TW200531997A - Sealer for organic substrate of ceramic industry series used before curing by autoclave and method for coating the organic substrate of ceramic industry series by using same - Google Patents

Abstract

The present invention provides a sealer for organic substrate of ceramic industry series used before curing by autoclave and a method for coating the organic substrate of ceramic industry series by using same, which the said sealer has excellent properties of blocking resistance, binding and can prevent the efflorescence effectively. In the present of water and emulsifier, the present comprises a core/sheer emulsion containing (i) acrylic copolymer obtained by emulsifying and polymerizing the monomer mixture consisting of the alkyloxysilyl-containing polymeric unsaturated monomer and the other polymeric unsaturated monomer, and (ii) the acrylic copolymer obtained by emulsifying and copolymerizing the monomer mixture consisting of the alkyloxysilyl-containing polymeric unsaturated monomer, optionally the hydroxyl-containing polymeric unsaturated monomer, the cycloalkyl-containing polymeric unsaturated monomer and the other polymeric unsaturated monomer; and the core/sheer emulsion which the glass transition temperature of (i) copolymer and (ii) copolymer set on the specific range as the main component.

Description

200531997 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an autoclave sealant before curing for a kiln industry inorganic substrate and a coating method for the kiln industry inorganic substrate using the same. Good blocking and adhesion, and can fully prevent the occurrence of weathering. [Prior art]

After building materials such as roof paving materials and wall materials of conventional buildings are molded into a plate shape with an inorganic base material consisting of cement as the main component, the sealing material before curing by autoclave is coated by one curing, and after drying, After autoclave curing, cutting processing, and preheating, coating with a second sealant is followed by drying to obtain a sealant coating plate, or after this preheating, a secondary sealant is sequentially performed. Coating, drying, topcoat coating, and drying to obtain a topcoat coating board. This pre-curing sealant is mainly used to improve the properties such as mildew resistance, salt damage resistance, weather resistance, weather resistance, and adhesion of the secondary sealant coating film. It has been conventionally known that an aqueous humic acid solution or a thermoplastic propylene-based resin emulsion has been used as such an autoclave sealant before curing. However, it has the disadvantage that the adhesion between the aqueous humic acid solution and the secondary sealant coating film is poor. In addition, When the thermoplastic acrylic resin emulsion is cured by autoclave (usually, 160 ~ 170 ° C, 8 ~ 9Kgf / cm2, 4 ~ 8 hours, in the presence of water vapor), the substrates adhere to each other and cause blockage. It has the disadvantage of being difficult to handle. ‘Here, the present applicant proposes an aqueous sealant containing a water-soluble resin having good permeability to a substrate and having a crosslinkable functional group (for example, refer to Patent Document 1 and Patent Document 2). According to this water-based sealant, it is possible to form a coating film having excellent water resistance, blocking resistance, and weathering resistance. 200531997 On the other hand, the base material of this inorganic building material is mixed with asbestos, which is cheap and has good fire resistance and reinforcement, into the cement, and it is shaped into a flat plate or corrugated plate. However, this asbestos has been listed as one of the possible carcinogens. In recent years, it has gradually been changed to use asbestos-free building materials. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-204285 [Patent Document 2] WO00 / 07960 [Summary of the Invention] The technical problem to be solved by the invention is not clear. However, for the base material for building materials that does not contain asbestos, The strength thus increases the cement content, but the occurrence of weathering will become more significant compared to the conventional substrate, and for the conventional pre-maintenance sealant as described above, there will be a problem that this weathering cannot be fully prevented. The object of the present invention is to provide a sealant for curing autoclave for kiln industry inorganic substrates and a coating method for kiln industry inorganic substrates using it, which does not damage the weather resistance and can sufficiently prevent the occurrence of weathering. Technical means to solve the problem In order to solve this problem, as a result of drilling collars, the inventors found that a sealant containing a specific core / shell emulsion as the main component is applied as a sealant before autoclave curing and applied once. The curing board has excellent blocking resistance and can fully prevent the occurrence of weathering, and further has good adhesion with the substrate and the top coat layer, and thus completed the present invention. That is, the present invention is related to: 200531997 1. An autoclave sealant for curing kiln industry inorganic substrates, which is a core / shell emulsion, which contains: in the presence of water and emulsifier, it will be from 0.01 to 20% by weight A monomer mixture composed of an alkoxysilyl-containing polymerizable unsaturated monomer and 80 to 99.99% by weight of other polymerizable unsaturated monomers is further added in the presence of an acrylic copolymer (i) through emulsification polymerization. 0.01 to 20% by weight of an alkoxysilyl-containing polymerizable unsaturated monomer, 0 to 10% by weight of a hydroxyl-containing polymerizable unsaturated monomer, and 0 to 70% by weight of a cycloalkyl-containing polymerizable unsaturated monomer Acrylic copolymer (ii) obtained by emulsifying polymerization of a monomer mixture composed of a saturated monomer and 0 to 99.99% by weight of other polymerizable unsaturated monomers, which is characterized by: the glass transition temperature of the copolymer (i) (TgA) is -40 ~ 30 ° C; the glass transition temperature (TgB) of the copolymer (Π) is 35 ~ 100t; and the core / shell emulsion with the TgB at least 20 ° C higher than TgA as the main component . If the autoclave sealant before the application of the patent scope item 1, Among them, the polymerizable unsaturated monomer containing an alkoxysilyl group is vinyltriethoxysilane. 3. —The coating method of the inorganic substrate of the kiln industry is applied to the primary curing plate of the inorganic substrate of the kiln industry, and the autoclave is applied after applying the sealant before the autoclave curing of the patent scope 1 or 2. Curing; and its characteristics are: pre-heating the curing plate before coating the sealer before curing by the autoclave, and / or curing the autoclave after drying after coating the sealant before curing by the autoclave. 4. If the kiln industry is the coating method of inorganic base material according to item 3 of the patent application, after the autoclave curing, the top coat is applied. 200531997 5.-Kind of kiln industry inorganic building materials', which is obtained by applying the coating method of item 3 or 4 of the patent scope. [Embodiments of the invention] The core / shell emulsion used as the main component of the present invention contains: in the presence of water and an emulsifier, an alkoxysilyl-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers In the presence of the acrylic monomer (i) obtained by emulsification polymerization of the formed monomer mixture, a polymerizable unsaturated monomer containing an alkoxysilyl group is further added, and a polymerizable unsaturated monomer containing a hydroxyl group is added if necessary. Acrylic copolymer (ii) obtained by emulsion polymerization of a monomer mixture composed of a cycloalkyl-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers. For example, vinyltrimethoxy Silane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, (meth) propenylmethyloltrimethoxysilane, (meth) propenylhydroxyethyl Trimethoxysilane, (meth) propenylhydroxypropyltrimethoxysilane, (meth) propenylhydroxyethyltriethoxysilane, (meth) propenylhydroxypropyltripropyloxy Silane, etc., as Polymerizable silicon alkyl alkoxy unsaturated