WO2001085859A1

WO2001085859A1 - Water-based sealer composition

Info

Publication number: WO2001085859A1
Application number: PCT/JP2001/003628
Authority: WO
Inventors: Yasuyuki Sanai; Hiroaki Ishii; Hiroshi Iesako; Satoshi Kayamori; Hideki Kurita; Ken Takeda
Original assignee: Toagosei Co., Ltd.
Priority date: 2000-05-12
Filing date: 2001-04-26
Publication date: 2001-11-15
Also published as: CN1427875A; AU2001252602A1; KR20020094035A

Abstract

A water-based sealer composition which forms a coating film having excellent adhesion to substrates. The composition comprises as the active ingredient an aqueous dispersion obtained by polymerizing a vinyl monomer by emulsion polymerization in the presence of a macromonomer having carboxyl groups. The aqueous dispersion highly infiltrates into inorganic materials such as a slate, calcium silicate plate, and cement mortar.

Description

Aqueous sealer composition

Technical field

The present invention relates to a sealer composition, and more particularly to an aqueous sealer yarn composition for inorganic materials. Background art

For the interior and exterior of buildings, inorganic building materials such as slate, calcium silicate plate, cement mortar, etc. are used. Usually, these building materials are coated with various top coats. However, if a topcoat is applied directly to these building materials, the coating is liable to peel or deteriorate, making it difficult for the topcoat to exhibit its original performance. In addition, when applying a top coat on a brittle base coat or a base coat with deterioration or chalking, it is necessary to prepare the base coat or base coat. In order to avoid such preparation trouble and to eliminate the influence of the base material on the top coat, an undercoat agent called a sealer is usually applied to the base material before forming the top coat. Conventionally, as a sealer for undercoating, a synthetic resin thread containing an organic solvent has been used. However, in recent years, an aqueous synthetic resin composition containing little or no organic solvent is preferable in order to reduce toxicity and danger of ignition.

For example, Japanese Patent Application Laid-Open Nos. Sho 62-28316 and Hei 11-198925 disclose a conventional aqueous sealer using an aqueous vinyl polymer. . However, conventional water-based sealers have insufficient adhesion to the substrate, and their use has been limited. Summary of the Invention

An object of the present invention is to provide an aqueous sealer composition that forms a coating film having excellent adhesion to a base material.

In order to achieve the above object, the present invention provides a macromonomer having a carboxyl group. An aqueous sealer composition comprising an aqueous dispersion containing a vinyl polymer obtained by polymerizing a vinyl monomer in the presence of a nomer is provided.

It is preferable that the Mac monomer includes a monomer having a carboxyl group and a hydrophobic monomer. Among the monomers constituting the macromonomer, 10 to 75 mass of a monomer having a carboxyl group. It is preferably contained at a ratio of / ₀ .

The macromonomer is preferably obtained by radical polymerization of a monomer mixture containing a monomer having a carboxyl group at a reaction temperature of 180 to 350 ° C.

In another aspect of the present invention, there is provided an aqueous sealer composition applied to an inorganic material. The aqueous sealer composition includes an aqueous dispersion containing an aqueous solvent and a vinyl polymer dispersed in the aqueous solvent. The aqueous dispersion is produced by emulsion polymerization of a vinyl monomer in the presence of a macromonomer having a carboxyl group.

In a further aspect of the present invention, there is provided a method of making an aqueous sealer composition applied to an inorganic material. The method includes a step of preparing a macromonomer having a carboxyl group, and a step of obtaining an aqueous dispersion by emulsion-polymerizing a Bier monomer in the presence of the macromonomer. The aqueous dispersion includes an aqueous solvent and a vinyl polymer dispersed in the aqueous solvent. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the water II raw sealer composition according to one embodiment of the present invention will be described in detail. The main component or active ingredient of the aqueous sealer composition of the present invention is an aqueous dispersion, and the aqueous dispersion is obtained by polymerizing a vinyl monomer in the presence of a macromonomer having a carboxyl group.

The macromonomer having a carboxyl group has an ethylenically unsaturated bond at at least one terminal of the macromolecule molecule, and has a carboxyl group or a carboxylate in the macromonomer molecule. Mac mouth monomers essentially have carboxyl group-containing monomers. Hydrophobic monomer units may be included in the monomer units constituting the macromonomer. Cal for all monomer units of macromonomer The proportion of the monomer unit having a boxyl group is preferably from 10 to 75% by mass. In particular, when the proportion is 10 to 60% by mass, the stability of the aqueous dispersion is better.

