TW200932849A - Emulsion composition, composition for waterproof coating material using same, waterproof coating material, and method of forming waterproof coating material - Google Patents

Abstract

To provide an emulsion composition which has excellent miscibility with cement and develops a particular coloration when favorable miscibility is attained, and which in its hardened form following curing of the cement suppresses cracking and exhibits excellent tensile strength and elongation, and also to provide a composition for a waterproof coating material, a waterproof coating material and a method of forming a waterproof coating material that use such an emulsion composition. An emulsion composition in which the dispersed material is a synthetic resin (X), wherein the average particle size of the synthetic resin (X) is within a range from 100 to 500 nm, and the variation coefficient (α) of the particle size is 40% or less.

Description

200932849 VI. Description of the invention: - [Technical field to which the invention belongs] [0001], shouting _ mixing with cement to make a composition and using the emulsion, 'Do not apply coating film waterproof material', especially polymerized cement coating film Waterproofing material, in particular, is about the roof of a building such as a roof of a platform, a balcony of a building, a wall, a terrace, a bathroom, an exterior, etc., and an emulsion group used for waterproof coating technology to coat the emulsion. A method for forming a gambling water material, a coated film waterproof material, and a coated film waterproof material. ® [Prior Art] [0002] Conventionally, a synthetic high-concentration agent such as an acrylic emulsion or a vinyl acetate emulsion has been mixed with cement or the like, and is known as a waterproof material. However, the milk, the composition, due to insufficient dispersibility to the cement, may cause hardening of the cement after hardening due to internal factors such as shrinkage with hardening, or temperature changes, external factors such as east knot melting and substrate movement. The problem is prone to cracks. , raw, for the damage as the main reason for the performance of waterproofing materials, so Yin Qixi, hope f traces [0003] 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥 水泥- Vinyl acetate vinegar copolymer as a dispersing polyvinyl alcohol aqueous aqueous emulsion (refer to Patent Document η. [0004] In addition, in order to improve the elongation of the coating film which is qualified for cement hardening at low temperatures, and to improve the surface viscosity It is proposed that aluminum cement is added to an emulsion of a copolymer of ethylene and a vinyl acetate copolymer having a Tg of -5 to Μ °c (see Patent Document 2). Emulsification [Patent Document 1] Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Although the elongation is excellent, the literature has a low film and a low viscosity on the surface of the coating film. Moreover, the above-mentioned special considerations for the water cause the need to make the emulsion match and judge the mixture, etc., which is very large. 'Must be confirmed after construction 【0007】 The secret Γ Γ 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 , , , , , , , , , , , , , , , , , , , , 0007 0007 0007 0007 0007 0007 0007 0007 Color, hardened material's occurrence of cracks, tensile strength and length ratio ❹ 敝 敝 之 之 赌 赌 赌 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 。 。 。 。 。 。 。 。 ( ( ( ( ( ( ( In the case of the above-mentioned circumstances, the inventors of the present invention have found that the synthetic resin which is a quality is required to have a larger particle diameter, and the water is hardened in the hardened cement. 'The emulsion composition which is suppressed in crack occurrence and excellent in elongation and elongation' is completed in the present invention. Moreover, even if it is not, the first one of the present invention is not carried out [0009]. S is: - an emulsion composition, the dispersion is 200932849 ::: == 3⁄4 the average particle size is in the range of 100~500nm and its [0010] and: the formed film waterproofing material formed and 4$ The above emulsion group; and the formed material forms a coating film waterproof material . · Said method ', to find the coating film 5 made of ❹ sub $ 2: A means of Regulation 2: Since the synthetic resin emulsion composition of the particles