monomer. These monomers may be used alone or in combination of two or more. In addition, "(meth) acrylfluorenyl" in this patent specification means "acrylfluorenyl or methacrylfluorenyl." Examples include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, -2,3-dihydroxybutyl (meth) acrylate, and 4-hydroxy (meth) acrylate Monoesters of polyols such as butyl ester, polyethylene glycol mono (meth) acrylate, and acrylic acid or methacrylic acid, and monoesters of the polyol and acrylic acid or methacrylic acid-10-200531997 A compound of ε-caprolactone ring-opening polymerization as a hydroxyl-containing polymerizable unsaturated monomer. These monomers may be used alone or in combination of two or more. Examples include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, ^ butyl cyclohexyl (meth) acrylate, (meth) Hydroxymethylcyclohexyl acrylate, cyclooctyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclododecyl (meth) acrylate, etc., as the cycloalkyl-containing polymerizable unsaturated mono body. These monomers may be used alone or in combination of two or more. φ Examples include methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl (meth) acrylate, isopropyl (meth) acrylate, η-butyl (meth) acrylate , Isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl acrylate, η-octyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid such as norbornyl ester, stearyl (meth) acrylate, or alkyl methacrylic acid; carboxyl group-containing polymerizable properties such as acrylic acid, methacrylic acid, maleic acid, and anhydrous maleic acid Saturated monomer; (meth) acrylic acid-N, N-dimethylaminoethyl ester, (®meth) acrylic acid-N, N-diethylaminoethyl ester, (meth) acrylic acid-N, N-diethyl (Meth) acrylic acid urethanes such as methacrylamide; acrylamide, methacrylamide, N, N-dimethylaminoethyl (meth) acrylamide, Ν, N-di Ethylaminoethyl (meth) acrylamide, Ν, Ν-dimethylaminopropyl (meth) acrylamide, N-hydroxymethylacrylamide, N-hydroxymethyl (Meth) acrylamide or its derivatives such as acrylamide methyl ether, N-methylol acrylamine butyl ether; acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyl toluene,- 11 _ 200531997 α_methylstyrene; 2- (2, -hydroxymethacrylfluorenylhydroxyethylphenyl) -2H-benzotriazole, 4- (meth) acrylfluorenylhydroxypentamethylpiperazine UV-absorbing or UV-stabilizing polymerizable unsaturated monomers, such as pyridine, are used as other polymerizable unsaturated monomers. These monomers may be used alone or in combination of two or more. The core / shell emulsion used in the present invention is 0.001 to 20% by weight of an alkoxysilyl-containing polymerizable unsaturated monomer, preferably 0.1 to 10% by weight; and 80 to 99.99% by weight The other polymerizable unsaturated monomer is preferably a monomer mixture composed of 90 to 99.9% by weight, and an acrylic copolymer obtained by emulsion polymerization (in the presence of 0, further containing 0.01 to 20% by weight of an alkane-containing compound Oxysilyl polymerizable unsaturated monomer, preferably 0.1 to 10% by weight; 0 to 10% by weight of a hydroxyl-containing polymerizable unsaturated monomer, preferably 1 to 5% by weight; 0 to 70% by weight The cycloalkyl-containing polymerizable unsaturated monomer is preferably 5 to 50% by weight and 0 to 99.99% by weight of other polymerizable unsaturated monomers, and preferably 35 to 9 3.9% by weight. The acrylic copolymer (Π) obtained by emulsification polymerization of the mixture. For the propylene copolymer (i) as a core component, the copolymerization amount of the alkoxysilyl-containing polymerizable unsaturated monomer exceeds this range because The obtained coating film has poor water resistance and weathering resistance, and is therefore not suitable. In addition, from the viewpoint of the balance between reactivity and paint storage, the alkoxy group of the alkoxysilyl-containing polymerizable unsaturated monomer is particularly preferably ethoxy group. Especially if vinyl triethoxy group is used Silane, as a polymerizable unsaturated monomer containing an alkoxysilyl group, is more suitable because it has good balance between storage stability and polymerization stability during emulsion synthesis. -12- 200531997 On the other hand, it