The macromonomer is produced from a carboxyl group-containing monomer, if necessary, a hydrophobic monomer and / or an optional monomer.

The carboxyl group-containing monomer is a compound having a carboxyl group and an ethylenically unsaturated bond. For example, unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, atalyloxypropionic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, cyclohexanedicarboxylic acid, etc. Unsaturated dibasic acids can be used. Unsaturated acid anhydrides that generate carboxyl groups by hydrolysis of acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride can also be used. Among these carboxyl group-containing monomers, acrylic acid is particularly preferable because it has good polymerizability and forms an aqueous dispersion having excellent stability.

In the present specification, the hydrophobic monomer refers to a monomer having a solubility in water at 20 ° C. of 2% by mass or less. For example, methyl methacrylate, (meth) ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylate Lauryl acrylate and isobornyl (meth) acrylate can be used. In addition, methacrylic acid esters having 1 to 22 carbon atoms such as perfluoroalkyl (meth) acrylate and atalylic acid esters having 2 to 22 carbon atoms can be used, and butyl propionate and polystyrene can be used. Can also be used.

The optional monomer is a monomer other than the monomer containing a propyloxyl group and the hydrophobic monomer. Specific examples of the optional monomer include biel acetate, (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, and arylphosphonic acid. Acids, bierphosphonic acid and the like can be used.

The method for producing a macromonomer is described in, for example, Japanese Patent Application Laid-Open No. A known method disclosed in Japanese Patent Application Laid-Open No. Hei 11-181210 and "O99 / 077755" can be adopted. The gazette discloses a method of converting a specific group of a vinyl polymer having a radical polymerizable group bonded to one end to a carboxyl group, and Japanese Patent Application Laid-Open No. A method of reacting a dicarboxylic anhydride with a hydroxyl group-containing macromonomer having a radical polymerizable group is disclosed. WO 99/07755 discloses a monomer containing a carboxyl group-containing monomer A method for radically polymerizing a mixture at a high temperature of 180 ° C. or higher will be disclosed.

In producing the macromonomer, a known radical polymerization initiator can be used. Specific examples of the radical polymerization initiator include hydrogen peroxide, alkyl hydroxide peroxide, dialky peroxide, perester, percarbonate, persulfate, ketone peroxide, azo initiator and the like.

In the production of the macromonomer, the use of a solvent is optional. Preferred solvents are those that dissolve the raw material monomers (carboxyl group-containing monomer, hydrophobic monomer, optional monomer) and can avoid precipitation of the produced polymer. For example, aromatic alcohols such as benzyl alcohol, aliphatic alcohols such as isopropanol and butanol, ethylene glycol monoalkyl ethers such as methyl sorb and butyl sorb, diethylene glycol monoalkyl ethers such as carbitol, Solvents such as ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether and diglycol alkyl ethers such as diglycol methyl ether are preferred.

The macromonomer is preferably produced by subjecting a monomer mixture containing a monomer having a carboxyl group (raw material mixture) to radical polymerization at a reaction temperature of 180 to 350 ° C. It is particularly preferred that the radical polymerization reaction be performed continuously. According to such a macromonomer, an aqueous dispersion having excellent dispersion stability and excellent permeability to the underlying substrate can be obtained. In addition, an aqueous sealer in which the coating film after film formation has excellent adhesion to the base can be obtained. A more preferred reaction temperature is 220 to 350 ° C., which is particularly preferred. The reaction temperature is between 270 and 320C. According to such a macromonomer, an aqueous dispersion and an aqueous sealer having remarkable performance can be obtained.

The number average molecular weight of the macromonomer is preferably from 500 to 100,000. According to such a macromonomer, a water-based sealer composition that forms a coating film having excellent adhesion to a base can be obtained.

The macromonomer preferably has a carboxyl group neutralized by a base. Such macromonomers provide aqueous dispersions with excellent dispersion stability. Preferred bases are ammonia or low boiling amine compounds having a boiling point of below 140 ° C. For example, as the low-boiling amine compound, trimethylamine, getylamine, triethynoleamine, dimethinoleethynoleamine, N-methynolemonorephorin, t-butanolamine, morpholine, dimethylethanolamine and the like can be used. The neutralization of the macromonomer may be partial neutralization. The preferred neutralization ratio is 50 to 100%.