The 2 son caused the light to be interfered, and the coloration was observed. On the date of this issue, U is mixed with cement, so that the cement itself is lost to the shape of (four) color and 'this color' with the hardening of the cement (the effect of the invention) [0012] ο πτ, the present invention is a supplementary composition, the dispersion * is a synthetic resin and a mouth. The average particle diameter of the 曰 (χ) is in the range of 100 to 500 nm and the particle diameter variation is 40% or less. 'It has excellent blending property with cement, and has a certain color developability when mixing is good at the time of mixing. Therefore, it is easier to judge the mixing property based on color development when it is applied on site. Efficiently obtain an emulsion, and a uniformly solidified cement hardened material (for example, a coated film waterproof material). In this manner, if the emulsion composition is uniformly dispersed, the obtained cement cured product is inhibited from cracking, and tensile strength and elongation are changed. [0013] In addition, when the concentration of the non-volatile component of the emulsion composition is 45 wt% or more, the color developability is better when mixed with cement. [0014] X) glass transition temperature 'if Below 03⁄4, a cement hardened material of sufficient strength can be obtained even when it is applied at a low temperature. 200932849 [0015] The synthetic resin (X) is homopolymerized from an ethylenically unsaturated ethylenically unsaturated monomer (a) The present invention is not limited to the embodiment of the present invention. EMBODIMENT OF THE INVENTION The emulsion composition of the present invention is an emulsion composition of a synthetic resin (X) having a specific particle diameter. First, the synthetic resin (X) will be described. <<Synthesis Resin (X)>> The synthetic resin (X) of the present invention is required to be a synthetic resin having an average particle diameter of 100 to 500 nm and a particle diameter variation coefficient (α) of 40% or less. By setting the synthetic resin (X) to a specific particle diameter, it has good mixing property with cement, and can be sufficiently colored when mixed with cement. The average particle diameter and coefficient of variation (α) are described later. The emulsion composition is detailed in the project. 19] Like such a synthetic resin (X), for example, a homopolymer or a copolymer of an ethylenically unsaturated monomer (Μ) is preferred, and a fluorinated ethylenically unsaturated monomer (a) Among the homopolymer or copolymer, and the ethylenically unsaturated monomer (M), an acrylic copolymer containing, in particular, an alkyl (meth)acrylate as a main component and copolymerized with other ethylenically unsaturated monomers is also preferred. Hereinafter, the ethylenically unsaturated monomer (M) which forms the polymerization component of the synthetic resin (x) will be described in detail. [Polymerized component of synthetic resin (X)> The ethylene property of the above synthetic resin (X) is not formed. Saturated monomer (M), for example, ethylenically unsaturated monomer (a) with a mercapto group or alkyl (meth)acrylate, aromatic ethylenic acid non-200932849, and monomer, hydroxyl-containing ethylenically unsaturated single Ether, carboxyl group-containing ethylenically unsaturated, body, epoxy group-containing ethylenically unsaturated monomer, hydroxyindole-containing ethylenically unsaturated compound, alkoxyalkyl group-containing ethylenically unsaturated monomer, a cyano group-containing ethylenically unsaturated monomer, an ethylenically unsaturated monomer having two or more radically polymerizable double bonds, and an amine group An ethylenically unsaturated monomer, an ethylenically unsaturated monomer having a sulfonic acid group, an ethylenically unsaturated monomer having a phosphoric acid group, or the like, which may be used alone or in combination 2 [0021] wherein a mercaptoamine group is used. Preferably, the ethylenically unsaturated monomer (a) is further used, and the above-mentioned ethylenically unsaturated ethylenically unsaturated monomer (a) and the monomeric ethylenically unsaturated monomer (b) are preferably used together. . B β [0022] The above-mentioned ethylenically unsaturated monomer (8) having a mercapto group, such as (meth) propyl sulfonamide, sub: (meth) acrylamide, fluorenyl methoxymethyl (a) Ethyl propylene 醯 曱 曱 曱 ( 甲基 甲基 甲基 Ν 曱 曱 曱 曱 曱 曱 曱 曱 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 (salt) = ethyl citrate (salt), (methyl) propyl sulfonamide (salt), (methyl) propylamine 1 = salt), (meth) acrylamide butyl sulfonate (salt) , (mercapto) acrylamide methyl propyl; ❹: propyl amide, dimethyl red mineral acid (salt), (mercapto), methalic acid, U), (meth) acrylamide Butanesulfonic acid (salt), (decyl) acrylamide, ruthenium diacid (,), (meth) acesulfame amine ethyl propionic acid (salt), (methyl) acrylamide ethyl ethyl b Sulfonic acid (salt) and (meth) propyl glycine propyl sulfonate (salt), etc., having a carbon number of 〜5 二8 ς, a linear olefin group compound, and the like. These can be used alone to make more than two types of thieves: 兮 (methyl) propyl sulphate or (meth) propylene amide propyl propyl acrylate (sleep ') methine) acrylamide olefin qing). Further, the above-mentioned acid (salt) [0023] to (I2H, the above-mentioned monomer (a) copolymerized ethylene hetero and monomer (b), for example, the following (1) (1) (meth) acrylate acid ester. (2) Fangxiangzu ethylenically unsaturated monomer. 200932849 (3) Hydroxyl-containing ethylenically unsaturated monomer. (4) Carboxyl group-containing ethylenically unsaturated monomer. (5) Epoxy group-containing Ethylene unsaturated monomer (6) Hydroxyl group-containing ethylenically unsaturated monomer (7) Alkoxyalkyl group-containing ethylenically unsaturated monomer (8) Cyano group-containing ethylenically unsaturated monomer. (9) Ethylene-unsaturated monomer having two or more radically polymerizable double bonds (1) an ethylenically unsaturated monomer having an amine group (11) Ethylene-unsaturated monomer having a sulfonic acid group (12) Ethylene-unsaturated monomer having a phosphoric acid group. [0024] These monomers may be used singly or in combination of two or more. Further, in addition to the above (1) to (12), acetic acid vinegar and propylene Ethyl acetate vinegar, versatic ethylene vinegar, ethylene pyrrolidone, methyl vinyl ketone, butadiene, ethylene, propylene, vinyl chloride, ethylene oxide, etc., may also be used as appropriate. 0025] (Methyl)-glycolic acid calcination (1), for example, methyl (methyl)-propyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (曱) Base butyl acrylate, (butyl) methacrylate, hexanoic acid (meth) acrylate, (meth) propylene G acid & hexyl ester, 2-ethylhexyl (meth) acrylate An aliphatic (meth) acrylate such as (meth)acrylic lauric vinegar, preferably an aliphatic (meth) acrylate having a carbon number of 1 to 2 Å or a benzyl (meth) acrylate An aromatic (meth) acrylate such as phenyl (meth) acrylate, etc., which may be used singly or in combination of two or more. Among them, butyl (meth)acrylate and (b-)acrylic acid 2-B are preferred. An aliphatic (meth) acrylate having a carbon number of 1 to 1 Å of an alkyl group such as methyl hexyl ester, methyl (meth) acrylate or (cyclohexyl formate). The above aromatic ethylenically unsaturated monomer (2) For example, styrene, vinyl benzene, a methyl phenyl bromide, etc., these may be used alone or in combination of two or more. Among them, ethylene is preferred. [0027] 200932849 B/diethylene is not sufficient Monomer (3), for example: (meth) propylene _ diy (two or more kinds are used together. Among them, preferred f == [0028] ❹ 豆 Ϊ ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί (Methyl)acrylic acid, bar 3, benic acid, etc. 'These can be used alone or in combination with two kinds of hydrazines, and can be used with such single vinegar or = horse water Ϊ ί ̄ ̄ ̄ ̄ ̄ ̄ ̄ For example, (meth)acrylic acid condensate, ('acrylic acid thioglycolic acid vinegar, etc., Gan H phase or two or more sides. The towel is (meth) acrylic acid shrinkage [0030] ❹ The ethylenically unsaturated monomer (6), for example, Ν-(tetra)-based (曱^2). , "Zhao methyl (methyl) (four) _, etc., these may be used alone or in combination [0031] Amethyst ethylenically unsaturated monomer (7), for example, N-decyloxy, N_ alkoxymethyl (曱Base) propylene-amine, oxime-oxyethyl hydrazine - field = base (f-acrylic acid vinegar, etc. (meth) acrylic acid oxyalkyl vinegar, polyethylene glycol acrylate The oxy (▼-based) ruthenium ruthenium 0 or the like can be used singly or in combination of two or more kinds. [0032] [ ο ο 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 S] 200932849 The above ethylenically unsaturated monomer (9) having two or more radical polymerizable double bonds, for example, an ethyl phenyl benzene, a polyoxyethylene di (meth) acrylate, or a polyoxypropylene ( Di-(methyl)propionate such as decyl acrylate, neopentyl glycol di(meth) acrylate, butane diol di(meth) acrylate, trimethyl methacrylate trimethyl a tetra(meth)acrylate such as a tris(meth)acrylate such as acrylic acid ester or a tetrakis(meth)acrylate such as pentaerythritol tetra(meth)acrylate, which may be used singly or in combination of two or more.

