JPS63270369A - Reinforced molded product of water-hardening inorganic material - Google Patents

Abstract

PURPOSE:To enable formation of a formed product of excellent water resistance, solvent resistance, acid resistance, alkali resistance and high mechanical strength, by impregnating a formed water-setting inorganic material with an aqueous emulsion having particle size of less than a specific value, cross-linking structure and a specific glass transition point. CONSTITUTION:A formed product of a water-setting inorganic material is impregnated with an emulsion having an average particle size of less than 100nm, cross-linking structure and a glass transition point lower than that calculated by the weight fraction method. In this case, when the particle size of the emulsion exceeds 100nm, the adhesion becomes low, when a coating film is formed, resulting in low impregnation into the inorganic material. In some cases, further the gloss and transparency and smoothness of the coating film become unsatisfactory. Additionally, the aqueous emulsion has cross-linking structure and the coating films formed can meet the required properties. Further, the emulsion has the above-cited glass transition point, and shows good plasticizing effect to lower the lowest film-forming temperature, thus the coating films of desired properties can be readily formed at room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a reinforced hydraulic inorganic material molded article impregnated with a specific aqueous emulsion.

[Prior art]

Conventionally, monomers, polymerization initiators, crosslinking agents, and coupling agents have been used to strengthen hardened bodies (hereinafter referred to as hydraulic bodies) made by molding hydraulic inorganic materials such as mortar, concrete, and plaster into predetermined shapes. A hydraulic body impregnated with a polymer is produced by impregnating the surface of the hydraulic body with a mixture of agents and the like, and then performing radiation polymerization, thermal polymerization, or the like.

However, since the monomer has a high vapor pressure at room temperature, it has the disadvantage of creating a poor working environment unless large-scale equipment is provided.

In addition, as a method to solve the above problem, an aqueous emulsion of SBR latex, polyacrylic acid ester, and ethylene-vinyl acetate copolymer is impregnated from the surface of the hydraulic body, dried and solidified, and the hydraulic body impregnated with the polymer is Methods for manufacturing bodies have also been proposed.

However, these conventional hydraulic bodies impregnated with latex and water-based emulsions have poor water resistance, solvent resistance, acid resistance, alkali resistance, and mechanical strength, so the places where polymer-impregnated hydraulic bodies can be used are limited. Moreover, when used for a long period of time, the polymer-impregnated part deteriorates, causing various problems such as cracks and damage to the impregnated part.

〔the purpose〕

An object of the present invention is to provide a reinforced hydraulic inorganic material molded article that, unlike conventional molded articles, has excellent water resistance, solvent resistance, acid resistance, alkali resistance, and mechanical strength.

〔composition〕

According to the present invention, a hydraulic inorganic material molded body is impregnated with an aqueous emulsion having an average particle size of 1100 nm or less, a crosslinked structure, and a glass transition temperature lower than the value calculated by the weight fraction method. A reinforced hydraulic inorganic material molded article having the following characteristics is provided.

In the present invention, firstly, the aqueous emulsion impregnated into the hydraulic inorganic material molded article has an average particle diameter of 110
It is characterized by being 0n or less, preferably 80ni+ or less.

In an aqueous emulsion, a film is essentially formed by filling and fusing particles, so the average particle size is required to be small, but the aqueous emulsion used in the present invention preferably has an average particle size of 1100 nm or less. Since it has a diameter of 80 nm or less, it has good impregnation properties into the hydraulic inorganic material molded product, and forms a film with excellent smoothness and transparency. Glossiness can be maintained as is.

If the average particle size exceeds 100 m, the fusion properties (denseness) when forming a film will be poor, and the impregnability into hydraulic inorganic material molded bodies will also be reduced, and the glossiness and transparency of the film will be reduced. Since the hardness and smoothness may be insufficient, the intended purpose of the present invention cannot be achieved.

A second feature of the aqueous emulsion used in the present invention is that it has a crosslinked structure within and/or between its particles.

That is, the aqueous emulsion according to the present invention has an ionic bond, a hydrogen bond, or a condensation reaction between the functional groups of the raw unsaturated monomers, or between these and the functional groups of the emulsifier, within the particles and/or between the particles. Alternatively, since it is crosslinked by a polymerization reaction or the like, a film having excellent water resistance, solvent resistance, acid resistance, alkali resistance, and mechanical strength can be formed.

Furthermore, the third characteristic of the aqueous emulsion used in the present invention is that it is lower than the value calculated by the 1 weight fraction method, preferably 3
The glass transition temperature must be lower than 5°C, more preferably 5°C or lower.

Glass transition temperature (Tg) is the temperature at which a polymer changes from a glassy, hard state to a rubbery state when heated.If the glass transition temperature of a component, which is a structural factor of a polymer, is known, The glass transition temperature can be determined from the following equation using the weight fraction method.