The main component or the active ingredient of the aqueous sealer composition is an aqueous dispersion of a vinyl polymer obtained by emulsion polymerization of a vinyl monomer in the presence of a Macmouth monomer or a neutralized product thereof. The macromonomer functions as an emulsifier. The usage amount of the macromonomer is preferably 5 to 300 parts by mass, more preferably 10 to 150 parts by mass, per 100 parts by mass of the vinyl monomer. If the amount of the macromonomer is too small, the stability of the vinyl polymer is low, and the permeability of the aqueous dispersion into the substrate is relatively low. Further, such an aqueous sealer yarn composition has a relatively low wettability with the substrate, and thus has a relatively low adhesion between the substrate and the coating film. On the other hand, when the amount of the macromonomer used is too large, the polymerization reaction is unstable. In addition, such an aqueous sealer composition forms a coating film having low water resistance.

The type of the vinyl monomer is not particularly limited. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethyl (meth) acrylate. Hexyl, stearyl (meth) acrylate, lauri (meth) acrylate And (meth) acrylic acid esters having 1 to 22 carbon atoms, such as isobornyl (meth) acrylate and perfluoroalkyl (meth) acrylate. Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyacrylonitrile, vinyl acetate, styrene, glycidyl (meth) acrylate, diacetone acrylamide, N-methylol acrylamide, N-alkoxymethyl acrylamide and the like can be used.

Emulsion polymerization of a vinyl monomer can be performed by a known method. For example, a method in which a macromonomer and a vinyl monomer are charged and polymerized in an aqueous medium, a method in which a macromonomer and a vinyl monomer are continuously or intermittently dropped and polymerized in an aqueous medium, There is a method in which water is added to a vinyl monomer to prepare a monomer emulsion, and this is continuously or intermittently dropped into an aqueous medium and polymerized. In the emulsion polymerization reaction, a known polymerization initiator can be used. The method of adding the polymerization initiator is not particularly limited. For example, the polymerization initiator may be added all at once at the start of the polymerization, or may be added sequentially, or the polymerization initiator may be dissolved in the monomer mixture and dropped together with the monomer mixture. Further, two or more kinds of addition methods may be used in combination.

Examples of the polymerization initiator include azo-based initiators such as azobisisobutyronitrile and azobispallet nitrile, and organic initiators such as benzoyl peroxide, lauryl peroxide and t-butyl peroxide. Inorganic peroxide initiators such as peroxide initiators, hydrogen peroxide, ammonium persulfate, persulfuric acid lime, and sodium persulfate can be used. Further, a redox initiator using a reducing agent such as Rongalit, L-ascorbic acid, or an organic amine in combination may be used. One of these initiators may be used alone, or two or more of them may be used in combination. The amount of the polymerization initiator to be used is about 0.05 to 10% by mass, preferably about 0.1 to 5% by mass, based on the weight of the monomer.

If necessary, a chain transfer agent may be used during the emulsion polymerization reaction. For example, various mercaptans, α-methylstyrene, alkyl halides and the like can be used. The amount of the chain transfer agent is 0 0 1 based on the monomers:. L is about 0 wt%, rather preferably is 0 0 5-3 mass ^_0/0 approximately..

The emulsion polymerization temperature is preferably from 20 to 95 ° C, more preferably from 40 to 90 ° C. The emulsion polymerization time is preferably about 10 minutes to 10 hours.

The glass transition temperature (T g) of the vinyl polymer obtained by emulsion polymerization is 120 to 100. C, more preferably 0 to 100 ° C. The reason is that if the transition temperature Tg is too low, such an aqueous sealer composition has poor adhesion to inorganic materials, and a coating film having low water resistance is formed. On the other hand, if the transition temperature Tg is too high, it is difficult to form a coating from such an aqueous sealer composition.

A general-purpose emulsifier may be added to the sealer composition of the present invention as long as the characteristics are not impaired. In this case, the amount of the general-purpose emulsifier is preferably 50% by mass or less of the macromonomer.