The above-mentioned amino group-containing ethylenically unsaturated monomer (1〇), for example, N,N-dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl ( A' propylene/amp; ester, etc., these may be used individually or in combination of 2 or more types. The above-mentioned sulfonic acid group-containing ethylenically unsaturated monomer (11), for example, vinyl sulfonic acid, vinyl ethyl methacrylate (salt), etc., may be used alone or in combination of two or more. [0036] The above-mentioned ethylenically unsaturated monomer (12) having a phosphoric acid group, for example, vinylphosphonic acid, ethyl acetate, acid oxyethyl (T-based) acrylate, acid oxychloride Sodium (meth)propionic acid S 曰, bis[(methyl) propylene oxyethyl] vinegar, diphenyl-2-(methyl) propylene oxirane ethyl ester, dibutyl 2-(meth)acryloyloxyethyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, etc., these may be used alone or in combination of two or more. [0037] Further, in the present invention, (meth) propylene oxime, means propylene oxy propylene methoxy '(meth)acrylic acid, meaning acrylic acid or methacrylic acid, (methyl acid, And means acrylic acid or methacrylic acid, (meth)acrylic acid, meaning acrylic acid vinegar or methacrylic acid vinegar. [0038] As described above, in the synthetic resin (X) of the present invention, In the constitution of each of the polymerization components, it is preferred to use an ethylenically unsaturated ethylenically unsaturated monomer. The use of the above-mentioned ethylenically unsaturated ethylenically unsaturated monomer can improve the unmannedness and film formation. Since the modulus of elasticity is greatly changed to 4, the strength of the coating film tends to increase in addition to the crack of the hardened layer of 200932849. [0039] Further, it is preferable to use the above-mentioned amidino group. Ethylene lion monomer (sum of the combination (b). [0040] Like the combination of the monomer (8) and the monomer (9), f is in the group, and the ethyl group is unsaturated with an amino group. Ethylene unsaturated monomer (fish too little, f = P, tendency, if too much, the composition of the emulsion = see 2 points) The tendency to occur under the problem. *L, it will be seen that the workability is low [0041] In the synthetic resin (X), when the monomer (b) is used, it is preferable to use the secret (4)) C (10) (1) As the main component (), the unsaturated copolymer is copolymerized with an acrylic copolymer. It is /, /, and it is ethylenic [0042] The main component of the present invention means that the content is super = 5 of the butterfly. It is a material containing "=6〇乙重稀=time, its poly rt surfactant, plasticizer film starter, poly <polymerization initiator> above polymerization initiator, water-soluble, oil-soluble alkyl , tert-butyl hydroperoxide, fine m to oxidize peroxylated tert-butyl cumyl, peroxy; c, octyl decyl, benzyl, dicumyl peroxide, peroxidation - A Stuffed base, benzophenone peroxide, second butyl, 1,1 double (third butyl 200932849 trimethylcyclohexanone peroxidation) -3,3,5-trimethylcyclohexanide , organic peroxides such as peroxidized 3 3 5 — —ylcyclohexane=, di-isobutylperoxydicarbonate, ethylhexanoic acid, m-peroxy-p-butylene, gas, deβ-nitrobispyrene, two Methyl-2,2,- Nitrogen bis-butyric acid vinegar, 2, 2, - even over brewing, = valeronitrile), 2, 2'-azobis(2_f-butyronitrile), persulfate unloading, sodium sulphate, persulfate, Weihua hydrogen, 4,4,-azobis-tetradecanoic acid--salt, 2,2'-azobis(2~T-decylamine) dihydrochloride, 2,2,-azobis ( 2 dimethyl butyl amide oxime) dihydrochloride tetrahydrate, 2, 2, azobis {2-methyl-N ['1 bis (transyl fluorenyl) 2- 2 - ethyl] Acrylic amine}, 2,2'-azobis[2- ❹ΐϋ-(2_ethyl)-propanol], various redox catalysts (in this case, oxygen agents, such as ammonium persulfate, Examples of reducing agents such as potassium persulfate, sodium persulfate, hydrogen peroxide, third hydrogen peroxide, benzamidine oxide, cumene hydroperoxide, p-methylperoxy gas, etc. , acidic sodium sulfite, R standard], ascorbic acid, and the like. )Wait. [0045] These polymerization initiators may be used alone or in combination of two or more. Among these, the viewpoint of excellent qualitative properties of polymerization f, potassium persulfate, ammonium persulfate, sodium persulfate, oxidation, &amp; catalyst (oxidant: potassium persulfate, persulfate, sodium persulfate, reducing agent: sulfurous acid) Sodium, acidic sodium sulfite, R〇ngalit [trademark ascorbic acid), and the like are preferred. ❹ [0046] The amount of the polymerization initiator to be used is preferably in the range of 0.01 to 5 parts per 100 parts by mass of the ethylenically unsaturated monoterpene (hereinafter referred to as "parts"). 〇 3 to 3 servings are better. The reason is that if the amount of the polymerization initiator used is too small, there is a tendency to become slow, and if too large, the molecular weight of the copolymer obtained is lowered, and the water resistance is not good. Further, the above polymerization initiator may be added to the polymerization tank in advance, or may be added immediately before opening and closing, and may be additionally added during the polymerization as needed. Alternatively, the pre-addition, the early-form mixture, or the addition of the emulsion composed of the above-mentioned monomer mixture, and the addition of the initiator, may dissolve the polymerization initiator in another solvent 13 ί S3 200932849 or After the monomer is dissolved and dissolved, the hydrazine is dissolved and added. The σ initiator is further emulsified. [0048] <Polymerization adjuster> Further, during polymerization, blending polymerization can be adjusted. a chain transfer agent, pH buffer, etc. Further, the adjustment agent, for example, [_] the above chain transfer agent, for example, methanol, ethanol, propanol propionaldehyde, n-butyraldehyde, furfural, benzaldehyde and other aldehydes; positive / known alcohol; acetaldehyde, Alcohol, thioglycolic acid vinegar, glycerol and other alcohols. =$Alcohol or thioglycol is used in two or more types. ^ Waiting for early use or [0050] The use of this chain transfer agent, in the stable polymerization, can reduce the degree of polymerization of the synthetic tree (X), get the coating 'but can be, in particular, , chain _ such as _ low. For all 100 parts, preferably 0.010~1 parts, 0 010~〇5 Saturated early (M) chain transfer agent is used too little as chain shift _: because: if too much, it will be mixed There is a tendency for the rate to decrease, and there is a tendency to be insufficient. [0051] ❹ Further, the above pH buffering agent, for example, soda ash (sodium carbonate), acid reading, citric acid, yue unloading, acid-filled di-nano, can acid ) Lingling acetic acid, sodium formate, citric acid and so on. These can be used alone or in combination with sodium, [0052] 4 μ. The amount of use of the pH _ agent is less than 1 part by weight, preferably 0.01 to 10 parts, preferably M~5 parts. The reason is (): If the amount used is too small, it is used as a polymerization. If the effect of the regulator is insufficient, if there is too much, there is a tendency to hinder the reaction. '[0053] <Interfacial Agent> Further, the above surfactant, for example, an alkyl group or an alkyl allylate Sulfate, 200932849 base or silk lion base salt, di-filament gamma _, dodecapine benzoic acid sodium, polyoxyethylene sulphur sulphur, silk __ sub-interface activity Cationic surfactants such as di-f- chlorinated*, sulphide-based gasification; poly-vinyl wire fine, polyoxyethylene contact, polyoxyethylene phthalate, polyoxyethylene glycol, polyoxyethylene Non-ionic surfactants such as propylene glycol; and recording = sulfonate 1-b (allyloxymethyl) acetonyloxypolyoxyethylene, contiguous 1 - = -(alkoxy)methyl-2 -(2-propenyloxy)ethoxy-poly(oxygen_u_ethyl bromide), oxyethylenic (tetra), finely divided, etc., may be used singly or in combination of two or more. ~ ❹ [0054] trait (four) amount, Not off, If the total number of H(10) is not 100, then it is better, and it is preferably 5 to 1 part, especially preferably 0.5 to 5 parts. The reason is: that is, if there are too few boundaries, in terms of polymerization, It will become uncomfortable, and the anti-use will be too small. _ 'The result is that the viscosity of the emulsion composition is too low, and there are problems such as reduced workability. [0055] <Plasticizer and film formation Auxiliary> ❹ Further, the above plasticizer: for example, an adipate plasticizer, a linonic acid plasticizer, etc. can be used. Also, a boiling point of 26 〇 ° C or more can be used [0056] The plasticizer or the like The amount of the other components such as the filming agent is not particularly limited as long as it does not hinder the object of the invention, and may be appropriately selected depending on the purpose. [0057] "Production of Emulsion Composition" A synthetic resin (χ) formed of the above-exemplified polymer component is used as the The emulsion composition of the invention is dispersed. Here, the preparation of the emulsion composition of the present invention will be described, and the production of the above synthetic resin (X) will be further described. [0058] 15 200932849 [0059] , Μ, Λ ° green, for example There are the following methods: [1] ethylenically unsaturated monomers ^), The surfactant, water, etc. are added in full, and the temperature is raised. The monomer ΪΞΪ5 water 1 boundary? live, the ethyl-unsaturated monomer (10) - part, 'heating [2] in the reaction ΐ ί ί E-saturation monomer (10)), and continue to gather. The method, [3] adding the water, the surfactant, etc. in the reaction tank, the ethylenically unsaturated monomer (M) is added or divided in total, and the polymerization polymerization temperature is controlled by the face, the above [ The methods of 2] and [3] are preferred. The polymerization conditions in the polymerization method shown in the above [Q] to [3], for example, the above [the polymerization condition of the oral method] is usually a temperature of 4G to Wt, and the reaction is about 1 to 8 after the start of the well temperature. hour. Further, in the polymerization conditions of the polymerization method of the above [2], for example, 1 to 50% by weight of the ethylenic unsaturated monomer (M) is usually 40 to 9 (TC is polymerized for 0.1 to 4 hours, and then © The remaining ethylenically unsaturated monomer (M) is added dropwise or divided and added in about 1 to 7 hours, and then matured at the above temperature for about 1 to 3 hours, etc. Table [0062] Further, the polymerization method of the above [3] The polymerization conditions are, for example, adding water to the polymerization tank to '40 to 90 ° C' and adding the monomer mixture to the mixture for about 2 to 7 hours or adding it, and then aging at the above temperature for about 1 to 3 hours, etc. Knive [0063] In the above polymerization method, the ethylenically unsaturated monomer (M) is prepared by first dissolving the surfactant (or a part of the surfactant) in the ethylenically unsaturated monomer (M), or pre-formed. The 0/W type emulsion state is preferred from the viewpoint of polymerization stability. [0064] 200932849 (4) Shang Laicheng ο/w Wei Huaquan Green, if the interface is live, dissolved in water, adding the above monomer , the method of affinity _ emulsification, the active agent is dissolved in water, and the above monomer is added while stirring. The above-mentioned emulsion is stirred during emulsification, and the components can be mixed and stirred by a stirrer or a blade stirring blade. The temperature at the time of emulsification is not affected by the temperature at the time of emulsification. , usually about 5 to 60 2 is suitable for production. Further [0066] Ο "Emulsion composition" Disperse the tree sputum secret, and side material crane composition [0067] The leakage composition of the present invention, the dispersion is the above synthesis _(χ), and j is a dispersion medium in which the synthetic resin (X) is a dispersoid, that is, a water-based medium is not particularly limited. The aqueous medium is preferably an alcohol solvent, preferably water. A is mainly based on water [0068] 概要 Ϊ Ϊ ' 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要 概要(α)> In the above emulsion composition, the average particle size of the synthetic resin (χ), 500 = the fineness of '······························ In the case of Linhe, the emulsion group does not have sufficient mixing property, so the coating film will be mixed after hardening = although the r particle size is If it is larger than the above-mentioned upper limit, when the money is mixed, the film may not be obtained with sufficient strength. Further, when the cement is mixed, it is not possible to obtain the color of the film. [0070] ♦ and 'the above synthetic resin (X The particle size variation coefficient (〇1) must be 40% or less, more preferably 35% or less, and particularly preferably 鄕. If the coefficient of variation is greater than the above upper limit, the particle size is not The uniformity is large, the stress is not accumulated when the cement is mixed or the fineness of the coating is formed, and the crack is likely to occur after the cement is hardened. Moreover, the lower limit of the coefficient of variation (8) is usually 25%. [0071] The above synthetic resin ( X) The average particle size and the particle size variation coefficient (α) are measured according to the following formula ❹ (1) using NiC 〇 mp380 (partition Sizing System), and the average particle size and standard of the composite f tree 爿 a (X) are measured. After the deviation, calculate the coefficient of variation. [Equation 1] [0〇3 coefficient (%) = standard deviation (4) / average particle diameter (4) x100 (1) Further, the method for measuring the particle size of the synthetic resin (X) is not limited to the above method, and the method of shooting • Subsequent, sedimentation method, electronic display [_] ❹ The average particle size and particle size variation coefficient (α) of the synthetic resin (X) are appropriately adjusted in the case of use, and are set within a predetermined range. For example, when an anionic surfactant is used together with a nonionic surfactant, a part of the agent is pre-charged with a polymerization tank, a cesium anion active agent and a non-ionic interface are used, and a female polymer 2 is used. Get it when. However, it is not limited to these methods. (Four Glass Transfer Temperature (Tg)> Further, the glass transition temperature (Tg) of the above synthetic resin (X) is preferably 〇1 or more preferably -lire or less. ——······································································ Further, the lower limit 値 of the glass transition temperature (Tg) is usually a 70 [0076] and the glass transition temperature (Tg) of the synthetic resin (X) in the present invention, and the Fox represented by the following formula (2) is used. The formula is calculated. [Expression 2] l/Tg=W1/Tg1 +w2/Tg2 +...+ Wn/Tgn (2) [0078] In the above formula (2), '^% to Wn, Represents the weight fraction of each monomer used, Tgn ' represents the glass transition temperature of the homopolymer of each monomer (the unit is the absolute temperature K), and the absolute temperature is the absolute temperature "κ" = photo 273.15 calculation. ” 【0079】 <non-volatile concentration> The age of the human body (5) thief concentration), from the cement mixed j color Χ Μ 4%, preferably 45 to 75 wt%, ^^ is 5G to 7G% by weight 'sometimes, 52 to 6 (% by weight) is preferable from the viewpoint of workability. Also, too 狢昍 狢昍 丨 u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u