is suitable for shell components. In the propylene copolymer (ii), if the copolymerization amount of the alkoxysilyl-containing polymerizable unsaturated monomer exceeds this range, the water resistance of the resulting coating film, adhesion with the substrate, and emulsion synthesis will occur. It is not suitable due to poor polymerization stability and the like. In addition, if the copolymerization amount of the polymerizable unsaturated monomer containing a hydroxyl group or the polymerizable unsaturated monomer containing a cycloalkyl group exceeds this range, the resulting coating film may occur. For the core / shell emulsion, the weight ratio of the core to the shell is 10/90 ~ 90/10, preferably 20/80 ~ 80. The range of / 20 is more appropriate. Beyond this range If the core portion is reduced, the film forming property of the coating film is deteriorated, and if the core portion is increased, the weather resistance of the coating film is deteriorated, so it is not suitable for the core / shell emulsion polymerization. Emulsifiers, depending on the required characteristics, include, for example, sodium dialkylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, and polyhydroxyethylene alkylphenyl ether. Anionic emulsifiers such as sodium sulfate and alkyl diphenyl ether disulfate; and nonionic emulsifiers such as poly (ethylene glycol) higher alcohol ethers and poly (ethylene glycol) alkyl phenyl ether. Further, examples include: An anionic or cationic reactive emulsifier having a radical polymerizable double bond. Examples include a radically polymerizable unsaturated group having (meth) allyl, propenyl, butenyl, and polyhydroxyalkane. As the reactive emulsifier, the sodium sulfonate or ammonium sulfonate of the sulfonyl group is listed as "LATEMUL" (trade name, manufactured by Kao Corporation of Japan), "ELEMINOL" (trade name, Japan Sanyo Chemical Co., Ltd.) Company-made), "AQUARON" (brand name, Japanese first industry Pharmaceutical Joint Stock Company, Ltd.). For this core / shell emulsion, the glass transition temperature of propylene copolymer (i) (-13-200531997

TgA) is -40 ~ 30 ° C, preferably -30 ~ 20 ° C, and the glass transition temperature (TgB) of propylene copolymer (ii) is 35 ~ 100 ° C, preferably 40 ~ 80 ° C. TgB must be at least 20 ° C higher than T g A ', preferably at least 30 ° C. If the TgA is lower than -40 ° C, weathering resistance may be inferior. If higher than 30 ° C, film forming properties or low-temperature physical properties (freeze dissolution test) will be reduced, which is not suitable. In addition, if the TgB is lower than 35 ° C, weathering resistance may be inferior. If the TgB is higher than 100 ° C, the film forming property and low-temperature physical properties (freezing and melting test) may be degraded, which is not suitable. In addition, if the TgB is not lower than TgA by at least 20 ° C or higher, weathering resistance and film-forming properties or low-temperature physical properties cannot be obtained at the same time, which is not suitable. In this patent specification, the glass transition temperature (° C) of the copolymer can be calculated by the following formula. 1 / Tg (° K) = (Wl / Tl) + (W2 / T2) + · ·

Tg (° C) = Tg (0K) -273 In the formulas, W1, W2, ·· represent the respective weight% of the monomers used in the copolymer, and T1, T2 ··· represent the average of each fluorene monomer Tg (.K) of the polymer. In addition, ΤΙ, T2, ·· are based on the numbers of Polymer Hand Book (Second Edition, edited by J. Brandup · E · H. Immergut). The glass transition temperature (° C) where the Tg of the monomer homopolymer is unknown is set to the static glass transition temperature. For example, a differential scanning calorimeter "DSC-50Q" (manufactured by Shimadzu Corporation) , Trade name), put the sample in the measuring cup, and then completely remove the solvent by evacuating, then measure the heat change in the range of -100 ~ + 100 ° c at a temperature rising rate of 3 ° C / min, and lower the temperature The change point of the initial baseline on the side is the static glass transition temperature. • 14- 200531997 The sealant before autoclave curing for the inorganic substrate of the kiln industry of the