Specific examples of general-purpose emulsifiers include anionic surfactants such as sodium dodecyl sulfate, sodium anoalkyl benzene sulfonate, sodium polyoxyethylene alkyl sulfate, sodium dialkyl quinole sulfosuccinate, and formalin condensate of naphthalene sulfonic acid. Can be used. Nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester and sorbitan fatty acid ester are used, and high molecular emulsifiers such as polyvinyl alcohol and formalin condensate of sodium naphthalene sulfonate are used. Can be used. These general-purpose emulsifiers may be used in combination as an emulsifier for emulsion polymerization at the time of polymerization of a vinyl monomer, or may be added after polymerization of milk.

The sealer composition of the present invention preferably has a vinyl polymer concentration of 5 to 50% by mass in an aqueous medium, more preferably 10 to 30% by mass.

In addition, the sealer composition of the present invention may contain a pigment, a filler, a wetting agent, a dispersing agent, a preservative, an antifungal agent, and a plasticizer, if necessary. The sealer composition is a polyhydrazide compound that can crosslink with carbonyl, epoxy, urethane, and carboxyl groups. It may contain a crosslinking agent such as a substance or a metal. The content of these additives was 50 mass in the sealer composition. It is preferable that / ₀ be the following. To the sealer composition of the present invention, a water-swellable clay mineral may be added to prevent warpage and decay of the base material. Such a sealer composition can be used as a moisture-proof sealer. Water-swellable clay minerals that effectively improve the moisture resistance of the sealer composition include layered silicate minerals belonging to the genus Smectite, such as montmorillonite, beidelite, nontronite, saponite, hectorite, and synthetic fluoromica-based minerals. , Stevensite and bentonite. Further, a swellable fluoromica-based mineral synthesized by the method described in Japanese Patent Application Laid-Open No. 5-270815 is exemplified. The size of the water-swellable clay mineral when dispersed in water is preferably 1 to 20 μm, more preferably 3 to 20 μm. A preferable addition amount of the water-swellable clay mineral is 50% by mass or less in the sealer composition.

The sealer composition of the present invention may contain a low-boiling solvent to promote drying after application and to improve wettability with respect to a substrate or a substrate. Preferred low-boiling solvents are, for example, alcohols such as methanol, ethanol and isopropanol, and ketones such as acetone and methyl ethyl ketone. The amount of the low boiling solvent added is preferably not more than 40% by mass based on the aqueous sealer composition.

Further, the sealer composition may contain a film-forming aid for assisting the formation of a film. As specific examples of the film-forming aid, dialkyl esters of aromatic dibasic acids such as dibutyl phthalate and dioctyl phthalate can be used. In addition, aliphatic dialkyl esters such as dibutyl succinate and dioctyl succinate can be used. Cellosolve compounds such as ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, etc. can be used. A pyrene glycol ether ether compound such as propylene glycol monomethyl ether and propylene glycol monoethyl ether can be used, and a canolebitonele resin such as diethylene glycol monobutyl ether ethyl ether and diethylene glycol monobutyne iron ether can be used. Compounds can be used, and triglycol ether compounds such as triethylene dalicol monomethyl ether and trippyrene glycol monomethyl ether can be used. The amount of the film forming aid used is preferably about 1 to 10% by mass with respect to the bull polymer in the aqueous sealer composition.

The sealer composition of the present invention has excellent permeability to inorganic materials such as slate, calcium silicate plate and cement mortar. Then, the sealer composition forms a film having excellent adhesion to the base after evaporation of volatile components such as water.

The reason why the sealer composition of the present invention exhibits the above-mentioned excellent characteristics is presumed as follows. That is, since the macromonomer has a high emulsifying power and has a copolymerizability with a vinyl monomer, an aqueous dispersion having a hydrophilic component can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples. In Examples, "%" represents% by mass, and "part" represents part by mass.