Uj Rinnu forward component concentration (solid viscosity concentration). <Viscosity> 10000^^ 1〇- Especially good. Good 10~50000mPa · s better, 10~l〇〇〇〇mPa · s [0081] Cloth film waterproofing The emulsion composition of the present invention is blended with cement to become a coated TooS ship, especially in the water Coating gambling water hunger composition. Said owe / Nie such as 'ordinary Portland cement, oxidized Shao cement, early strong Portland 200932849 early, Portland water%, moderate hot Portland cement, low heat Portland cement, Lai cement, blast furnace cement, Dry ash cement, oxygen cut cement, etc., of which Portland cement is preferred from the viewpoint of workability. The blending amount of the supernatant is preferably from the weight of the transfer component of the milk-aged product of 100 to f 2 乂 3 to 500 parts by weight, more preferably from 3 to 35 parts by weight. Further, the amount of water is more preferably 5 to 5 10 to 30% by weight based on the total amount of the coating film waterproofing material.戛权住 [0084] ❹ F-&gt;; 1 or more kinds of aggregates are used in combination. [0085] ^ hair day ^ coated gambling water material test object towel, the village adds force to the other water agent or fluidizer (for example: lignin, naphthalene, cold (such as chlorination), water repellent (for example, stearic acid, etc.), anti-recording agent (= 乙 E-agent (for example, methyl cellulose, ethyl cellulose, poly-slurry agent, for example, multi-drug, inorganic phosphorus, etc.), defoaming The agent (example [0086], this method] can obtain the human skin waterproofing material for the coating film waterproof material of the present invention. (4) The construction can be formed by the nozzle spray nozzle construction [0087] The object of the above-mentioned coating film waterproof material is formed. Concrete, weaving, leaching version of the slanting V oblique; ^ body (=) covering 20 tS] 200932849 ϊ ϊ: connecting the corridor, stairs, underground backfill part of the building, 4 Shi = contact material, ± tree reading [0088] However, the present invention is not particularly limited by the following examples and comparative examples, and is not limited to the following examples. [0089] Further, the following examples are shown. "Parts ""% by weight"."