present invention is mainly composed of the core / shell emulsion, and may also contain a thickener, a surface conditioner, a film-forming aid, and coloring if necessary. Pigments, extenders, fillers, hardening catalysts, defoamers, organic solvents, etc. The solid content of the sealant of the present invention is generally 1 to 40% by weight, preferably 3 to 30% by weight. If the solid content is less than 1% by weight, in order to ensure the coating film thickness, the number of paintings will increase, and the coating workability will be deteriorated. On the other hand, if it exceeds 40% by weight, the permeability to the substrate will be poor, and the wind resistance will be poor. Chemical properties also become poor. The coating method of the present invention is a primary curing board of an inorganic substrate of a kiln industry. After applying the pre-autoclave sealant of the present invention obtained in the above manner, the autoclave is cured, and then a top coat is applied. Painting. For example, it includes inorganic porous substrates based on inorganic materials such as cement, calcium silicate, and gypsum (for example, calcium silicate board, asbestos cement board, wood chip cement board, pulp cement board, and lightweight Use of construction materials, structural materials, civil materials, or industrial materials such as foam concrete slabs as the inorganic substrate. Especially suitable for asbestos-free building materials (asbestos does not contain building materials). The coating method of the autoclave curing agent is not particularly limited, and conventional coating methods can be used, such as rollers, bristles, spraying, dipping, spray applicators, and blade coating machines (leaf curtain coating). Installation, etc.). The coating amount (in terms of solid content) of the sealant is i ^ OOOg / m2, preferably in the range of 5 to 500g / m2. If the coating amount is not Si g / m2, weathering resistance will decrease, while if it exceeds 1000 g / m2, blocking resistance and the like will decrease, which is not suitable. '15 · 200531997 The present invention is based on the viewpoint of blocking resistance, and it is necessary to preheat the primary curing plate (front-stage heating) before applying the autoclave curing sealant, and / or seal before applying the autoclave curing. After the agent is dried (post-stage heating), the autoclave is cured. Either the first-stage heating or the second-stage heating can be performed, and preferably both methods are used. The sealant is heated at the front stage and the rear stage. For example, it is best to heat the substrate by a single curing, etc., and use the residual heat (about 60 ° C) of the substrate produced by the primary curing to dry. In addition, although the substrate does not generate residual heat, although it varies depending on the type of the substrate, it is usually dried in a range of about 20 to 200 ° C and about 3 seconds to 60 minutes. For this drying, especially using the residual heat of the substrate, since the substrate is coated with a sealant in a slightly hot state, the permeability to the substrate is excellent because the cross-linking will proceed to the inside of the substrate. Extended, so it has the advantages of excellent water resistance, weather resistance, blocking resistance and other properties. The autoclave curing is not particularly limited, and it can be carried out using the kiln-based substrates under the conditions already adopted. Usually about 160 ~ 17 (TC, 8 ~ 9 kg / cm2, 4 ~ 8 hours, in the presence of water vapor. For the top coat, the conventional top coat can be used, and there is no particular limitation. Top coat Coatings, for example, acrylic resin, urethane resin, vinyl chloride resin, fiber resin, silicon resin, polyester resin, alkyd resin, fluororesin resin, and two or more of them can be used. Quality resin, blended resin, etc. In addition, the topcoat paint can use either natural paint type or crosslinked type. When this resin paint is pigmented, topcoat is applied, and In the case of applying a transparent coating with no pigment added to it-16-200531997, the sealant of the present invention can be used as a primer in any case. In addition, the topcoat coating can be water-based, organic solvent-based, or solvent-free. Either type of coating. [Examples] Hereinafter, examples are given to explain the present invention in detail. In addition, "parts" and "%" represent "parts. Weight" and "% by weight" respectively. Polymer emulsion (A) Zhihao Production Example 1