A. Production of macromonomer and production of neutralized macromonomer

A— 1. Production of Macromonomer MM1 and Mac Mouth Monomer Neutralized Product MM1N A 300 ml pressurized stirred tank reactor equipped with an electric heater is filled with 3-ethoxypropionate. Was. The temperature in the reactor was set at 275 ° C. A monomer mixture was prepared by mixing 65 parts of butyracrylate (hereinafter referred to as BA), 35 parts of acrylic acid (hereinafter referred to as AA), and 0.08 part of di-tert-butyl peroxide. The monomer mixture was stored in a raw material tank. While maintaining the pressure in the reactor at a predetermined value, the monomer mixture was continuously supplied from the raw material tank to the reactor. At this time, the feed rate was set so that the residence time of the monomer mixture in the reactor was 12 minutes. A reaction solution corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet of the reactor. During continuous supply of the monomer mixture, the temperature inside the reactor was set to 288 to 300. C maintained. 90 minutes after the start of the monomer mixture supply, The collection of the reaction solution was started. Use a thin film evaporator to remove unreacted monomers in the reaction solution.

The macromonomer MM 1 was obtained.

The molecular weight in terms of polystyrene of the macromonomer MM1 was measured by gel permeation chromatography using a tetrahydrofuran solvent (hereinafter referred to as GPC). The number average molecular weight (Mn) of the macromonomer MM 1 was 156, and the weight average molecular weight (M w) was 610. ^{By 1} H-NMR, the ratio of double bonds introduced into the terminals of the macromonomer MM1 (terminal double bond introduction ratio) was measured. It was found that double bonds were introduced in 84% of all macromonomer molecules.

By adding the same amount of ammonia and water as the acid number of the macromonomer MM1, the canolepoxinole group of the macromonomer MM1 is neutralized, and the macromonomer neutralized product MM IN (aqueous solution with a solid concentration of 40%) is obtained. Obtained.

A— 2. Manufacture of Mac mouth monomer MM 2 and macro monomer neutralized product MM 2 N

A macromonomer MM2 was produced in the same manner as in A-1, except that a monomer mixture was prepared from 0.08 parts of BA80, 20 parts of AA, and 0.08 parts of tert-butyl peroxide. What is the molecular weight of macromonomer MM2? ^ 11 was 1500, Mw was 3,000, and the terminal double bond introduction rate was 80%.

The carboxyl group of the macromonomer MM2 is neutralized by adding ammonia and water in the same amount as the acid value of the macromonomer MM2, and the macromonomer neutralized product MM2N (aqueous solution having a solid concentration of 40%) is obtained. Obtained.

A— 3. Production of McMouth Monomer MM 3 and Macromonomer Neutralized Product MM 3 N In the production of Macromonomer MM1, 80 parts of cyclohexyl acrylate (hereafter referred to as CHA), 0 parts of AA20, A macromonomer MM3 was produced in the same procedure as in A-1, except that a monomer mixture was prepared from 0.08 parts of butyl peroxide. The molecular weight of the macromolecule MM3 was Mn 144, Mw 390, and the terminal double bond introduction rate was 75%.

By adding ammonia and water in the same amount as the acid value of MM3, the lipoxyl group of the macromonomer MM3 is neutralized, and the macromonomer neutralized product MM is added. 3N (40% solid content aqueous solution) was obtained.

A—4. Production of Macromonomer MM4 and Macromonomer Neutralized Product MM4N 105 parts of butyl acetate was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube. While maintaining the temperature at 90 ° C, 1 part of azobisisobutyronitrile and 2 parts of 3-mercaptopropionic acid were added to the reaction vessel. Under a nitrogen stream, 70 parts of methyl methacrylate and 30 parts of hydroxyshethyl methacrylate were added dropwise to carry out radical polymerization. A solution of a polymer having a carboxyl group at the terminal was obtained. To the polymer solution, 1 part of tetrabutylphosphonium bromide, 0.1 part of hydroquinone monomethyl ether, and 2.7 parts of glycidyl methacrylate were added and reacted at 90 ° C. for 6 hours. As a result, a polymer solution having a double bond introduced into the terminal was obtained. Next, 20 parts of succinic anhydride and 80 parts of butyl acetate were added to the polymer solution, and the mixture was reacted at 90 ° C. for 6 hours to introduce a carboxyl group into the polymer. Thus, a macronomonomer MM4 was obtained. The acid value of the macromonomer M M4 was 1.67 meqZg, the number average molecular weight (Mn) was 3600, the weight average molecular weight (Mw) was 8000, and the terminal double bond introduction rate was 98%. By adding triethylamine and water in amounts equivalent to the acid value of the macromonomer MM4, the carboxyl group of the macromonomer MM4 was neutralized to obtain a macromonomer neutralized product MM4N (aqueous solution having a solid content of 30%). .