&lt;Preparation of Emulsion Composition&gt; [Example 1] 26 parts of water were weighed in a container in advance, and surfactant a2 5 shown in Table i to be described later was inoculated with a surfactant of Cl. 62 parts (Table 1) 90%), 66.2 parts of butyl acetonate, 32 parts of styrene, and 4.6 parts of 40% acrylamide were prepared to prepare a monomer emulsion mixture. [0091] Next, 0.1 parts of soda ash, 31 parts of water, and cO.18 parts of surfactant were dissolved in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a dropping funnel (Table 1). 1〇〇/0). [0092] 10% of the previously prepared monomer emulsion mixture was added to the above glass reaction vessel, the temperature was raised to 85 ° C, and after heating at 85 ° C, '10% sodium persulfate (polymerization initiator) 1.6 parts were added to the above glass reaction vessel, and the reaction was carried out. Thereafter, the remaining monomer emulsion mixture and 5 parts of 10% sodium persulfate were added dropwise to the glass reaction vessel for 3 hours to carry out polymerization at 85 °C. After the completion of the dropwise addition, the mixture was aged at 85 ° C for 180 minutes to complete the polymerization. After cooling to room temperature (25°, an antifoaming agent [Nopco 8034 (manufactured by San Nopco)] 0.4 parts, a preservative [Melgar K9N (manufactured by Clariant)] 0.3 parts, and a neutralizing agent (caustic soda) 〇·12 were added. In addition, water was added to obtain a non-volatile component (solid content) of 55.5%, and the pH was adjusted to 7 to 10, and the emulsion group 21 200932849 was obtained. [0093] [Examples 2 to 5, 8] The age of Z and the interface The composition of the active agent was carried out in the same manner as shown in Table 1 below, and an emulsion composition was obtained. [Example 6] 160 parts of the emulsion composition of Example 1 was mixed with the emulsion of the emulsion of Example 3, and it was obtained. Emulsion composition J,, [0095] [Example 7] In the preparation of the monomer emulsion mixture, the surfactant b〇81 was added. Above: Sexual gas c2: 34 parts (the release of Table 1 was added to the agent) In addition to the glass reaction, the emulsion composition was obtained. # [0096] [Comparative Example 1] In the preparation of the monomer emulsion mixture, 5 parts of the surfactant a2 was added (Table i 50) %), surfactant surfactant cl. 8 parts (5% of the table i), the remaining interface activity is added to the glass reaction vessel, except for the same as in the example [Comparative Example 2] The composition of the monomer and the composition of the surfactant were carried out in the same manner as in Example 1 except that the composition of the surfactant was carried out in the same manner as in Example 1 to obtain an emulsion composition. [Comparative Example 3] 100 parts of the emulsion composition of the above Example 1 and 100 parts of the emulsion composition of Example 3 were mixed to obtain an emulsion composition. ' [0099] 22 200932849 [Comparative Example 4] In the preparation of the bulk emulsified liquid mixture, 8 parts of the surfactant (cl. 100%) was added, except that the same procedure as in Example 1 was carried out to obtain a milk mash group 1 01 1 Ω 01 ' [0100] [Table 1] Table 1 · List of composition of emulsion composition❹

