JPS5964557A - Reformed cement composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention involves mixing a specific styrene-acrylic acid ester copolymer emulsion and a specific ethylene-vinyl acetate copolymer emulsion in a specific ratio into a cement composition. and water resistance (water absorption, water permeability),
This invention relates to a cement composition with improved wrinkle resistance, adhesive properties, etc.

Currently, cement compositions used in the architecture and civil engineering fields have a wide variety of applications, but the common performance requirements for these applications are workability (kneadability, coatability), water resistance (water absorption, Examples include water permeability), scratch resistance, and apron resistance. Particularly recently, the method of applying a thin layer of cement mortar as a base preparation material for concrete surfaces has become popular, and the above-mentioned performance is particularly required.

Conventionally, synthetic resin emulsion or synthetic rubber latex is used as an admixture for cement and sand.

A method of modifying the cement composition by mixing it with the pond aggregate has been proposed.

For example, in Japanese Patent Publication No. 5B-85816, C is HLB.
Polymerization was carried out using nonionic surfactants ranging from No. 14 to No. 1965. It has been shown to incorporate styrene-acrylic acid or glycidyl methacrylate copolymer emulsions into cement compositions.

In addition, in 'FJli 1985-48.285F3' publication, the glass transition temperature of unsaturated carboxylic acid ester and styrene in the presence of a nonionic emulsifier ranges from -10"C to +2"C.
It has been shown that 0°C and -10°C to +10°C can be polymerized in two stages and used for cement mixing. For example, Japanese Patent Publication No. 47-88054 discloses that an ethylene-vinyl acetate copolymer emulsion using polyoxyethylene nonylphenyl ether as an emulsifier is mixed into a cement composition. In addition, in Japanese Patent Publication No. 55-19913, C is polyvinyl/L'
7 II/: Incorporating a saturated monocarboxylic acid vinyl ester copolymer compound represented by ethylene-vinyl acetate as a protective colloid into a cement composition, and C in Japanese Patent Publication No. 52-25406. Japanese Patent Publication No. 54-27 (1983), by incorporating an ethylene-vinyl acetate-branched fatty acid vinyl ester copolymer emulsion using polyvinyl alcohol and polyoxyethylene octylphenyl ether as an emulsifier into a cement composition.
No. 870 discloses that an ethylene-vinyl acetate copolymer emulsion containing 5 to 2.5 hydroxyethyl cellulose as a protective colloid with an addition molar ratio of ethylene oxide and polyoxyethylene nonylphenyl ether as an emulsifier is used as a cement. In Japanese Patent Publication No. 55-19913 and Japanese Unexamined Patent Application Publication No. 56-11987, an ethylene-vinyl acetate-vinyl chloride copolymer emulsion using polyvinyl alcohol or polyvinyl alcohol and a nonionic emulsifier is mixed into a cement composition. 55-x99t4 discloses ethylene-saturated monocarboxylic acid vinyl ester using polyvinyl alcohol or polyvinyl alcohol and a nonionic emulsifier, such as polyoxyethylene nonylphenyl ether. The same thing is disclosed in JP-A-55-85444, in which a methyl methacrylate copolymer emulsion is mixed into a cement composition.

However, cement compositions containing these synthetic resin emulsions are still unsatisfactory in terms of water resistance (water absorption, water permeability), cracking resistance, adhesion, etc. ]
In view of the above-mentioned circumstances, the present inventors have conducted various studies aimed at improving the above-mentioned drawbacks of cement compositions. Water resistance (water absorption, water permeability), cracking resistance, and adhesion can be improved by mixing an emulsion made by mixing a vinyl acetate copolymer emulsion in a specific ratio into a cement composition. Heading This invention has led to this invention.

That is, in the present invention, (A) polyvinyl alcohol is added in an amount of 1 part by weight per 100 parts by weight of the resin solid content of the copolymer emulsion.
1 to 15 parts by weight of a styrene-acrylic acid ester copolymer emulsion containing 15 to 15 parts of polyvinyl alcohol per 100 parts by weight of the resin solid content of the copolymer emulsion, and a polyvinyl alcohol having an HLB of 10 or less. An ethylene/vinyl acetate copolymer emulsion containing 0.1 to 10 parts by weight of higher fatty acid ester of alcohol is prepared so that the resin solid content of (A) and that of (B) are 5:95 to 70:80. This is a modified cement composition made by mixing an emulsion blended with a cement composition.

This composition is a cement composition that has extremely low water absorption, excellent waterproof properties, and extremely high adhesive strength. That is, according to the present invention, when used as a groundwork preparation cement mortar for buildings, a cement mortar for repairs, a cement mortar for tiling, or a repair mortar for civil engineering, it not only enhances the adhesion to the base, but also improves the adhesive strength of conventional cement. The water absorption and waterproof properties, which were disadvantages of compositions, have been greatly improved, and a cement composition that does not cause cracks can be obtained.Also, the coating properties of old paints are good and there is no peeling or falling off. A cement composition for treatment is obtained.

Styrene-acrylic acid ester co-71 in the present invention
ft coalesced emulsion is styrene and 1 or α-
A copolymer emulsion of methylstyrene and an unsaturated carboxylic acid or ester represented by the general formula CH,,=C0OR' (wherein R is a hydrogen atom or a methyl group and R/ is an alkyl group having 1 to 8 carbon atoms) Typical examples of those represented by the general formula include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and 2-ethylhexyl esters of acrylic acid and methacrylic acid. It is also possible to use a mixture of two or more species. Furthermore, the glass transition temperature <Tf) of the copolymer is -10 to +20
in the range of °C.

Optionally, monomers copolymerizable with these monomers, such as acrylonitrile, acrylic acid, methacrylic acid, crotonic acid, mal/inic acid, itaconic acid, acrylamide, are added to a total of 100 parts by weight of these monomers. , N-methylolacrylamide, N-butoxymethylacrylamide, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, allylsulfonic acid, sodium vinylsulfonate, 2-acrylamide-2-methylpropanesulfonic acid, etc. may be used in a range of less than 10 multiple bearing parts.

In the present invention, the ethylene-vinyl acetate copolymer emulsion is one in which the Tf of the polymer is in the range of 110 to +20°C, and in some cases, the Tf of the polymer is in the range of 10 to +20°C.
For example, vinyl esters other than vinyl acetate, vinyl chloride, (meth)acrylic acid esters may be used in an amount of less than 50 parts by weight, and acrylic acid, Methacrylic acid, crotonic acid, maleic acid, itaconic acid.

Acrylamide, N-methylol acrylamide.

N-butoxymethylacrylamide, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxyethyl acrylate allyl sodium sulfonate, vinyl sulfonate sodium, 2-acrylamide-2-
Methylpropanesulfonic acid or the like may be used in an amount of less than 10 parts.

The polyvinyl alcohol used in the present invention has a degree of tenization of 70 to 99.5 mol% and an average degree of polymerization of about 200 to 2,70.
0 is preferably used.

It is also possible to use rc-modified polyvinyl alcohol, which is obtained by modifying the L polyvinyl alcohol with carboxylic acid, sulfonic acid, glyoxal, or the like. These polyvinyl alcohols are added to 100 parts by weight of the resin solid content of the styrene-acrylic acid ester copolymer emulsion and the ethylene-vinyl acetate copolymer emulsion.
It is preferable to use 1 to 15 parts by weight. More preferably, it is 1.5 to 10 parts by weight. If this amount is less than 1,000, it is difficult to obtain a stable emulsion, and if the nail exceeds 15 ffi, the water resistance will be poor.

Furthermore, the higher fatty acid ester of polyhydric alcohol used in the ethylene-vinyl acetate copolymer emulsion has an HLB of 1.
It is necessary that the HLB is 0 or less, preferably 8 or less, and more preferably 6 or less; if the HLB exceeds 10, the desired effect cannot be obtained. The polyhydric alcohols mentioned here include ethylene glycol, propylene glycol, butanediol, bentanediol, glycerin,
Watt, PentaL Ridolith, Arabit, Sorbitan, Sorbitan, Seven Nittu, Mannitan, Diethyle
□ Nglycol, diglycerin, taglycerin,
These include dipropyrene glycol, 1, 2, and 8 butanetriol, and higher fatty acid esters such as mono, di, tri, tetra, and penta are used. Higher fatty acids include saturated and unsaturated fatty acids, and C stands for oleic acid, linoleic acid, lyluic acid, capric acid, pelargonic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, and palmitic acid. acids, monogallic acid, stearic acid, nonadecanoic acid, arachidic acid, hepenic acid, (IJ-cyclohexyl fatty acid, o
l-phenyl fatty acid, 0)-cyclopentenyl fatty acid,
These include oxyfatty acids, abietic acid, and tall oil fatty acids. HLB of higher fatty acid esters of these polyhydric alcohols
If it is 10 or less, it may be an adduct of polyethylene oxide.