B. Production of aqueous sealer composition

Example 1: Production of water'1 raw sealer composition S1

A flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 725 parts of water and 500 parts of MM IN (40% aqueous solution), a Mac-mouth monomer neutralized product. The temperature of the mixed solution was raised to 80 ° C. while stirring under a nitrogen stream. Two parts of ammonium persulfate were added to the flask. After a lapse of 5 minutes, a monomer mixture comprising 75 parts of styrene, 175 parts of methyl methacrylate, 50 parts of 2-hydroxyxyl methacrylate, and 200 parts of isoptyl acrylate was dropped into the flask over 3 hours. After dripping, 9 0. The temperature was raised to C, and 0.5 parts of ammonium persulfate was added. Emulsion was obtained by continuing the polymerization reaction for 1 hour. The ion exchange water was added to the emulsion to adjust the solid concentration in the emulsion to 20%. An aqueous sealer composition S1 was produced by adding 5% of isopropyl alcohol and 5% of diethylene glycol monobutyl ether to the emulsion.

Example 2: Production of aqueous sealer composition S2

An aqueous sealer composition S 2 was produced in the same procedure as in Example 1, except that the macromonomer neutralized product MM 2 N used in Example 1 was replaced by a macromonomer neutralized product MM 2 N.

Example 3: Production of aqueous sealer composition S3

200 parts of water, 125 parts of neutralized macromonomer MM2 (40% aqueous solution) 125 parts of styrene, 75 parts of styrene, 175 parts of methyl methacrylate, 50 parts of 2-hydroxyshethyl methacrylate A mixture of 200 parts of isobutyl acrylate was emulsified with a homomixer to prepare a monomer emulsion. A flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 450 parts of water. The mixture was heated to 80 ° C while stirring the mixture under a nitrogen stream. Two parts of ammonium persulfate were added to the flask.

After 5 minutes, the monomer emulsion was dropped into the flask over 3 hours. After completion of dropping, 90. The temperature was raised to C, and 0.5 parts of ammonium persulfate was added to the flask.

Emulsion was obtained by continuing the polymerization reaction for 1 hour. Ion-exchanged water was added to the emulsion to adjust the solid concentration in the emulsion to ²⁰ %. An aqueous sealer composition S3 was produced by adding 5% of isopropyl alcohol and 5% of diethylene glycol monobutyl ether to the emulsion.

Example 4: Production of aqueous sealer composition S4

An aqueous sealer composition S4 was produced in the same procedure as in Example 3, except that the macromonomer neutralized product MM3N used in Example 3 was replaced by a macromonomer neutralized product MM3N.

Example 5: Production of aqueous sealer composition S5 The neutralized macromonomer MM3ND (30% aqueous solution) was diluted to prepare a diluted macromonomer neutralized product MM3ND (30% aqueous solution). Water consists of 250 parts, diluted macromonomer neutralized product MM 3 ND 17 parts, styrene 300 parts, 2-hydroxyethyl methacrylate 25 parts, 2-ethylhexyl acrylate 175 parts A monomer emulsion was prepared by emulsifying the monomer mixture using a homomixer.

In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 345 parts of water and MM 3 ND 1667 of diluted macromonomer neutralized product were charged. The mixture was heated to 80 ° C. while stirring the mixed solution under a nitrogen stream. Two parts of ammonium persulfate were added to the flask. After 5 minutes, the monomer emulsion was dropped into the flask over 3 hours. After completion of the dropwise addition, the temperature was raised to 90 ° C, and 0.5 parts of ammonium persulfate was added. An emulsion was obtained by continuing the polymerization reaction for one hour. The emulsion was mixed with ion-exchanged water to adjust the solid concentration in the emulsion to 20%. To the emulsion was added 5% of isopropinoleanolonecone and 5% of diethyleneglyconolenobutylether, respectively, to produce a water-I raw sealer composition S5. Example 6: Production of aqueous sealer composition S6

In place of the monomer mixture used in Example 5, 200 parts of styrene, 25 parts of 2-hydroxyethyl methacrylate, 125 parts of 2-ethylhexyl acrylate, 125 parts of diacetone acrylamide 1 A monomer mixture solution consisting of 50 parts was used. The emulsion obtained using the monomer mixture solution was added with adipic dihydrazide corresponding to 0.5 equivalent of a carbonyl group derived from diacetone acrylamide. Other than that, the aqueous sealer composition S6 was manufactured in the same procedure as in Example 5. Example 7: Production of aqueous sealer composition S7