(Parts by weight) Example Comparative Example 1 2 3 4 5 6 7 8 1 2 3 4 Monomeric acrylamide (a) (40% acrylamide) 1.85 (4.6) 1.85 (4.6) 1.85 (4.6) 3.85 (9-6) 0.04 (0-1) 1.85 (4.6) — 1.85 (4.6) 1.85 (4.6) 1.85 (4.6) 1.85 (4.6) 1.85 (4.6) 曱ί acrylamide (a) 2.0 曱i acrylic acid曱 vinegar (1) 16.6 butyl acrylate (1) 66.2 66.2 66.2 64.8 67.4 66.2 78.0 50.7 66.2 66.2 66.2 66.2 styrene (2) 32.0 32.0 32.0 31.3 32.6 32.0 — 47.4 32.0 32.0 32.0 32.0 itaconic acid (4) 0.5 — One - one acrylonitrile (8) - _ _ one _ - 2.9 one by one - surfactant surfactant a*l 2.5 2.0 2.8 2.4 2.6 2.5 — 2.5 5.0 1.4 2.5 2.5 surfactant b*2 0.9 — — — — — Interface activity 剤c*3 1.8 1.3 1.9 1.7 1.9 1.8 2.6 1.8 3.6 1.1 1.8 1.8 [S] 23 200932849 Physical average particle size (nm) 250 395 200 240 280 240 250 250 90 520 224 250 Coefficient of variation (%) 16 10 20 17 14 39 16 16 20 19 54 48 Non-volatile content concentration 55.5 55.5 55.5 50 55.5 55.5 55.5 55.5 55.5 55.5 55.5 55.5 Tg (calculated 値) rc) -22 -22 -22 -22 -22 -22 -30 -1 -22 -22 -22 -22 *1 : Triisobutylphenol ether sulfate with 7EO, sodium salt ( HOSTAPAL BV —cone., manufactured by Clariant Co., Ltd. *2: Alkyl ethoxylate with 28 EO (Emulsogen EPA073, manufactured by Clariant) *3 : Emulsogen EPN287, manufactured by Clariant (alkyl ether sulfate, with 7 Mo) Ear EO, sodium salt) [0101] Further, the physical properties of the average particle diameter, the coefficient of variation, the concentration of the nonvolatile component, and the glass transition temperature [Tg] were measured for each of the emulsion compositions obtained above. The results of these are shown in Table 1 above. 【0102】