Tic Tv, A Tgn W^; Weight fraction W of component A; Weight fraction TgA of component B; Glass transition temperature of component A Tgll; Glass transition humidity of component D This glass transition temperature is influenced by various structural factors. Generally, in the case of polymers with a crosslinked structure, the glass transition temperature is high, and depending on the degree of crosslinking, it may rise by 5 to 7 degrees Celsius, and adding a plasticizer to the polymer may lower the glass transition temperature. Are known.

On the other hand, for polymer latex, the minimum film-forming temperature is known as the lowest temperature at which a film is formed by filling and fusing particles, and there is a proportional relationship between this minimum film-forming temperature and the glass transition temperature. Recently, the present inventors have developed ultrafine particles that have a crosslinked structure and have a minimum film-forming temperature or glass transition temperature of the formed film that is lower than the value calculated by the weight fraction method (1) and form a film with excellent mechanical strength. A polymer latex was discovered and found to be useful as a reinforcing impregnating agent for hydraulic inorganic material moldings.

That is, the aqueous emulsion used in the present invention.

Despite having a crosslinked structure, it has the ability to form a film that exhibits a glass transition temperature lower than the value calculated by the weight fraction method as described above, so unlike conventional products, it exhibits an excellent plasticizing effect and is easy to form. Since the glass transition temperature of the film is lowered, the minimum film-forming temperature is also lowered in proportion to this, resulting in excellent transparency, adhesiveness, and smoothness even at room temperature. Furthermore, it is possible to form a hard film with good mechanical strength such as tensile strength and modulus strength. In this case, as is clear from the comparative example below, if the glass transition temperature of the film to be formed is higher than the value calculated by the Grave Fraction method, the aqueous emulsion will not have sufficient plasticizing effect, so the minimum film formation Because the temperature also rises, a film may not form at room temperature, or even if it does, cracks or mesh-like streaks may occur in the film, making it difficult to obtain a film with excellent transparency, smoothness, and adhesiveness as in the present invention. cannot be formed.

Furthermore, it is hard and lacks mechanical strength such as tensile strength and modulus strength, making it difficult to obtain a hard and strong film.

In addition, other characteristics of the aqueous emulsion used in the present invention are:
It has excellent dispersion stability over a long period of time.

That is, the aqueous emulsion used in the present invention has an average particle diameter of 100n+a or less;
Even when subjected to a forced heating dispersion stability test for one week, there is virtually no change in the average particle size, and even if there is a change, it is usually a single peak distribution of particles with an average particle size of 150r+a+ or less. Even when the rate of change is large, the first peak of the particle size distribution with an average particle diameter of less than 15 On1 is 97% or more, and the second peak due to particle aggregation is a particle size distribution of 300 nm or more. 3 has
% or less, and the particle size distribution of the average particle diameter is extremely small.

Furthermore, the aqueous emulsion used in the present invention is heated at 25°C and 6°C.
Even when subjected to a long-term storage stability test for several months,
The rate of change in the average particle diameter is extremely small.

Therefore, in the aqueous emulsion used in the present invention, particles do not substantially coalesce or aggregate over time, and do not generate coarse particles, so there is no change in particle size or decrease in transmittance over time. Since there is no change in viscosity or change in appearance, it shows excellent dispersion stability over a long period of time and has extremely high storage stability.

The reason why the aqueous emulsion used in the present invention exhibits excellent dispersion stability as described above is not necessarily clear, but
Because the average particle diameter is 1100 nm or less, Brownian motion between particles is relatively active, and due to the fact that no polymerizable emulsifier remains in the system and the properties of the surface of each particle, each The basic factor is presumed to be that since the particles are sufficiently protected, coalescence and aggregation of the particles are prevented, and the formation of coarse particles is not promoted.

In addition, in the present invention, in order to further improve the dispersion stability of the aqueous emulsion, conventionally known compounds such as P-hydroxydiphenylamine, N,N'-diphenyldiamine, and 2,5-di-tert-butylhydroquinone are used. A polymerization inhibitor or a polymerization terminator may also be added.

In addition, the average molecular weight of the crosslinked aqueous emulsion used in the present invention is generally more than 100 degrees, in most cases tens of millions to hundreds of millions, and in the case of those with a high degree of crosslinking, it is several thousand degrees. In some cases, the molecular weight is about 10,000 to 1 billion, and even higher.

The present invention will be explained in more detail below.

The aqueous emulsion used in the present invention can be obtained by emulsion polymerization of unsaturated monomers in the presence of a specific emulsifier described later.