Specifically, fluvitan monooleate, fluvitan se antichiolate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, sorbitan trioleate, sorbitan tritol oil fatty acid ester, sorbitan monotol oil fatty acid ester, sorbitan castor Oil ether, stearic acid monoglyceride, lauric acid monoglyceride, oleic acid monoglyceride, polyglycerin laurate, polyglycerin stearate, pentaerythritol monostearate, and polyethylene glycol dilaurate, polyethylene glycol distearate below HLBIO,
Examples include esters of higher fatty acids of polyethylene glycol such as polyethylene glycol dioleate, polyethylene glycol monostearate, polyethylene glycol monolaurate, and polyethylene glycol monooleate.

If the amount of these is less than 0.1 parts by weight based on the resin solid content of the ethylene-vinyl acetate copolymer emulsion, there will be no improvement effect, and if it exceeds 10 parts by weight, the stability of the emulsion will be impaired, and the cement This is not preferable because the adhesive strength of the composition decreases.

The amount of the higher fatty acid ester of poly (ly II/coal) added is preferably 0.2 to 8 parts by weight, more preferably 0.8 to 6 parts by weight.

What is important in the present invention is that in the case of a styrene-acrylic acid ester copolymer emulsion, a small amount of an anionic surfactant or nonionic surfactant, which is usually used in emulsion polymerization, may be used in the polyvinyl alcohol base. but,
For ethylene/vinyl acetate copolymer emulsions, nonionic emulsifiers used in general emulsion polymerization such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether, or block copolymers of polyoxyethylene and polyoxypropylene are used. Even if it is an emulsifier with a low HL B, such as a general emulsifier such as Bell HLB, it cannot be used because it will not have the effect of the present invention. In the present invention, the ester is a higher fatty acid ester of a polyhydric alcohol and has an HLB of 10 or less.

The method for producing the ethylene-vinyl acetate copolymer fluoride used in the present invention is not particularly limited, but for example, polyvinyl alcohol and HLB are
A method of emulsion polymerization of ethylene, vinyl acetate, and other monomers as necessary in an aqueous medium by a conventional method in the presence of a higher fatty acid ester of a polyhydric alcohol of 0 or less, and a method in which the above monomers are polymerized in the presence of polyvinyl alcohol. Preferably, a method is employed in which a higher fatty acid ester of a polyhydric alcohol having an HLB of 10 or less is mixed into an emulsion obtained by emulsion polymerizing the body in an aqueous medium by a conventional method.

In the present invention, the blending ratio per resin solid content of the styrene-acrylic ester copolymer emulsion (A) and the ethylene-vinyl acetate copolymer emulsion (B) is (A):(B) 5 = 95 ~ The proportion of (A) is 70:80, preferably 10:90 to 60:40. If the proportion of (A) is less than this range, the adhesiveness will be poor, and if it is too much, the water absorption will be poor. Not yet (B)
If it is less than this range, the water absorption property will be poor, and if it is more than this range, the adhesive property will be poor and the purpose cannot be achieved.

There is no particular restriction on the amount of the mixed emulsion of the technical fulms (A) and (13) to be added to the cement composition, but the amount generally used for each purpose is sufficient.

That is, since economic efficiency is important for C in a cement composition, it is appropriate to add 3 to 100 parts by weight of the fluorophore in terms of solid content per 100 parts by weight of cement in the cement composition.

However, it is also within the scope of the present invention to separately mix the upper fusion (Δ) and CB> with the cement, since the effects of the present invention can be exhibited.

The present invention will be specifically explained below with reference to °C Examples, but the present invention is not limited thereto.

Example 1 A resin solid content of 40.2% (by weight) containing 8 parts of sulfonic acid-modified polyvinyl alcohol with a degree of tenization of 88 mol% (the same applies below) and 0.2 parts of sodium polyacrylate per resin solid content. % (same as below) Styrene at 18℃
Butyl acrylate co-claw coalescing emulsion (A') and 4.5 parts of polyvinyl alcohol with a tenation degree of 88 mol% per resin solid content and sorbitan trioleate (HL
B, 1.8) Resin solids containing 1.0 parts 56
．． 1%, TyooC's ethylene-vinyl acetate copolymer solution (B') was added to the resin surface J: per minute (A') 30
1 part and 70 parts of (B') were mixed to obtain a uniform and stable fulsion. The resin solid content was adjusted to 45%, and 10 parts of the powder was mixed uniformly with 100 parts of cement, 100 parts of silica sand No. 7, and 0.2 parts of Hymetrose 90Sf14,000 (manufactured by Shin-Etsu Chemical Co., Ltd.). A cement mortar composition was obtained by adding 25 parts of water and uniformly kneading the mixture.

This cement mortar composition was tested for normal adhesive strength and water absorption according to the cement filler evaluation method of the Housing and Urban Development Corporation. The results are shown in the table.