&lt;Production of Coating Film Waterproof Material&gt; [Examples 9 to 16 and Comparative Examples 5 to 8] Each of the emulsions of Examples 1 to 8 and Comparative Examples 1 to 4 obtained in this manner was composed of the following Table 2 The blending ratios of the components shown are each blended, and kneaded in a mixer for 3 minutes to prepare each slurry. Next, the release paper is attached to the slate, and the frame of the acrylic plate (long diameter 3 〇 cm, short diameter 25 cm, thickness 2 mm) is fixed and the above-mentioned slabs are respectively flowed into the frame, and the surface is troweled. After smoothing, it was hardened for 1 week at room temperature 耽 + H for thief 65% ± 1 G%. Thereafter, the slurry was rotated and further cured for one week, and the obtained examples and comparative coatings were applied = 24 200932849 - [0103] Further, in Example 12 and Comparative Example 6, no water was added to the emulsion composition. In Example 12, a water-repellent (W)/cement amount (C) = 100%, a milk dose (polymerization: py cement amount (C) = 100% of a coating film waterproof material) was produced, and in Comparative Example 6, w/C = = 122%, P/C = 100% of coating film waterproofing material. [0104] [Table 2] Table 2. Blending table of coating film waterproofing material (parts by weight) Ordinary Portland cement*1 100 Shixi sand 7 No.*2 — ~~&quot; 50 Adekanate 13-107F (antifoaming agent)*3 0.75 Emulsion (essential) 100 Moisture 85 W/C (%) 85 P/C (%) One-- * 1 · Ancient female 7k system 1 100 ❹ *2 : Use of commercially available enamel, particle size range 〇〇7~〇2〇^*3: ADEKA company system [0105] [0106] 1 piece. "Color development" The waterproof material (slurry) is visually observed for the color of the outer composition and the cement powder, etc. (2) t S1 25 200932849 x : for wavelength 400 ~800nm hue, small chroma i: Δ: hue of wavelength 400 to 800 nm, chroma 1. 〇: hue of wavelength 400 to 800 nm, chroma 2 or more. [0107] "Mechanical evaluation: tensile strength, elongation" [Jis K 6301 (3. Tensile test)] The dumbbell No. 2 model specified in the paper was cut into three pieces, and three test pieces were produced. In the longitudinal center portion of the test piece, the width was correctly and clearly drawn. The thickness of the film of 2 〇mm was measured, and the thickness of the total thickness of the three parts was measured, and the average 値 was used as the thickness tmm of the test piece. [0108]