Swellable fluoromica (degree of swelling 29 m 1 Z 2 g, force thione exchange capacity 60 mg Z 100 g) is dispersed in ion-exchanged water so as to have a solid content of 4% by mass and brought to 80 ° C. The mixture was heated and stirred with a homogenizer for 1.5 hours to obtain a mica dispersion. The mica dispersion was added to the sealer composition S4 of Example 4 to obtain an aqueous sealer composition S7. Aqueous sealer set The content ratio of mica to the total solid content of the product S7 was 5% by mass.

Example 8: Production of aqueous sealer composition S8

An aqueous sealer composition S8 was produced in the same procedure as in Example 3, except that the macromonomer neutralized product MM4N used in Example 3 was replaced with a macromonomer neutralized product MM4N.

C. Comparative example

Comparative Example 1: Production of aqueous sealer composition S9

The aqueous sealer composition S9 of Comparative Example 1 was produced in the same procedure as in Example 1 except that 5 parts of sodium dodecyl sulfate was used in place of the macromonomer neutralized product MM 1 N used in Example 1. Manufactured.

Comparative Example 2: Production of aqueous sealer composition S10

Except that 15 parts of Adeliky rear soap SE-1ON (manufactured by Asahi Denka Kogyo KK, a surfactant having an aryl group) was used instead of the macromonomer neutralized product MM 1 N used in Example 1 By the same procedure as in Example 1, the aqueous sealer composition S10 of Comparative Example 2 was produced.

Comparative Example 3: Aqueous sealer composition S11

In Comparative Example 3, a commercially available aqueous sealer composition S11 was used.

D. Evaluation of aqueous sealer composition

The properties of the aqueous sealer compositions of the examples and comparative examples were evaluated as follows. 1. Dry adhesion with sealer coating alone

First, each sealer composition was applied on a calcium silicate plate at a thickness of 100 g / m ² . The sealer film was formed by allowing to stand at room temperature for 24 hours. The adhesion between the sealer coating and the calcium silicate plate was tested as follows.

The sealer film on the calcium silicate plate was cut into a grid at intervals of 4 mm using a force cutter to form 25 cells. Adhesive tape (Nichiban Mouth tape). The adhesive tape was peeled off at a stretch. From the area (number of cells) of the sealer coating piece remaining on the calcium silicate plate without peeling, the adhesion was evaluated according to the following formula. Table 1 shows the results. The closer the value is to 100, the better the adhesion.

Adhesion (%) = Number of remaining cells Z 25 X 100

2. Waterproof adhesion of sealer film alone

Each sealer composition was applied on a calcium silicate plate at a thickness of 100 g / m ² . The sealer coating was formed by allowing to stand at room temperature for 24 hours. The sealer film together with the calcium silicate plate was immersed in warm water at 60 ° C for 24 hours and allowed to stand at room temperature for 24 hours. Thereafter, the adhesion was tested in the same manner as in (1). The results are shown in Table 1.

3. Normal adhesion of sealer coating and topcoat coating

Each sealer composition was coated on a calcium silicate plate having a thickness of 1 00 gZm ^2. The sealer coating was formed by allowing to stand at room temperature for 24 hours. A commercially available water-based overcoat was applied to the sealer coating to a thickness of 75 gZm ² and dried at room temperature for 3 days. After that, the adhesion was tested in the same manner as in (1). Table 1 shows the results.

4. Water adhesion resistance of sealer coating and overcoat coating

Each sealer composition was coated on a calcium silicate plate having a thickness of 100 gZm ^2. The sealer coating was formed by allowing to stand at room temperature for 24 hours. A commercially available water-based overcoat was applied to the sealer coating to a thickness of 75 gZm ² and dried at room temperature for 3 days. Thereafter, the water adhesion resistance was tested in the same manner as in section (2). Table 1 shows the results.

table 1

It was found that the sealer compositions of Examples 1 to 4 formed a coating film having higher adhesion than that of the comparative example.

