, ethyl acrylate, butyl acrylate, methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, vinyl acetate, styrene, acrylonitrile, acrylic acid, main Taku acrylic acid, the use of hydroxyethyl methacrylate are preferable. The insoluble polymer (C) of the present invention can be used in the monomer, a copolymer consisting of a single polymer or two or more.

The resin composition for a sealer of the present invention contains the insoluble polymer (C), whereby the permeability to the inorganic porous substrate can be adjusted, and the surface of the substrate can be adjusted. Reinforcement also improves. The insoluble polymer (C)
Is a copolymer of prior SL-soluble (B) with respect to 100 parts by weight
It is used in a proportion of 20 to 150 parts by weight. Ratio copolymer (B) of the soluble polymer of the insoluble (C) is, if it exceeds the upper limit, since permeability and adhesion to inorganic porous substrate of the sealer composition is reduced Not preferred. Generally, the particle size of the insoluble polymer (C) is preferably in the range of 0.05 to 5 μm, but can be changed to a certain extent as needed.

The soluble copolymer (B) used in the present invention is prepared by directly performing solution polymerization in an organic solvent mainly containing an aliphatic hydrocarbon solvent and / or an alicyclic hydrocarbon solvent. Although it can be produced, it can also be obtained by performing solution polymerization in another low-boiling point organic solvent, and then concentrating in vacuo to perform solvent replacement. The soluble copolymer (B) is usually
Prior to the polymerization of the insoluble polymer (C), in the same organic solvent as the organic solvent (A) mainly containing the aliphatic hydrocarbon-based solvent and / or the alicyclic hydrocarbon-based solvent, Monomer (i), (ii) and (iii) with a suitable polymerization initiator,
In addition, it can be produced by heating and reacting for several hours while stirring in a nitrogen stream or at the reflux temperature of an organic solvent using a chain transfer agent used as necessary.
In this case, these organic solvents, monomers, polymerization initiators and / or
Alternatively, at least a part of the chain transfer agent may be sequentially added. The polymerization temperature for polymerizing the soluble copolymer (B) is generally about 30 to 180 ° C, preferably about 6 ° C.
The range of 0 to 150 ° C is good.

In general, a resin dispersion containing an insoluble polymer can be easily produced by polymerizing an insoluble polymer in a solution of a soluble copolymer in a medium. The copolymer and the insoluble polymer are separately manufactured, and then both polymers are dissolved in a common solvent of both polymers, and then appropriately manufactured by a method such as dropping with stirring into a hydrocarbon-based medium. be able to. Therefore, the resin dispersion containing the insoluble polymer (C) of the present invention can be obtained by the above-mentioned production method.

The resin dispersion containing the insoluble polymer (C) is mixed with the soluble solvent in an organic solvent mainly containing an aliphatic hydrocarbon solvent and / or an alicyclic hydrocarbon solvent. In the presence of the polymer (B), a monomer which gives the insoluble polymer (C) as a dispersed particle component is mixed with a suitable polymerization initiator and, if necessary, a chain transfer agent using a nitrogen stream. It can be produced by heating for several hours while stirring at a medium or reflux temperature of an organic solvent to carry out copolymerization. In this case, the same polymerization initiator, chain transfer agent, and the like as those used in the production of the soluble copolymer (B) can be used. Further, at least a part of the organic solvent, the monomer, the polymerization initiator and / or the chain transfer agent may be sequentially added. The polymerization temperature when polymerizing the insoluble polymer (C) is generally in the range of about 30 to 180 ° C, preferably about 60 to 150 ° C, as in the case of the soluble copolymer (B). Good.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate and t-butylperoxy. Organic peroxides such as bivalate; for example, 2,2'-azobis-i-butyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4-methoxy-2, An azo compound such as 4-dimethylvaleronitrile; and the like can be used alone or in combination. The amount of the polymerization initiator to be used is generally about 0.01 to 5 parts by weight, preferably about 0.02 to 5 parts by weight, based on 100 parts by weight of the total of the monomers (i), (ii) and (iii). 2 parts by weight are used.

The chain transfer agent includes, for example,
Cyanoacetic acid; alkyl cyanoacetic acid esters having an alkyl group of 1 to 8 carbon atoms: bromoacetic acid; bromoacetic acid esters having an alkyl group of 1 to 8 carbon atoms; fragrances such as anthracene, phenanthrene, fluorene, and 9-phenylfluorene Aromatic compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol and p-nitrotoluene; benzoxone, 2,3,5,6-tetramethyl-p Benzoquinone derivatives such as benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane, Halogenated hydrocarbons such as 3-chloro-1-propene Aldehydes such as chloral and furaldehyde; alkyl mercaptans having 1 to 18 carbon atoms; aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid; alkyl esters having 1 to 10 carbon atoms of mercaptoacetic acid; To 12 hydroxyalkyl mercaptans; terpenes such as binene and terpinolene; and the like. When the chain transfer agent is used, its amount is about 0.005 to 3.0 parts by weight based on 100 parts by weight of the total of the monomers (i), (ii) and (iii). Is preferred.

The resin composition for a sealer of the present invention is used by mixing an alkyd resin, an acryl-modified alkyd resin, an epoxy resin, an amino resin, a fluororesin, a silicone resin and the like within a range not to impair the excellent effects of the present invention. can do. The resin composition for a sealer of the present invention,
As it is, or in the resin composition for a sealer, if necessary, for example, an organic or inorganic coloring agent such as titanium oxide, carbon black, and phthalocyanine blue;
Inorganic fillers such as calcium carbonate, silica, clay, talc, aluminum hydroxide and glass powder; antioxidants; preservatives; antifungal agents; ultraviolet absorbers; antistatic agents; Can be. Further, the non-aqueous resin composition of the present invention may optionally contain a cross-linking agent such as an epoxy resin, an amino resin, an isocyanate compound, or a metal chelate in a range of use that does not impair the excellent effects of the present invention. Can also be used.

The resin composition for a sealer of the present invention can be diluted with an appropriate organic solvent, if necessary, and applied to various substrates by various methods such as dipping, spraying, and coating. As a substrate to which such a resin composition for a sealer of the present invention can be suitably applied, for example, mortar, concrete, glass, ceramic, slate plate,
Inorganic base materials such as rocks, silica plates, ALC plates, cement-based building materials, ores; and metal base materials used for outer walls and roofs of buildings and structures, particularly tin and colored tins, and the like. In addition, the resin composition for a sealer of the present invention can be applied to new and existing painted surfaces such as sprayed tile coatings, alkyd resin-based rust-resistant coatings, and epoxy resin-based rust-resistant coatings. it can.

The resin composition for a sealer of the present invention further includes, for example, a metal plate such as an aluminum plate, a zinc plate, an iron plate, and a stainless steel plate; for example, a vinyl chloride resin, a vinylidene chloride resin, a vinyl acetate resin, a styrene resin, Acrylic resin, polyester resin, polycarbonate resin, AB
Molding of thermoplastic synthetic resin such as S resin, AS resin, urethane resin, SBR; molding of thermosetting synthetic resin such as phenol resin, melamine resin, urea resin, epoxy resin, unsaturated polyester resin, polyimide resin object;
It can be suitably used for substrates such as The resin composition for a sealer of the present invention can be applied by various methods such as a brush, a roller, a spray, a roll coater, and a knife coater, and can be dried at room temperature or forcedly dried by heating.

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The methods for preparing the coated plates and testing the physical properties of the coated films in the examples and comparative examples are shown below.

(1) Preparation of test coated plate 1-1) Water permeability test (a) Asbestos cement silica plate [JIS A 5418] having a relatively low surface strength and an apparent specific gravity of about 0.7 was added to a solvent (“Loose”). Sample) diluted to 25% solids by
Apply with a 00 g / m ² brush and dry at room temperature for 7 days. (B) Flexible board [JIS A 5403 (F)]
, A sample diluted to a solid content of 25% is applied with a 100 g / m ² brush, and dried at room temperature for 7 days. 1-2) Surface Reinforcement In the same manner as in (a) of 1-1), a sample was applied and dried at room temperature for one day. Then, a water-based paint having elasticity was coated to a thickness of about 800.
A doctor blade is applied so as to have a thickness of μm and dried at room temperature for 7 days. 1-3) Adhesion and alkali resistance A sample diluted to a solid content of 25% is applied to a flexible board [JIS A 5403 (F)] with a brush of 100 g / m ² and dried at room temperature for 3 days.

(2) Permeability test Regarding the test coated plate of 1-1), JIS A 6910
A water permeability test was performed by a method according to the above. However, the silicon permeate of the substrate (a) was examined for water permeation after 1 hour, and the flexible plate of (b) was examined for water permeation after 24 hours.

(3) Surface Reinforcement Test The coated surface of the test coated plate of 1-2) was peeled 180 ° at a width of 2 cm and a pulling speed of 100 mm / min, and the peel strength was measured. The higher the peel strength, the greater the surface reinforcement.

(4) Adhesion test With respect to the test coated plate of 1-3), 5 mm was measured with a cutter knife.
Cut 5 x 5 gobang eyes at intervals, JIS K 5400
The test was performed by the Goban-mesh tape method according to the above. The evaluation of adhesion was evaluated according to the following criteria. ○: The coating film was not peeled at all △: The coating film was partially peeled ×: The coating film was completely peeled

(5) Alkali Resistance Test The test coated plate of 1-3) was immersed in saturated calcium hydroxide water for 7 days, and the presence or absence of blisters on the coating film was observed and evaluated according to the following criteria. ○ ・ ・ ・ No blisters △ ・ ・ ・ Partly blisters × ・ ・ ・ Blurs all over

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 2-ethylhexyl acrylate (2EHA) 1 was placed in another container.
600 parts by weight of a monomer mixture consisting of 5% by weight, 45% by weight of styrene (St), and 40% by weight of i-butyl methacrylate (iBMA) were prepared, and 200 parts by weight thereof were charged into a reactor. After replacing with nitrogen, 100 ° C
To t-butylperoxy-2 as a polymerization initiator.
0.6 parts by weight of ethylhexanoate (tBPOO) was added, and the mixture was kept at the same temperature for 30 minutes. Further, 400 parts by weight of the remaining monomer mixture, 50 parts by weight of “loose” and tBP
A mixture consisting of 2 parts by weight of OO was sequentially added dropwise over 2 hours, and after completion of the addition, the mixture was maintained at the same temperature for 30 minutes.
2 parts by weight of BPOO were added, and the mixture was kept at the same temperature for another 3 hours, and then 500 parts by weight of "loose" was added and cooled. As a result, the nonvolatile content was 49.5% and the weight average molecular weight was 98,000.
To obtain a resin solution having a viscosity of 7500 cps.

Reference Example 2 In the same reactor as used in Reference Example 1, "Loose" 50
Parts by weight, and then 600 parts by weight of a monomer mixture composed of 30% by weight of 2EHA, 69% by weight of St, and 1% by weight of methacrylic acid (MAA) are prepared in another container, and 200 parts by weight of these are charged into the reactor. After the inside of the reactor was replaced with nitrogen, the temperature was raised to 100 ° C., and tBPO was used as a polymerization initiator.
0.6 parts by weight of O was added and kept at the same temperature for 30 minutes. Further, a mixture composed of the remaining monomer mixture (400 parts by weight), toluene (50 parts by weight) and tBPOO (4.8 parts by weight) was successively added dropwise over 2 hours. After completion of the addition, the mixture was kept at the same temperature for 30 minutes, and then tBPOO (2 parts by weight) was added. The mixture was kept at the same temperature for another 3 hours, and then 500 parts by weight of "loose" was added and cooled. As a result, a resin solution having a viscosity of 2000 cps and comprising a polymer having a nonvolatile content of 49.5% and a weight average molecular weight of 60000 was obtained.

Example 1 In a reactor similar to that used in Reference Example 1, "Loose" 20
0 parts by weight and 700 parts by weight of the resin solution obtained in Reference Example 1 were charged and purged with nitrogen, and then heated to 100 ° C.
Weight%, ethyl acrylate (EA) 33 weight%, methyl methacrylate (MMA) 20 weight%, n-butyl methacrylate (nBMA) 20 weight%, MAA 2 weight% 350 parts by weight of a monomer mixture, "Loose" 1
50 parts by weight and 3.5 parts by weight of tBPOO were successively added dropwise over 2 hours, and after completion of the addition, the mixture was maintained at the same temperature for 30 minutes. Then, 3 parts by weight of tBPOO was added, and the mixture was further maintained at the same temperature for 3 hours. As a result, a milky white emulsion resin dispersion having a viscosity of 5000 cps and comprising a polymer having a nonvolatile content of 50.0% was obtained.

Comparative Example 1 Toluene 150 was placed in the same reactor as used in Reference Example 1.
Parts by weight, and then EA 40% by weight, M
600 parts by weight of a monomer mixture composed of 59% by weight of MA and 1% by weight of MAA were prepared, 200 parts by weight of the monomer mixture were charged into a reactor, and the inside of the reactor was purged with nitrogen. And added 0.6 parts by weight of tBPOO, and kept at the same temperature for 30 minutes. Further remaining monomer mixture 4
A mixture consisting of 00 parts by weight, 50 parts by weight of toluene and 2 parts by weight of tBPOO was successively added dropwise over 2 hours. After completion of the addition, the mixture was kept at the same temperature for 30 minutes, then 2 parts by weight of tBPOO was added, and the mixture was kept at the same temperature for 3 hours. Then, 400 parts by weight of toluene was added and the mixture was cooled. As a result, the nonvolatile content 5
A resin solution having a viscosity of 6500 cps and consisting of a polymer having a weight average molecular weight of 95,000 and 0.0% was obtained.

Comparative Example 2 "Loose" 50 was added to the same reactor as used in Reference Example 1.
Parts by weight, and then 70% by weight of 2-ethylhexyl methacrylate (2EHMA), iBMA
A monomer mixture consisting of 30% by weight (600 parts by weight) was prepared, 200 parts by weight of the mixture was charged into a reactor, the inside of the reactor was replaced with nitrogen, and the temperature was raised to 100 ° C. to obtain tBPOO 0.6 as a polymerization initiator. Parts by weight were added and kept at the same temperature for 30 minutes. Further, a mixture consisting of 400 parts by weight of the remaining monomer mixture, 50 parts by weight of "loose" and 2 parts by weight of tBPOO was successively added dropwise over 2 hours. After completion of the addition, the mixture was kept at the same temperature for 30 minutes, and then 2 parts by weight of tBPOO was added. The mixture was kept at the same temperature for another 3 hours, and then 500 parts by weight of "loose" was added and cooled. As a result, a viscosity 540 consisting of a polymer having a nonvolatile content of 49.6% and a weight average molecular weight of 110,000 was obtained.
A resin solution of 0 cps was obtained.

Comparative Example 3 "Loose" 50 was added to the same reactor as used in Reference Example 1.
Parts by weight, then 600 parts by weight of a monomer mixture composed of 10% by weight of 2EHA and 90% by weight of St was prepared in another container, 200 parts by weight of the mixture was charged into a reactor, and the inside of the reactor was purged with nitrogen. The temperature was raised to 100 ° C., 0.6 parts by weight of tBPOO was added as a polymerization initiator, and the temperature was maintained for 30 minutes. 400 parts by weight of the remaining monomer mixture,
A mixture consisting of 50 parts by weight of toluene and 4.8 parts by weight of tBPOO was successively added dropwise over 2 hours. After the completion of the addition, the mixture was kept at the same temperature for 30 minutes. Then, 2 parts by weight of tBPOO was added, and the mixture was kept at the same temperature for 3 hours. From "Loose" 50
The mixture was cooled by adding 0 parts by weight. As a result, the non-volatile content 49.
A resin solution having a viscosity of 16000 cps and comprising 2% of a polymer having a weight average molecular weight of 57000 was obtained. The resulting resin solution had low solubility in "loose", became cloudy when diluted, and separated the resin layer over time.

Comparative Example 4 "Loose" 20 was placed in the same reactor as used in Reference Example 1.
0 parts by weight and 250 parts by weight of the resin solution obtained in Reference Example 1, were charged with nitrogen, and then heated to 100 ° C.
Weight%, ethyl acrylate (EA) 33 weight%, methyl methacrylate (MMA) 20 weight%, n-butyl methacrylate (nBMA) 20 weight%, MAA 2 weight% 350 parts by weight of a monomer mixture, "Loose" 1
50 parts by weight and 3.5 parts by weight of tBPOO were successively added dropwise over 2 hours, and after completion of the addition, the mixture was maintained at the same temperature for 30 minutes. Then, 3 parts by weight of tBPOO was added, and the mixture was further maintained at the same temperature for 3 hours. As a result, a milky white emulsion resin dispersion having a viscosity of 4000 cps and comprising a polymer having a nonvolatile content of 50.0% was obtained.

Reference Examples 1 and 2, Example 1, and Comparative Example 1
Using the resin solution and the resin dispersion obtained in Nos. 1 to 4, test coating plates were prepared by the above method, and various physical property tests were performed. The results are shown in Table 1.

[0049]

[Table 1]

[0050]

Industrial Applicability The resin composition for a sealer of the present invention has an excellent alkali barrier effect and adhesion due to a proper penetration into a substrate and a surface reinforcing property. In addition, when the composition is applied to various old coating films, the old coating film is not eroded, and no smearing or lifting phenomenon occurs.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09D 5/34 C09D 5/34 123/08 123/08 125/04 125/04 127/06 127/06 131/02 131/02 133/08 133/08 C09K 3/10 C09K 3/10 E (56) References JP-A-2-88608 (JP, A) JP-A-60-166354 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C08L 33/08 C08L 23/08 C08L 25/04 C08L 27/06 C08L 31/02 C09D 5/34 C09D 123/08 C09D 125/04 C09D 127/06 C09D 131/02 C09D 133 / 08 C09K 3/10

Claims (2)

(57) [Claims] (1) An organic solvent (A) containing an aliphatic hydrocarbon-based solvent and / or an alicyclic hydrocarbon-based solvent as a main component is copolymerized with the following (i), (ii) and (iii). (B) and a polymer (C) insoluble in the organic solvent, wherein the aliphatic hydrocarbon-based solvent and / or the alicyclic group are contained in 100 parts by weight of the copolymer (B). The amount of the hydrocarbon solvent is 30 to 1200 parts by weight, and the polymer (C) is obtained by (co) polymerizing a monomer containing no fluororesin, and the copolymer (B) 100 The amount of the polymer (C) is from 20 to 150 parts by weight based on the weight of the polymer,
The fluororesin-free monomer giving (C) is
Styrene and its derivatives, alkyl acrylate
, Methacrylic acid alkyl ester, cyclohexylurea
Acrylate, cyclohexyl methacrylate, acrylic
Luic acid, methacrylic acid, maleic anhydride, N-vinylpyro
Lidone, maleic acid mono- or di-alkyl esters,
Fumaric acid mono- or di-alkyl esters, itacone
Acid mono- or di-alkyl esters, acrylonitrile
, Methacrylonitrile, vinyl acetate, vinyl propionate
Nil, dimethylaminoethyl (meth) acrylate, di
Ethylaminoethyl (meth) acrylate, hydroxy
Ethyl (meth) acrylate, hydroxypropyl (meth
T) Acrylate, vinyl pyridine, vinyl imidazo
Ethoxyethyl (meth) acrylate, methoxyethyl
Tyl (meth) acrylate, vinyl sulfonic acid, p-bi
Nylbenzenesulfonic acid, vinylamine, and p-vinyl
A resin composition for a sealer, which is one or more kinds selected from lunitrobenzene . (I) at least one kind of alkyl acrylate and / or alkyl methacrylate having 6 to 18 carbon atoms in the alkyl group; 15 to 60% by weight; (ii) a vinyl monomer represented by the following Chemical Formula 1;
~ 85% by weight (iii) Monomers other than the above (i) and (ii); 0 to 55% by weight [provided that the total of (i), (ii) and (iii) is 100% by weight. ] 2. The sealer according to claim 1, wherein the aliphatic hydrocarbon-based solvent and / or the alicyclic hydrocarbon-based solvent are contained in the organic solvent (A) in an amount of 50% by weight or more. Resin composition.