The test piece was attached to a tensile tester (AUTOGRAPH AGF-5D, manufactured by Shimadzu Corporation), and a tensile load was applied until the test #龙 or 10 times the distance between the lines, and the maximum tensile load (PB) was measured. The distance between the lines. The distance between the lines at the time of the breakage causes the gauge to be visually defeated. The test conditions were: 2 (8) mm/min, the distance between the initial chucks was 6 Gmm, 23 °C ± rC, and the humidity of the yarn was 5 G% + 1%. [0109] - <Tensile strength>, the "tensile strength" of the test piece was calculated according to the following formula (3)', and evaluated according to the following criteria. 〇: 0.8N/mm2 or more. Less than 0.8N/mm2 △ : 0.4N/mm2 or more, x : less than 0.4N/mm21 [0110] [Expression 3] TB=PB/A ......(3) [0111] 浐大T, piece Tensile strength (four) - 2). PB is the calculation of the test piece ί · The sectional area of the piece ' is from the width of the test piece 26 [0112] 200932849 <Elongation rate> Price 0 From the following formula (4), the "elongation rate" of the crack is measured, 〇: 100 %the above. And evaluated according to the following criteria: △ 30% or more, less than 100 〇 / 〇. X : less than 30%. [0113] [Expression 4] (4)

E = (L - 20) / 20 χ 1 〇〇 [0114] L is the reticle spacing at break. In the above formula (4), Ε is the elongation at break (%). From (mm). [Appearance] The coating film preventing material was visually observed, and the basis was judged according to the following: no crack occurred. ° △: 3 or less cracks with a length of 5 mm or less. X: More than 4 cracks of 5 mm or less in length or more than 5 mm in length. ❹ 【〇116】 【Table 3】 Table 3. List of evaluation results of coated waterproofing materials Example---« Comparative example Qualification standard 9 10 11 12 13 14 15 16 — ~ —— 8 Paste coloring 〇〇 〇〇〇〇〇〇---- XX Δ △ 〇: The tensile strength of the chromonic coating film is clearly observed 〇〇〇〇〇〇〇〇---- 〇(N/mm2) 〇〇0 0 _ 6&lt ; 27 [S] 200932849 Elongation (%) 〇〇〇〇〇〇〇〇〇〇〇0 100% &lt; Appearance 〇〇〇〇〇〇〇〇△ △ △ Δ ο: No abnormalities such as cracks (Examples 1 to 8) (Comparative Examples 1 to 4) 1 2 3 4 5 6 7 8 1 2 3 4 [0117] From the above results, the coating films of Examples 9 to 16 were all obtained to prevent color development. Excellent results in properties, tensile strength, elongation, and appearance. Further, it can be seen that the emulsion compositions of Examples 1 to 8 used in the coated film waterproof materials are excellent in the miscibility with cement and have a certain color when mixed, and can be visually judged and mixed at the time of construction on site. Sex 'is easier to inhibit cracking of hardened materials. On the other hand, in Comparative Examples 5 and 6, since the emulsion compositions of Comparative Examples 1 and 2 used were outside the range of the average particle diameter of the synthetic resin of the present invention, the coloring property was poor and the appearance was poor. result. Further, in Comparative Examples 7 and 8, the emulsion compositions of Comparative Examples 3 and 4 which were used exceeded the coefficient of variation of the average particle diameter of the synthetic resin of the present invention by 〇', and thus were inferior in color developability and appearance. Further, the color development properties of each of the pastes of Example 9 and Comparative Example 6 were visually confirmed. The result is shown in Figure 1. Fig. 1 shows the slurry of Example 9, which is a faithful reproduction of the emulsion composition of Example 1 and the kneaded material of the cement. The slurry of Comparative Example 6 is shown in Fig. 1 to faithfully reproduce the emulsion of Comparative Example 2. The composition and the kneaded material (slurry) of the cement. Results The cement slurry of Example 9 was a bluish gray, and the cement slurry of Comparative Example 6 was gray. In addition, the camera equipment and conditions are also displayed together. (Industrial Applicability) [0120] The emulsion composition of the present invention is excellent in the miscibility with cement, and is used in the construction of the building; the construction is connected to the second row: in the civil, trough, and mantle. Water storage in the upper water channel [Simplified description of the drawings] Fig. 1 shows the use effects of the emulsions of Example 9 and Comparative Example 6. [Main component symbol description] None

29

Claims (1)

200932849 VII. Patent application scope: 1. An emulsion composition, the dispersoid is synthetic resin PQ, characterized in that the average particle diameter of the synthetic resin (X) is in the range of 1 〇〇 500 500 nm, and the particle size variation coefficient is 2. The emulsion composition of claim 1, wherein the emulsion composition has a nonvolatile content concentration of 45% by weight or more. 3. The emulsion composition according to claim 1 or 2, wherein the synthetic resin (X) has a glass transition temperature of 〇 ° C or less. 4. The emulsion composition of claim 1 or 2, wherein the synthetic tree resin (X) is a homopolymer or copolymer of a sulfhydryl-based ethylenically unsaturated monomer (&amp; Composition. 5. If applying for a full-time or second crop, the grade is used for membrane waterproofing. A composition for a coating film waterproofing material, which is characterized in that the emulsion composition according to any one of claims 1 to 5 is further blended with cement. A coating film waterproofing material comprising: the emulsion composition of any one of claims 1-5 to 5%. 8. A method for forming a coating film waterproof material, characterized in that the composition for a coating film waterproof material according to item 6 of the patent application is formed into a coating film waterproof material according to the following method (A method of construction: (A) Coating with a roller, applying with a brush, coating with a trowel, and spraying with a mist. 、, 八, 图: 30 iS】