5. Evaluation of moisture resistance of sealer coating

The sealer composition S7 was applied on the upper surface of the sheet I at a rate of 100 g / m ² . The sealer film was formed by allowing to stand at room temperature for 24 hours. The sealer composition S7 was not applied to the lower surface and side surfaces of the slate plate, but was sealed with a waterproof material. The slate plate was left in a constant temperature and humidity chamber at 40 ° C and 90% RH for 24 hours to test the moisture proof property. The moisture proof was determined from the weight change of the slate before and after the test. The moisture resistance of the sealer composition S7 was 45 gZm ² . A comparative slate plate without the sealer composition S7 was tested. Its moisture resistance was 200 gZm ² . This result indicated that the sealer composition S7 had excellent moisture resistance. Industrial applicability

An aqueous primer is provided that has high adhesion to inorganic materials such as slate, calcium silicate plate, and cement.

Claims

The scope of the claims

1. An aqueous sealer composition comprising an aqueous dispersion containing a vinyl polymer obtained by polymerizing a vinyl monomer in the presence of a macromonomer having a carboxyl group.

2. The constituent monomers of the macromonomer include a monomer having a carboxylic acid group and a hydrophobic monomer, and the monomer having a carboxyl group is included in the constituent monomers in a range of 10 to 7 The aqueous sealer composition according to claim 1, which is contained in a proportion of 5% by mass.

3. The aqueous sealer composition according to claim 1, wherein the macromonomer is obtained by subjecting a raw material mixture containing a monomer having a carboxyl group to radical polymerization at 180 to 350 ° C. object.

4. An aqueous sealer composition applied to an inorganic material, comprising: an aqueous dispersion containing an aqueous solvent and a vinyl polymer dispersed in the aqueous solvent, wherein the aqueous dispersion has a hydroxyl group. An aqueous sealer composition produced by emulsion polymerization of a vinyl monomer in the presence of a McMouth monomer.

5. The aquatic sealer composition according to claim 4, wherein the emulsion polymerization is carried out at 20 to 95 ° C for 10 minutes to 10 minutes.

6. The aqueous sealer composition according to claim 4, wherein the macromonomer is obtained by subjecting a raw material mixture containing a monomer having a carboxyl group to radical polymerization at 180 to 350 ° C. object.

7. The constituent monomer of the macromonomer includes a monomer having a carboxyl group and a water-hydrophobic monomer, and the monomer having a carboxyl group is included in the constituent monomer. The aqueous sealer composition according to claim 4, which is contained in a proportion of 10 to 75% by mass.

8. The hydrophobic monomers include methyl methacrylate, (meth) ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic acid. Stearyl, (meth) acrylonitrile, (meth) isobornyl acrylate, methacrylate having 1 to 22 carbon atoms, acrylate having 2 to 22 carbon atoms, biel propionate, and styrene The sealer composition of claim 7, which is at least one selected.

9. The sealer composition of claim 1, further comprising a water-swellable clay mineral.

10. The sealer composition according to claim 9, wherein the size of the water-swellable clay mineral is 1 to 20 / m.

11. The water-swellable clay mineral is at least one selected from the group consisting of montmorillonite, beidellite, nontronite, savonite, hectorite, synthetic fluoromica-based mineral, stevensite and bentonite. Sheila One composition.

12. A method for producing an aqueous sealer composition applied to an inorganic material,

A step of preparing a macromonomer having a carboxyl group,

Emulsion polymerization of a vinyl monomer in the presence of the macromonomer to obtain an aqueous dispersion, wherein the aqueous dispersion comprises an aqueous solvent and a vinyl polymer dispersed in the aqueous solvent. A manufacturing method including:

13. The method according to claim 12, wherein the emulsion polymerization is performed at 20 to 95 ° C for 10 minutes to 10 hours.

14. The macromonomer preparation step includes a radical polymerization step of a raw material mixture containing a monomer having a carboxyl group, and the radical polymerization step is performed at 180 to 350 ° C. 2. Manufacturing method.

15. The method according to claim 12, further comprising a step of mixing a water-swellable clay mineral with the aqueous dispersion.

16. The method according to claim 15, wherein the size of the water-swellable clay mineral is 1 to 20 tm.

17. The method according to claim 15, wherein the water-swellable clay mineral is at least one selected from the group consisting of montmorillonite, beidellite, nontronite, savonite, hectorite, synthetic fluoromica-based mineral, stippnsite, and bentonite. Method.