A 2-liter reaction vessel with a thermometer, thermostat, stirrer, circulation cooler, and titration device has been installed, and 50 parts of deionized water and 0.05 parts of "AQUARON HS-1 025" (trade name, Japan Reactive emulsifier made by Daiichi Kogyo Pharmaceutical Co., Ltd.), and the temperature was raised to 85 ° C. In another container, add 38 parts of deionized water, 3 parts of "AQUARON HS-1025" and 0.15 parts of ammonium peroxysulfate as a polymerization initiator, and after stirring well, add the monomer mixture into it and stir Thus, a monomer emulsion (1) was obtained. 10 parts of cyclohexyl methacrylate

18 parts of styrene, 18 parts of isobutyl methacrylate, 20 parts of 2-ethylhexyl acrylate, 20.6 parts of vinyltriethoxysilane, 0.7 parts of methacrylic acid, and 0.7 parts of this emulsified product ( 1) Drop into the reaction container. Next, in another container, add 16 parts of deionized water, 1.5 parts of "AQUARON HS-1 025", and 0.05 parts of ammonium peroxodisulfate. After stirring well, add the monomer mixture -17-200531997 to it, and stir Thus, a monomer emulsion (2) was obtained. 8.4 parts cyclohexyl methacrylate styrene 16 parts isobutyl methacrylate 2 parts 2-ethylhexyl acrylate 2 parts vinyltriethoxysilane 0.3 parts hydroxyethyl methacrylate 1 part After the titration of 0.3 parts of acrylic monomer (1) based on acrylic acid was finished, the monomer emulsion (2) was dropped into the bottle for 1 hour, and then the reaction was completed at 85 ° C for 2 hours and cooled to 40 ° C to obtain a milky copolymer emulsion (A-1). The solid content of the obtained copolymer emulsion (A-1) was 47.7%, and the average particle diameter of the core / shell emulsion particles was 130 nm. Production Examples 2 to 6 Production Example 1 was performed in the same manner as in Example 1 except that the monomer compositions for monomer emulsion (1) and monomer emulsion (2) shown in Table 1 below were used. Copolymer emulsions (A-2) to (A-6) were obtained. In Production Example 3, instead of the emulsifier "AQUARON HS-1 025" (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., reactive emulsifier), an equivalent amount of "UNICOL 707SF" (trade name , Non-reactive emulsifier made by Japan Emulsifier Co., Ltd.). -18- 200531997 [Table 1] Manufacturing example 1 2 3 4 5 6 Copolymer emulsion name A-1 A-2 A-3 A-4 A-5 A-6 Emulsion (1) Monomer composition methacrylic acid ring Hexyl 10 10 10 10 40 Styrene 18 25 18 18 18 21 Butyl acrylate 20 23 20 20 20.7 5.6 2-Ethylhexyl acrylate 20.6 20.6 20.6 20.6 20.6 2 Vinyltriethoxysilane 0.7 0.7 0.7 0.7 0.7 Methacrylic acid 0.7 0.7 0.7 0.7 0.7 0.7 Emulsion (2) Monomer composition cyclohexyl methacrylate 8.4 8.4 9.4 8.4 8 Styrene 16 22.4 16 16 16 3 Butyl acrylate 2 4 2 2 2.3 10 Acrylic-2 -Ethylhexyl ester 2 2 2 2 2 7.4 Vinyltriethoxysilane 0.3 0.3 0.3 0.3 0.3 Hydroxyethyl methacrylate 1 1 1 '1 1 0.3 0.3 0.3 0.3 0.3 0.3 Tg (° C) Core Part 1.4 0 1.4 1.4 1.2 60.7 Shell part 62.1 60.8 62.1 62.5 61.9 0 Manufacturing Example 7 A 2 liter reaction vessel equipped with a thermometer, thermostat, stirrer, circulation cooler, and titration device was charged with 50 parts of deionized water. .05 parts AQUARON HS-105 (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., reactive emulsifier) 'Warmed to 85 ° C. In another container, add 54 parts of deionized water, 200531997, 4.5 parts of AQU ARON HS-l 025, 0.2 parts of ammonium persulfate as a polymerization initiator, and after stirring well, add the monomer mixture into it. Stir to obtain a monomer emulsion (1). Cyclohexyl methacrylate 18.4 parts Styrene 3 4 parts Isobutyl methacrylate 22 parts 2-Ethylhexyl acrylate 22.6 parts Ethyldiethoxy sand house 1 part