Example 2 The same procedure as in Example 1 was carried out except that (A') was changed to 60 parts and (B') was changed to 40 parts. The results are shown in the table.

Example 3 30 parts of (A') in Example 1 and tenation degree of 88 mol%
Resin solids content 58.2%, containing 4.8 parts of polyvinyl alcohol and 2.0 parts of sorbitan trioleate, T
70 parts of an ethylene-vinyl acetate-vinyl chloride copolymer emulsion (B') having an fI of 5 DEG C. was mixed and the same procedure as in Example 1 was carried out to obtain a cement composition C, which was then tested. The results are shown in the table.

Comparative Example 1 A cement composition was obtained and tested in the same manner as in Example 1 except that only C(A') was used as an emulsion. The results are shown in the table. The solid content of the tazoshi resin was 40.2%, and a C test was conducted by adding 11.2 parts and 28.8 parts of water to 100 parts of powder as a composition of cement 4 and r-retal.

Comparative Example 2 A C cement composition was obtained and tested using the same method as in Example 1 except that only (B') was used instead of C (A'). The results are shown in the table.

Comparative Example 3 A cement composition was obtained and tested in the same manner as in Example 3, except that (A') was not used as the emulsion and only (B') was used. The results are shown in the table.

Comparative Example 4 A mixture of 80 parts of (A') and 20 parts of (B') in Example 1 was used. The resin solid content of this emulsion ζ is 42.6%, and the cement mortar composition is powder X.
A test was conducted by adding 15 parts of 10 and 24.5 parts of water to 00 parts. The results are shown in the table 0 Comparative Example 5 80 parts of (A') and 20 parts of (B') of Example 3 were mixed and used. As desired, this emulsion has a resin solid content of 4
2.3%, powder 10 as cement mortar composition
The test was conducted by adding 10.6 parts to 0 parts and 24.4 parts of water. The results are shown in the table.

Procedural amendment (voluntary) J February 1, 1980 Commissioner of the Patent Office Mr. Aio Wakasugi 1, Indication of the case 1982 Patent Application No. 175172 2, Name of invention Modified cement composition 3, Amendment Relationship with the case of a person who does
209) Sumitomo Chemical Co., Ltd. Representative Hijikata
Take 4, Agent address Sumitomo Chemical Co., Ltd., 5-15 Kitahama, Higashi-ku, Osaka, -1 Shishi 5, Column 6 for detailed explanation of the invention in the specification subject to amendment, Contents of amendment (+,) Details Book tube 1, line 1, page 5, line 12, page 6, line 2, page 7, line 8, page 9, line 14, page 12, line 16~
In line 17 and page 14, line 4, "acrylic acid" is corrected to "unsaturated carbonic acid."

(2) On page 2, line 11, the word "epoxy resistance" was replaced with "efflorescence resistance" and the color was corrected.

(3) On page 3, lines 2-3, the phrase "polymerized styrene-acrylic acid" is corrected to "polymerized styrene-unsaturated carboxylic acid."

(4) Equation (5) on page 7, line 6. Delete "and 1" from pages 4 to 5 on page 7.

(6) On page 7, line 8, the phrase “unsaturated carboxylic acid, ester” is corrected to “unsaturated carboxylic acid ester J.”

(7) 1 more on page 7, lines 15-16...
It is in. ” will be deleted.

(8) In the same No. 7 M, line 4, amend the statement ``emulsion is styrene-1, but 1-emulsion is styrene in which the glass transition temperature ('rg) of the polymer is in the range of -10 to +20°C.''

(9) 1″ on page 7, line 17, depending on the case, -・te-1
The statement was corrected to "further depending on the circumstances."

(]O) On page 9, line 3 of the same page, "toarylsulfonic acid" should be corrected to "toallylsulfonic acid."

(11) On page 13, line 7, the word ``level'' is corrected to ``1-level''.

(12) In the 11th line of page 13, the phrase ``It is a thing.'' is corrected to ``It must be a thing.''

that's all

Claims (1)

[Claims] (A) a styrene-unsaturated carboxylic acid ester copolymer toggle containing 1 to 15 parts by weight per 100 parts by weight of resin solid content of R-marinated vinyl alcohol; (B) Ethylene containing 1 to 15 parts by weight of polyvinifle alcohol per 100 parts by weight of resin solid content of the copolymer emulsion and 0.1 to 10 parts by weight of higher fatty acid ester of polyhydric alcohol with HLB of 10 or less. - Vinyl acetate copolymer emulsion (A)
The weight ratio of the resin solid content of (B) to that of (B) is 5:95 to
A modified cement composition obtained by mixing an emulsion blended at a ratio of 70:80 into a cement composition.