Examples of the unsaturated monomer include (meth)acrylic esters represented by the following general formula (1) (wherein R and R
2 is hydrogen or a methyl group, R3 is an alkyl group having 1 to 18 carbon atoms), lower fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylonitrile,
Nitriles such as methacrylonitrile, styrene, α-
Examples include styrenes such as methylstyrene and chlorostyrene, vinyls such as vinyl chloride and vinyl bromide, vinylidenes such as vinylidene chloride and vinylidene bromide, dienes such as butadiene, chloroprene and isoprene, and vinylpyridine. , (meth)acrylic esters, lower fatty acid vinyl esters, nitriles and styrenes are preferably used.

In addition, in the present invention, the unsaturated monomer to be copolymerized with the above unsaturated monomer is used to further strengthen the crosslinked structure within and/or between particles of the aqueous emulsion to be produced. Although unsaturated monomers having reactive functional groups are preferably used to promote crosslinking during film formation, even unsaturated monomers having no reactive functional groups can be used.
In the emulsion polymerization system, it is also possible to use unsaturated monomers that can be converted into compounds with active hydrogen.

Examples of unsaturated monomers having such reactive functional groups include compounds represented by the following general formulas (n) to (■). These monomers can be used alone or in combination of two or more, and if necessary, other copolymerizable unsaturated monomers can also be used in combination.

Ks LNMI RgOH (wherein, nx lR2 -R4 1Rs , Rc'+R
t +Rs tRg, A, B+D+E+ t, +t2 and t3 are as follows.

Rx tRz + ; hydrogen atom or methyl group R. ; Carbon-i1 Alkylene group having 2 to 4 atoms Rs: Direct bond, alkylene group having 1 to 3 carbon atoms, phenylene group or substituted phenylene group role group R parahydrogen;
Also an alkylol group having 1 to 5 carbon atoms? Alkyl group R having 1 to 5 carbon atoms; Alkylene group A having 1 to 4 carbon atoms; Methylene group or carbonyl group B; -CH■0- or carboxyl group D; hydrogen atom,
Alkyl group having 1 to 3 carbon atoms, carboxyl group, -CON
IICHCH3 or I COOH -CONHCONH, E; hydrogen atom, alkyl group having 1-3 carbon atoms or -CH
, COOH t,; Real number t2 of 1 to 20; Integer t of 0 or 1; Integer of 0 to 10) General formula (n), (m), (IV), (V), (Vl),
Specific examples of the compounds (■) and (■) include those shown below.

Examples of general formula (II) Glycidyl acrylate Glycidyl methacrylate Glycidyl tonate Glycidyl allyl ether Examples of general formula (III) Hydroxyethyl acrylate Hydroxyethyl methacrylate Hydroxyethyl crotonate Hydroxypyl acrylate Hydroxypyl methacrylate Hydroxypyl Piruku Tonate Hydroxybutyl acrylate Hydroxybutyl methacrylate Polyoxyethylene monoacrylate Polyoxyethylene monomethacrylate Polyoxyethylene monocrotonate Polyoxypropylene monoacrylate Bolioxypropylene monomethacrylate Bolioxypropylene monocrotonate Polyoxybutylene monoacrylate Polyoxybutylene Monocrotonate Hydroxyethyl allyl ether Hydroxybutyl allyl ether Hydroxybutyl allyl ether Polyoxyethylene allyl ether Polyoxypropylene allyl ether Polyoxybutylene allyl ether Examples of general formula (IV) Allylamine Acrylamine Methacrylamine Aminostyrene α - Methylaminostynone Example of general formula (V) Acrylamide Methacrylamide Aminopropyl methacrylamide Monomethyl acrylamide Monoethylacrylamide Diethylolaminoprobyl acrylamide General formula (V
Examples of I) Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and its monoester or anhydride of an alkyl group having 1 to 5 carbon atoms, fumaric acid and its monoester or anhydride of an alkyl group having 1 to 5 carbon atoms, maleic acid Alanid fumaric acid Alanid N-carbamoylma! Twin acid amide N-carbamoyl fumaric acid amide Example of general formula (■) Methylallylthiol Methylmercaptostyrene Example of general formula (■) 2- and droxyethyl)acrylic acid amide N-(
2-hydroxyethyl) methacrylic acid amide N-(2-
Hydroxypropyl) acrylic acid amide N-(2-hydroxypropyl) methacrylic acid amide The ratio of the above unsaturated monomer to the unsaturated monomer having a reactive functional group is 9
9/1 to 60/40 (weight).

Preferably it is 99/1 to 90/10 (weight). When this usage ratio is greater than 99/1, the degree of crosslinking within and between particles of the aqueous emulsion to be produced becomes small;
If the ratio is less than 60/40, emulsion copolymerizability may be poor, a large amount of aggregates may be formed, film forming properties may be poor, or cracks may occur in the formed film.

The emulsifier used when emulsion polymerizing the aqueous emuldigone of the present invention using the unsaturated monomer described above forms a film exhibiting a glass transition temperature lower than the value calculated by the weight fraction method, as described above. Any emulsifier that can be used can be used, but particularly preferred emulsifiers include polyoxyalkylene ethylenically unsaturated carboxylic acid polyesters (hereinafter referred to as poly(
It is abbreviated as meta)acroyl emulsifier. ), general formula (X
), (X[), (X[I), (Xm) and (X IV)
Betaine ester type emulsifier and general formula (XV
), (XVI) and (X■).

(In the formula, R□lR21R1ll +RXI IRE□1
R131R14tR1stRIGIR1? tRtsfa
ttaxtaata4yasla! 1a7tasla9
patolGIJ+L, M, T, X, Y, and V are as follows.

RxtRz; hydrogen or methyl group R1゜=alkylene group having 2 to 4 carbon atoms R;; alkyl group or alkenyl group having 8 to 30 carbon atoms, which may be linear or branched, preferably 8 carbon atoms
-18 R□2; Alkylene group having 1 to 5 carbon atoms R13, R*+Rts; Alkyl group having 1 to 3 carbon atoms or -0, H40H, each of which may be the same or different.

Rzs + Rtt ; An alkyl group having 6 to 20 carbon atoms or hydrogen, at least one of which is an alkyl group having 6 to 20 carbon atoms; ; Hydrogen, an alkyl group having 1 to 30 carbon atoms or an alkenyl group a1r82+az la4 yas +as ga7:
Indicates the average number of moles added; a is a real number of 1 to 50, and the preferred number of moles of alkylene oxide added in the molecule is 8 or more; a2 is a real number of 0 to 20; a is a real number of 0 to 20; when either Rx4 or Ris is an alkyl group; is a real number from 0 to 20; when both Rlg and RlG are an alkyl group, a real number a4 from 1 to 30; a real number a from 1 to 30; a real number a6 from 0 to 20; a real number a7 from 0 to 20; Real number ao from 0 to 20; integer a from 0 or 1; real number P from 2 to 20; integer q from 2 to 5; integer from O to 3 10-P-0- OR, □ -O-CnH2n- gz (RzJ&-〇-RL9 t
R2°; hydrogen or alkyl group having 1 to 2 carbon atoms R21; hydrogen or % R-. O+TT-oH or →R1゜0+-rT
OC:O CR2=CHR□ g; integer gz from 0 to 5; integer n from 0 to 10; integer 8 from 1 to 10. : Real number from 1 to 50 (CI,)2-CI-0- or (CI+l)z-
CH-0-CHx - and y: a real number of 1 to 5 Rlg tRza ; hydrogen or alkyl group having 1 to 20 carbon atoms Y'; alkylene group having 3 to 8 carbon atoms, oxygen or carbonyl group with nitrogen, "; co -o- or) -〇- L; C1-5 fullkylene group or -CH-CH,C
OOM T; direct bond, oxygen, sulfur M: hydrogen or inorganic anion
In particular, if the average particle size is ultra-fine particles, inside the particles and/or
In order to obtain an ultrafine particle pre-crosslinked aqueous emulsion that forms a film that has a dense and more advanced crosslinked structure between particles and exhibits a glass transition temperature lower than the value determined by the calculation formula,
As an emulsifier used in the emulsion polymerization of the above unsaturated monomer,
(a) A poly(meth)acroyl emulsifier represented by the above general formula (IX), (b) the above general formula (X), (XI),
Betaine ester emulsifiers represented by (Xll), (x or ), (x rv ) and (c) the above general formula (
The ether carboxylic acid type emulsifiers represented by X V ), (XVI), and (X
/1 or (a)/(c) = 1/9 to 971 weight ratio,
It is preferably used in a weight ratio of 1/4 to 4/1. If this ratio is less than 179, the degree of crosslinking within and/or between particles of the aqueous emulsion produced may be small, and if it is greater than 9/1, the average particle diameter of the aqueous emulsion produced may become large. These emulsifiers are used in an amount of 0.1 to 15% relative to the unsaturated monomer to be emulsion polymerized.
Approximately 0.5 to 10% by weight is appropriate, and preferably 0.5 to 10% by weight.

Additionally, known anionic, nonionic and cationic surfactants may be added as necessary, specific examples of which include higher alcohols, higher alcohol oxidized alkylene adducts, alkylphenol oxidized alkylene adducts, and styrenated surfactants. Sulfate type of phenol alkylene oxide adduct, olefin sulfonate type such as α-olefin, long chain alkyl amine alkylene oxide adduct and di-long chain alkyl amine alkylene oxide adduct
Examples include ammonium salt type, sodium salt of N-(1,2-dicarboxyethyl)-N-octadecylsulfonic acid monoamide, and dialkylsulfosuccinate.

In addition, when using betaine ester as an emulsifier when obtaining the aqueous emulsion of the present invention, it is desirable to adjust the pH in the emulsion polymerization step to less than 6, preferably 3 to 6. This is undesirable because, in the emulsion polymerization step, aggregates exhibiting physical properties significantly different from those of the aqueous emulsion of the present invention are produced.

In obtaining the aqueous emulsion of the present invention,
Conventionally known emulsion polymerization methods can be used as they are in the presence of the unsaturated monomer and the emulsifier. For example, in the presence of a polymerization initiator corresponding to 0.1 to 5% by weight of the unsaturated monomer, a polymer of the unsaturated monomer is emulsified and dispersed in water at a concentration of 20 to 60% by weight, and emulsion polymerization is carried out. All you have to do is make it happen.

As a polymerization initiator, a water-soluble independent initiator or a water-soluble redox initiator used in ordinary emulsion polymerization is used, such as hydrogen peroxide, hydrogen peroxide and tartaric acid, citric acid, etc. In addition to combinations with acids, carboxylic acids such as ascorbic acid, combinations of hydrogen peroxide with oxalic acid, sulfinic acid, their salts, oxyaldehydes, water-soluble iron salts, etc., persulfates, percarbonates, etc. salts, peroxides such as perborates, and 2,2'-azobis(
Water-soluble products such as 2-amidinopropane) and its salts, 2,2'-azobis(N,N'-dimethylene-isobutyramidine) and its salts, 4°4'-azobis(4-cyanovaleric acid) and its salts, etc. Azo initiators can be used.

Furthermore, water-soluble nonionic polymer substances, anionic polymer substances, cationic polymer substances, and the like can be used in combination. Furthermore, plasticizers and pH adjusters commonly used in conventional methods can also be used in combination, if necessary.

Examples of nonionic polymeric substances include polyvinyl alcohol, dextrin, hydroxyethyl starch, starch derivatives such as hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.

Examples of anionic polymeric substances include polymers such as anionized hydroxyethyl cellulose, anionized starch, anionized guar gum, anionized chitosan, carboxymethyl cellulose, and anionized polyvinyl alcohol.

Further, examples of the cationic polymer substance include cationized hydroxyethyl cellulose, cationized starch, cationized guar gum, cationized chitosan, and polymers such as cationic (meth)acrylic acid amide and dimethyldiallylammonium chloride.

These nonionic polymeric substances, cationic polymeric substances, and nonionic polymeric substances can be used alone or in combination of two or more, but the amount added is relative to the monomer to be emulsion polymerized. 0.05-5% heavy view, preferably 0
．． It is appropriate to use 1 to 3% by weight.

Further, as the plasticizer, phthalate ester, phosphate ester, etc. can be used. Furthermore, ρ1 (salts such as sodium carbonate, sodium bicarbonate, and sodium acetate may be used in combination as regulators in the range of 0.01 to 3% by weight; however, as mentioned above, when a betaine ester emulsifier is used as an emulsifier) It is desirable to adjust the pH to less than 6.

The impregnation reinforcing agent for the hydraulic inorganic material molded body used in the present invention is:
Although the specific aqueous emulsion described above is an essential component, various additives commonly used as this type of impregnating reinforcing agent, such as rust preventives, anticorrosive agents, antibacterial agents, and preventive agents, may be added as necessary. mold agent.

Preservatives, colorants, fillers, pigments, etc. can be used in combination.

The reinforced hydraulic inorganic material molded article of the present invention is obtained by forming a hydraulic inorganic material such as mortar, concrete, or plaster into a predetermined shape using various methods, such as a mortar board, pile, pole, or humid pipe, in which the aqueous emulsion is an essential component. It is manufactured by impregnating it with a reinforcing agent and then drying it.

〔effect〕

The aqueous emulsion impregnated into the reinforced hydraulic molded product of the present invention has an average particle size of 1100 nm or less, has a crosslinked structure, has excellent static stability over a long period of time, and is calculated using the weight fraction method. Unlike conventional latex and water-based emulsions, it exhibits a glass transition temperature lower than the value of
It is possible to uniformly and stably impregnate the surface and interior of a hydraulic body with a polymer having good alkali resistance and mechanical strength.

Therefore, the reinforced hydraulic inorganic material molded product of the present invention can be used for various mortar, concrete, stone, etc. products.

Furthermore, it exhibits excellent effects when used in hume pipes, U-shaped grooves, etc. for domestic wastewater or wastewater from wastewater containing various inorganic and organic substances. Moreover, since the aqueous emulsion of the present invention is solvent-free and does not generate any harmful substances, it also has the advantage of being excellent in safety and being non-polluting.

〔Example〕

Next, in order to explain the present invention in more detail, Examples are shown below.

Example 1 Emulsifier 8 shown in Table 1 was placed in a glass reaction vessel equipped with a thermometer, stirrer, reflux condenser, nitrogen introduction tube and dropping funnel.
parts by weight and 150 parts by weight of water were charged and dissolved, and the inside of the system was purged with nitrogen gas. Separately, 156 parts by weight of an unsaturated monomer mixture consisting of 75 parts by weight of ethyl acrylate, 75 parts by weight of methyl methacrylate, 4.5 parts by weight of N-methylolacrylamide and 1.5 parts by weight of water was prepared. 15 parts by weight were added to the reaction vessel and emulsified at 40°C for 30 minutes. Then, after raising the temperature to 60°C, the polymerization initiator 2.2
9.'-azobis(N,N'-dimethyleneisobutyramidine) hydrochloride. OX 10-3mo Q e/water phase Ω
The unsaturated monomer was dissolved in 48.5 parts by weight of water and added to the reaction vessel, and immediately the remaining unsaturated monomer was continuously added dropwise into the reaction vessel over 30 minutes, and polymerization was carried out at 60°C. went. After dropping the unsaturated monomer, the mixture was aged at 60° C. for 60 minutes.

[Evaluation of Aqueous Emulsion] The average particle diameter, crosslinking property, film forming property, and glass transition temperature of the aqueous emulsion thus obtained were measured by the following methods.

Average particle size: Coulter Submicron Particle Analyzer (Coulter Electronics, Inc., USA, Coul
The average particle diameter was measured using a ter Model N4 type.

Cross-linking property: 30g of aqueous emulsion adjusted to have a solid content of 40% by weight + 12cm x 14cm
The mixture was uniformly cast onto a glass plate and air-dried at 25°C. The film obtained in this way is 2cm x 4cm
The sample was cut into pieces of 1.5 m, immersed in a Petri dish filled with benzene at 20°C for 48 hours, and evaluated as follows based on the degree of swelling and solubility of the film.

○; Film area before immersion in benzene (2cm x 4cm
) or slightly swollen.

Δ: The degree of swelling is large and the film shape is impaired.

×: The film was dissolved in benzene and became a uniform liquid.

Film forming property: A film was formed by air drying at 25°C, and the condition of the formed film was visually evaluated.

0: Forms a smooth and uniform film.

△: Forms a film with a reticulated surface.

×: No film is formed.

Glass transition temperature (Tg) Seiko Electronics Co., Ltd. thermal analysis measurement device (SSC5000)
Tg was measured using DS (1:200). The calculated value of Tg was calculated by the weight fraction method (described above).

[Evaluation of film characteristics]

The above aqueous emulsion 3 whose solid content was adjusted to 20% by weight 2
0 parts by weight was uniformly cast onto a 12 cm x 14 cm glass plate, air-dried to form a film, and the film properties were evaluated. Film properties were evaluated based on the following criteria.

Transparency: According to JIS K 6714, the haze value of the film was determined to be 41 g using an integral light transmittance 31 meter.

Water resistance: Cut the film into 2cm x 4cm pieces.

Immerse it in a petri dish filled with 20℃ water. Visually check the whitening of the film after soaking in the water. Judgment was made.

O: The film is transparent.

Δ: The film is translucent.

X: The film is opaque.

Adhesion: The surface of the film 1 was touched with a finger and the sticky feeling was evaluated based on the following criteria.

0; No sticky feeling Δ; Slightly sticky × = Sticky elongation and strength; Dumbbells were made according to JIS K-6781, and the strength at tensile break, elongation rate, and 50%, 100%, and 200% modulus strength was measured.

[Adjustment and performance evaluation of reinforced inorganic material molded bodies] 5, Ocm
X 5. Ocm X 1. A mortar board of Oc+a (cement/fine aggregate = 172 weight ratio) was washed with a polyoxyethylene nonylphenyl ether (EOP = 9.7) aqueous solution to remove scum from the surface, washed with water, and then air-dried at room temperature.

Next, this mortar plate is immersed for 5 minutes in a Petri dish containing a cloudy aqueous emulsion shown in Table 1 whose solid content concentration is 20% by weight, and then taken out from the Petri dish and air-dried at 25°C.

Next, the appearance (gloss), water resistance, acid resistance, alkali resistance, solvent resistance, and impact resistance of this impregnated polymer mortar board were evaluated according to the following criteria.

Outside [(Glossiness) 0; The surface of the mortar plate has a gloss similar to that of an aqueous emulsion and a dipping agent.

Δ: The surface of the mortar plate has poor gloss, and there is a coating film with some mesh-like stains.

×; The surface of the mortar plate does not exhibit the original gloss of the mortar plate.

A water-resistant, acid-resistant, alkali-resistant and solvent-resistant polymer mortar plate is prepared using deionized water, 1% by weight sulfuric acid aqueous solution, 1
Each sample was immersed in a Petri dish filled with a wt % aqueous sodium hydroxide solution and benzene at 25° C. for 6 months.

Next, water resistance, acid resistance, alkali resistance, and solvent resistance were evaluated according to the following criteria.

○: No whitening, swelling, or peeling on the surface of the mortar board.

Δ: There is some whitening, swelling, and peeling on the surface of the mortar board.

×: There is whitening, swelling, and peeling on the surface of the mortar board.

The impregnated polymer mortar plates used for determining impact resistance, water resistance, acid resistance, alkali resistance, and solvent resistance were air-dried at 25°C, dehydrated, and solvent removed, and then evaluated as follows according to JIS K-5400. did.

0; There are no cracks in the mortar plate.

Δ: There are some cracks in the mortar board.

×　; Mortar board cracks.

Samples Nos. 1 to 4 are examples of the present invention, and it can be seen that the reinforced inorganic material molded articles of the present invention exhibit excellent effects. Furthermore, the aqueous emulsion used in the present invention was good in that it did not generate any bad odor that would worsen the working environment during processing, and there was no problem of yellowing.

In addition, samples Nos. 5 to 7 are comparative examples.

Table 2 In accordance with JISK-6781, dumbbells were prepared from the aqueous emulsions of Sample Not (invention) and Sample No. 5 (comparative example), and a stress stress test was conducted. The results are shown in the drawing. As is clear from the drawings, the product of the present invention forms a film that is harder and more durable than that of the comparative example.

Example 2 Materials used: Cement: Portland cement made by Nippon Cement ■ (specific gravity 3.16) Fine aggregate: Fujitsuki river sand (surface dry specific gravity 2.61, coarse particle ratio 2.
65) Coarse aggregate: Fujitsuki Umagawa gravel (surface dry specific gravity 2.66, maximum dimension 20o++w) was used, and each material in the specified proportions shown in the table below was charged into a tilting mixer and kneaded for 3 minutes.

Next, reinforcing bars made up of axial reinforcements, spiral reinforcements, and diagonal reinforcements are put into a formwork, and the formed formwork of the hume pipe is placed on the rollers of a pipe making machine, and the above-mentioned process is carried out while rotating the formwork. The mixed raw materials were added and rotated until the inner surface of the mold was smooth.

After curing with steam as it is, demolding, and then curing in water, the inner surface of the hume tube was coated with the aqueous emulsion of samples Nos. 1 to 4 prepared in Example 1 (solid content concentration 4).
A reinforced humid tube was manufactured by impregnating the 0-layer fluorine to a solid content concentration of 2.5 kg/rrr and then air drying.

These reinforced fume pipes have been in good condition for many years without being eroded by industrial and domestic wastewater.

Example 3 Consisting of 8.0 parts by weight of the emulsifier shown in Table 3, 90 parts by weight of ethyl acrylate, 60 parts by weight of methyl methacrylate, 4.5 parts by weight of N-methylolacrylamide, and 2.5 parts by weight of water. 157 parts by weight of unsaturated monomer and 3.0 parts by weight of potassium persulfate as a polymerization initiator. OX 10-'mole/Mizusohi, Sodium Thiosulfate 3.OX 10-'mole
/Aqueous phase Ω and copper sulfate 5, OX 10-' mole/
It was dissolved in 47.5 parts by weight of water to form an aqueous phase Q, and emulsion polymerization was performed in the same manner as in Example 1 to prepare an aqueous emulsion.

Properties of the aqueous emulsion thus obtained, 20
The characteristics of the film formed by air-drying at .degree. C. and the performance as a reinforced hydraulic inorganic material molded article were measured and evaluated in the same manner as in Example 1. The results are shown in Table-3 and Table-4. Sample No.8-11
Sample N is an example of the present invention.

12 to 14 and 14' are comparative examples.

Table 4 Example 4 154.5 parts by weight of an unsaturated monomer mixture consisting of 60 parts by weight of n-butyl acrylate, 90 parts by weight of styrene and 4.5 parts by weight of 2-hydroxyethyl methacrylate and the following emulsifier 8 9.0 parts by weight 4.0 parts by weight and the polymerization initiator shown in Table 5. OX 10-'mo
Dissolve in 50 parts of water so that le/aqueous phase Q, and
Emulsion polymerization was carried out in the same manner as in Example 1 at the polymerization aging temperature shown in 5 to prepare an aqueous emulsion. The properties of the obtained aqueous emulsion, the film properties obtained by air drying at 20° C., and the performance evaluation of the reinforced hydraulic inorganic material molded article were measured according to Example 1. The results are shown in Table-5 and Table-6.

Samples Nos. 15, 16, 17, 19, 20 and 21 are examples of the present invention, and samples Nos. 18 and 22 are comparative examples.

In addition, the mechanical strength of the films of Sample Nos. 15-17, 19, 20 and 21 are all 150% or more in elongation, 150 Kg/aJ or more in tensile strength (strength at break), and the glass transition temperature is a calculated value of 24°C. On the other hand, all had good film-forming properties at temperatures below 20°C.

Table-6 Example 5 The following emulsifiers E-1 to E-5C and 2 of the heavy-duty section shown in Table-7
)1,50-C,90-(C-,1(,05COONa
E-2 separately, unsaturated monomer mixtures 11 to 3 shown below were prepared, and emulsion polymerization was performed in the same manner as in Example 1 to prepare an aqueous emulsion.

The properties of the obtained aqueous emulsion, the properties of the film formed by air drying at 25° C., and the performance evaluation of the reinforced hydraulic inorganic material molded article were measured according to Example 1. The results are shown in Table-7 and Table-8.

Samples Nos. 23 to 34 are examples of the present invention. In addition, the mechanical strength of the films of samples Nos. 23 to 34 all have an elongation rate of 1.
50% or more, tensile strength (strength at break) 150Kg/a
It was 1 or more.

Table 8 Example 6 The dispersion stability of the aqueous emulsions of Samples Nos. 1 to 34 was evaluated in the following manner. The results are shown in Table-9. The dispersion stability test was conducted as follows.

[Dispersion stability]

Aqueous emulsion 1 with solid concentration adjusted to 40% by weight 2
After putting 50 g in a 220 rm Q glass bottle and sealing it, it was left standing in a constant temperature room at 25 ° C for 6 months and in a constant temperature room at 45 ° C for 1 week, and the appearance, transmittance, viscosity, and average particle size were measured. The dispersion stability of the aqueous emulsion was evaluated.

The appearance, transmittance, viscosity, and average particle diameter were measured by the following methods.

External rating: Evaluated by visual judgment at 25°C according to the following criteria.

O: Transparent or translucent liquid Δ: Cloudy liquid ×: Cloudy paste or cloudy white separated into two layers Transmittance: Using a spectrophotometer (digital double beam spectrophotometer UVIDEC-320 manufactured by JASCO Corporation), wave light at 800 nm The absorbance under light irradiation was determined, and the light transmittance (%) was calculated.

Viscosity The viscosity at 25° C. was measured using a Nibruckfield viscometer (B-type viscometer manufactured by Tokyo Keiki Co., Ltd.).

Average particle size; Coulter Submicron Particle Analyzer (Coaltar Electronics, Inc., USA, Cou
The average particle diameter was measured using a 100% polyester (Model NJ).

The results are shown in Table 9 (1), (2) and (3).

In addition, samples 1 to 4.8 to 11.15 to 17.1 were subjected to a forced heating dispersion stability test that was left in a constant temperature room at 45°C for one week.
Example 1 Aqueous emulsions of 9-21 and 23-34
A film was formed according to Example 1, and the film characteristics were measured according to Example 1, and the performance of the reinforced hydraulic inorganic material molded product was evaluated. Transparency, water resistance, adhesive, solvent resistance (crosslinking), mechanical strength, and performance as a reinforced hydraulic inorganic material molded product were all almost the same as the results of Examples 1.2.3 and 4. The results were obtained. Figure 2 (A) and Figure 2 (B) show graphs of changes in particle size distribution before and after the dispersion stability test.
It is as follows.

In addition, sample No. 7 in Table 1-9 (1) had many extra large particles and could not be measured due to poor dispersion after testing at 45°C for one week. Therefore, both sample No. 1 and sample No. 7 were tested at 25°C,
Changes in particle size distribution after standing for 6 months were illustrated and compared.

[Brief explanation of drawings]

Figure 1 shows the product of the present invention (sample N) according to JISK-6781.
These are the measurement results when dumbbells were made from aqueous emulsions of o1) and a comparative amount (sample No. 5: film forming temperature: 35° C.) and a stress-strain test was performed on the dumbbells. Solid line: Inventive product Broken line: Comparative amount Figures 2 (A) and 2 (B) are for the inventive product (sample N).
ot) and a comparative amount (sample No.?) of the aqueous emulsion were left standing at 25° C. for 6 months.

Claims (1)

[Claims] (1) Molded reinforced hydraulic inorganic material characterized by being impregnated with an aqueous emulsion having an average particle diameter of 100 nm or less, a crosslinked structure, and a glass transition temperature lower than the value calculated by the weight fraction method. body.