1 part of methyl methacrylate 1 part of methacrylic acid After 3 hours, this emulsion (1) was dropped into a reaction container. After the titration of the monomer emulsion (1) was completed, the reaction was completed for another hour, and a milk-white copolymer emulsion (A-7) was obtained. The solid content of the obtained copolymer emulsion (A-7) was 47.9%, and the average particle diameter of the emulsion particles was 130 nm. Production (for comparison) of hardening resin aqueous solution Production Example 8

A 3,000 cc four-necked flask equipped with a thermometer, a stirrer, and a titration funnel was charged with 100 parts of propylene glycol monomethyl ether, and the temperature was raised to 80 to 90 ° C. Therein, after 3 hours, 30 parts of methyl methacrylate, 30 parts of butyl acrylate, 13 parts of styrene, 10 parts of N-η-butoxymethacrylamide, and 10 parts of 2-hydroxyethyl acrylate A mixed solution of an ester, 7 parts of acrylic acid, and 1 part of azobisisobutyronitrile was dropped into the reaction vessel. Then, at the same temperature, the reaction was completed after 1 hour, and then 1 part of azobisbutyronitrile was added as an additional catalyst, and the reaction was completed after 2 hours. The solid content was 50% and the resin acid value was obtained. It is a copolymer solution of 56 mg KOH / g -20-200531997 and the number average molecular weight of the resin is about 6,000. Next, 0.9 equivalents of triethylamine neutralizing agent was added to the obtained solution, and after stirring and mixing, deionized water was slowly dropped until the solid content was about 20%, and the resin aqueous solution was prepared by mixing and stirring. (A-8). The pigment paste was prepared by mixing 2 parts of "BYK-190" (Big Chemi Corporation, trade name, resin for dispersion), 50 parts of titanium white and 50 parts of talc, and using a paint shaker to disperse the mixed solution to make Pigment paste with 67% solids. Production of water-based sealant · Examples 1 to 5 and Comparative Examples 1 to 3 The copolymer emulsion obtained in Examples 1 to 7 was mixed with the combination shown in the following table 2 and then stirred and added 0.1 parts Ammonia was used to adjust the pH to about 8-9, and an appropriate amount of deionized water was added to obtain each aqueous sealant with a solid content of 30%. In addition, the composition of Table 2 shows a solid content. In addition, the water-based sealant of Comparative Example 4 was used as it was for the resin (A-8) obtained in Production Example 8. -21-200531997 [Table 2] Examples Comparative Examples 1 2 3 4 5 1 2 3 A-1 100 100 A-2 100 A-3 100 Copolymer emulsion A-4 100 A-5 100 A-6 100 A- 7 100 Pigment paste 100 2,2,4-trimethyl-I, 3-pentanediol monobutyrate 5 5. 5 5 5 5 5 5 Coating Examples 6 to 9 and Comparative Examples 5 to 8, The primary curing board not containing asbestos was heated at 100 ° C. for 5 minutes in advance (pre-stage heating), and then using the combination of Table 3, each of Examples 1 to 4 and Comparative Examples 1 to 4 prepared in this way was used. The water-based sealant was spray-coated on the surface, and the coating amount was 50 g / m2 (solid content). This was further dried at 100 ° C. for 5 minutes (post-stage heating) to obtain each coated plate. Next, the autoclave was cured at 170 ° C for 4 hours to obtain an autoclave curing plate. The following performance tests were performed on these coated boards. The results are shown in Table-22- 200531997. Example 1 〇 In Example 6, except that the first-stage heating is not performed, the same method as in Example 6 is performed to obtain the coated plate and autoclave before autoclave curing. Device maintenance board. The following performance tests were performed on the board. The results are shown in Table 3. Example 11 1 In Example 6, the same manner as in Example 6 was performed except that the rear stage heating was not performed to obtain a coating plate and an autoclave curing plate before the autoclave curing. The following performance tests were performed on the board. The results are shown in Table 3. Comparative Example 9 # In Example 6, the same manner as in Example 6 was performed except that the front-stage heating and the rear-stage heating were not performed, to obtain a coated plate and an autoclave curing plate before the autoclave curing. The following performance tests were performed on the board. The results are shown in Table 3.

[Table 3] Examples, Comparative Examples 5 6 7 8 9 10 11 5 6 7 8 9 Types of water-based sealants Implementation Implementation Implementation Implementation Implementation Comparison Comparison Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Example 1 Case 1 Case 2 Case 3 / Κ | ί Λ / K || i Weathering resistance 〇〇〇〇〇〇〇〇〇 △ 17 | J 〇I7U ^ X ΙΙΙ 1 〇 Performance blocking resistance 〇XX π ν Test substrate adhesion ◎ ◎ 〇 ◎ 〇〇〇Δ-△ Δ 〇Λ 〇 Topcoat adhesion ◎ ◎ 〇 ◎ 0 '〇〇Λ Λ Λ X 〇-23- 200531997 Method (* 1) Weathering resistance: observe the coating film of each autoclave curing plate. 〇Whether there is no whitening △ Which has been whitened and deteriorated XWhether significant whitening (* 2) Blocking resistance: each two pieces of autoclave shall be coated with each other before the curing of the coating boards, and the load shall be 400g / cm2 Press and heat it at 170 ° C for one hour and then cool to room temperature. Investigate the ease of peeling between two curing boards. Lu 〇 system does not adhere at all, good △ system slightly adheres, but can be peeled with a slight force X system cannot peel without strong force (* 3) substrate adhesion: set each autoclave The curing board was frozen in air at -20 ° C for 2 hours, and then fused in water at -2 ° C for 2 hours as a cycle. The cycle test of this board was performed 300 times. Thereafter, each test plate was cut with a cutter to a 4mm-spaced, 5x5 grid-like checkerboard-like cutting line, and a peeling test was performed after applying tape. · 〇 series without peeling, △ series peeling is less than two, X series peeling is more than three (* 4) Topcoat adhesion: on the curing plate of each autoclave, The base water-based topcoat "IM COAT 5111" (manufactured by Kansai Paint Co., Ltd., Japan) was coated to a film thickness of 50 // m, and dried at 100 ° C for 10 minutes. Set each autoclave curing plate in the air and freeze it at -20 ° C for 2 hours at Xiaoriji Temple-24-200531997, and then melt it in water at -20 ° C for 2 hours as a cycle. The board was tested for 300 cycles. Thereafter, each test plate was cut with a cutter to a 4 mm-space, 5x5 grid-like checkerboard-like cutting line, and a peeling test was performed after applying an adhesive tape. 〇 Series without peeling, △ Series peeling, two or less, X Series peeling, three or more [Effects of the invention] According to the present invention, by using a specific core / shell emulsion as the main component, The sealant is used as a sealer before the curing of the autoclave. In particular, even an asbestos-free primary curing board can be coated with it to obtain an inorganic building material, which has good blocking resistance and can fully prevent weathering. Furthermore, the adhesion to the substrate and the top coat layer is extremely high. [Simple illustration of the icon]: None.

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Claims (1)

200531997 Scope of patent application: 1. A kind of sealer before autoclave curing for inorganic substrates of kiln industry, a core / shell emulsion, which contains: in the presence of water and emulsifier, it will contain 0.01 to 20% by weight of A monomer mixture composed of a polymerizable unsaturated monomer of oxysilane and 80-99.99% by weight of other polymerizable unsaturated monomers is further added in the presence of an acrylic copolymer (i) obtained by emulsion polymerization. 0.01 to 20% by weight of an alkoxysilyl-containing polymerizable unsaturated monomer, 0 to 10% by weight of a hydroxyl-containing polymerizable unsaturated monomer, and 0 to 70% by weight of a cycloalkyl-containing polymerizable unsaturated monomer Acrylic copolymer (ii) obtained by emulsion polymerization of a monomer mixture composed of a saturated monomer and 0 to 99.99% by weight of other polymerizable unsaturated monomers; wherein: the glass transition temperature of the copolymer (i) (TgA ) Is -40 ~ 3 (TC; the glass transition temperature (TgB) of the copolymer (ii) is 35 ~ 100 ° C; and the TgB is at least 2 higher than the TgA (the core / shell emulsion above TC is mainly composed of 2 such as Sealant before autoclave curing for patent application item 1, The alkoxysilyl-containing polymerizable unsaturated monomer is vinyl triethoxy sand 3. A coating method for a kiln industry-based inorganic substrate, which is coated on a primary curing board of a kiln industry-based inorganic substrate. After applying the autoclave curing pre-sealing agent for the scope of patent application item 1 or 2, the autoclave curing is performed, in which the pre-heating of the curing board is preheated before the autoclave curing pre-sealing agent is applied, and / or After coating the sealant before autoclave curing, autoclave curing is performed after drying. -26- 200531997 4. If the kiln industry is applied for inorganic substrate coating method in the scope of patent application No. 3, after the autoclave curing, 5. Topcoat coating. 5.—Inorganic building materials of the kiln industry are obtained by applying the coating method in item 3 or 4 of the patent scope. 〇-27- 200531997 指定 Designated representative map: (I) The case The designated representative picture is: None. (2) Brief description of the element representative symbols of this representative picture: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: