JPS63191883A - Emulsified concrete sealer composition having excellent stability and its preparation - Google Patents

Abstract

PURPOSE:To obtain the title sealer composition which is not hazardous from safety and hygienic viewpoints, and has excellent adhesiveness and water resistance and in particular excellent low-temperature stability, by using as its principal constituents a chlorinated polymer, a plasticizer, and a thickening agent comprising a cellulose derivative. CONSTITUTION:This sealer composition is prepared by using as its principal constituents a chlorinated polyolefin (e.g., a chlorinated polyethylene) or modified chlorinated polyolefin (e.g., a maleic modified chlorinated polyethylene), a plasticizer, and a cellulose derivative (e.g., hydroxypropylmethylcellulose), and adding an organic solvent, an emulsifying agent, and water thereto. With conventional emulsified sealers of, e.g., acrylic base and vinyl chloride base, there may be neither fire hazard nor hazard from safety and hygienic viewpoints which may be encountered with solvent- type sealers; however, those conventional emulsified sealers are lacking in adhesiveness, water resistance, and in particular low-temperature stability. A sealer of this invention does not have these defects and has excellent adhesiveness and water resistance and in particular excellent low-temperature stability by virtue of the use of a chlorinated polymer and in addition the use of the above-mentioned thickening agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a concrete sealer for constructing elastic tiles, and particularly to an emulsion type sealer.

Elastic tiles have been widely used in recent years for new or renovated buildings, as they are extremely effective in preventing water from seeping through cracks due to their aesthetic appearance, waterproofness, weather resistance, and especially the elasticity of the paint film. .

When installing these elastic tiles, it is common to apply a sealer treatment to the concrete surface.The present invention uses chlorinated polyolefin or modified chlorinated polyolefin, which has excellent adhesion, water resistance, and particularly low-temperature stability. This article is about emulsion type sealers.

(Prior art) Conventionally, acrylic, epoxy,
Vinyl chloride type sealers, salt rubber type sealers, etc. are used as organic solvent type sealers or emulsion type sealers. However, solvent-based coatings are not only toxic to the installer, but also pose a fire risk, and also volatilize a large amount of organic solvent into the atmosphere after application, causing air pollution, which is a serious problem. Moreover, it is a big loss from the point of view of resource conservation.

Emulsion-type products made using conventional polymerization methods have extremely low safety and health risks, but they have various drawbacks in terms of performance. Compared to solvent-based products, they are inferior in adhesion and water resistance, and are generally unsatisfactory in terms of stability, especially in low-temperature stability.
It had major drawbacks.

On the other hand, when renovating and painting the exterior walls of buildings, it is not only necessary to simply repair deteriorated and damaged parts, but also to improve durability by impregnating and reinforcing treated materials such as concrete and making them water repellent. More than anything else, sealers are required to have high durability.

Therefore, we use chlorinated polyolefin or modified chlorinated polyolefin, which has excellent durability and chemical resistance, and is excellent against concrete, etc., and is less dangerous in terms of health and safety.
The emergence of an emulsion-type sealer with excellent adhesion, water resistance, and especially low-temperature stability has been awaited.

[Problem that the invention seeks to solve]

When applying a sealer in winter or in a cold region, it is desirable that the emulsion does not freeze during storage, and even if it freezes, it is essential that it returns to its original normal emulsion when heated.

However, even chlorinated polyolefins with polar groups do not have sufficient low-temperature stability, and emulsions of modified chlorinated polyolefins in particular do not aggregate and return to their original normal emulsion even after freezing and thawing, making them unusable. As a result, the original performance was not achieved, and a solution was strongly desired.

Various proposals have been made regarding emulsification using chlorinated polyolefin resins. For example, the special public service 53-87
According to No. 29, only an emulsion concentration of about 5 to 65% is proposed for use as a concrete sealer. Furthermore, according to Japanese Patent Application Laid-Open No. 54-153832, a chlorinated polyethylene water-based paint is proposed for coating SL tanks of ships and the like.

According to Zarani Tokuko Sho 61-49276@, 1. Apply chlorinated polyolefin as an emulsion type sealer,
Waterproofing construction methods have been proposed in which a waterproofing agent is then applied, and detailed explanations of emulsion formation have been provided for each method.

However, all of these are different from the problem that the present invention aims to solve, especially the improvement of low-temperature stability.

As a result of intensive studies on many emulsion formulations and their coating performance, the present inventors found that emulsion-type sealers made of chlorinated polyolefins or modified chlorinated polyolefins have low safety and health risks, and have good adhesion and water resistance. The present inventors have discovered that this material has excellent properties, particularly low-temperature stability, and has accomplished the present invention.

[Means for solving problems]

Usually, emulsion type products are required to have the following performance.

(1) The emulsion should be stable under normal conditions and should not separate and settle even after the addition of pigments, etc.

(2) No repellency during application.

(3) There is no breakage of the emulsion during coating by airless spraying, etc., and mechanical stability is good.

(4) Stable at low temperatures, especially fast freeze-thaw and no aggregation.

(5) It is easy to form a continuous coating film.

In order to have such performance, the present inventors created a sealer composition by dissolving chlorinated polyolefin or modified chlorinated polyolefin and a plasticizer in an organic solvent, dispersing it in water containing an emulsifier, and emulsifying it using an emulsifying machine. . However, the viscosity of the emulsion made here is low and it easily separates during storage, and it also causes cissing during coating.
When pigments were added, separation sedimentation was observed, which required thickening of the emulsion.

However, although they generally have a thickening effect, they are still insufficient because some have a significant drop in water resistance or cause emulsion aggregation at low temperatures.

Therefore, as a result of repeated studies on various substances with thickening effects, the inventors found that among water-soluble polymers, nonionic cellulose derivatives have excellent adhesion and water resistance, and are especially excellent in low-temperature stability. The present invention has been completed based on the discovery that

That is, the present invention uses 5 to 150 parts of plasticizer, 50 to 500 parts of organic solvent, 50 to 2000 parts of water, and 0.1 part of emulsifier to 100 parts by weight of chlorinated polyolefin or modified chlorinated polyolefin (hereinafter referred to as parts). ~10 parts, thickener 0.
This invention relates to an emulsion type sealer characterized in that it consists of 2 to 4 parts.

The solvent composition of the emulsion type sealer of the present invention is such that a part or most of the conventional solvent type organic solvent such as toluene is replaced with water, and the organic solvent is a higher boiling point solvent than the conventional solvent such as toluene. The aromatic solvent portion of the organic solvent used is reduced as much as possible, resulting in significant improvements in terms of flammability, toxicity during construction, air pollution, and resource conservation.

In addition, the significance of using some organic solvent in this emulsion type is that if no organic solvent is used, it is difficult to make an emulsion, and even if it is made into an emulsion, a continuous film will not be formed and the performance as a sealer will not be expressed. This is because you don't get it.

Next, each component of the present invention will be specifically described.

The chlorinated polyolefin used in the present invention is high density or low density polyethylene.

Included are crystalline or non-crystalline polypropylene, chlorinated ethylene-propylene copolymers, and the like. Although chlorination may be carried out by any method, it is preferably obtained by a solution method by blowing chlorine gas under irradiation of a catalyst or ultraviolet rays.

The chlorinated polyolefin used in the present invention, which is obtained by chlorinating a polyolefin modified with one or more compounds selected from the group consisting of unsaturated polycarboxylic acids and their acid anhydrides, is produced by a known method. can do.

One example of its manufacturing method is polyolefin resins, such as high-density or low-density polyethylene.

Crystalline or non-grade polypropylene, ethylene-propylene copolymer, etc. are thermally melted singly or in combination of two or more, and if necessary, the molten polyolefin resin is reduced in viscosity by thermal decomposition, and the molten resin is produced in a batch or continuous process. is obtained by modifying the polycarboxylic acid with an unsaturated polycarboxylic acid and its acid anhydride in the presence of a radical generator, and then reacting with the same chlorination method as described above.

Examples of the radical generator used in the modification reaction include di-tert-butyl peroxide.

These include peroxides such as tert-butyl hydroperoxide and benzoyl peroxide, and azonitrile such as azobisisobutyronitrile and azobisisopropionitrile. Examples of unsaturated polycarboxylic acids and their acid anhydrides used in the modification reaction include maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, and fumaric acid.

The saponification value of the polyolefin modified with the unsaturated polycarboxylic acid and its acid anhydride used in the present invention is 6 to 60.
and preferably 10 to 40.

If the saponification value is less than 6, no modification effect will be observed, and if the saponification value exceeds 60, the stability of the emulsion will deteriorate and it will be difficult to form an emulsion.

In addition, the chlorine content Φ of the chlorinated product used in the present invention is 40
~75% by weight, preferably 45-70% by weight. If the chlorine content is 40% by weight in the ungrooved area, the resin will be too soft, and if the chlorine content exceeds 75% by weight, the resin will be too hard and the coating will easily crack, and both will not perform well as a sealer. Not done.

The plasticizer is chlorinated polyolefin or modified chlorinated polyolefin (hereinafter abbreviated as chlorinated polyolefin, etc.) 1
The amount is 5 to 150 parts per 00 parts, preferably 10 to 150 parts.
It is 100 copies. If the amount used is less than 5 parts, it will be difficult to form a continuous film, and even if a film is formed, the resin will be too hard and cracks will easily occur in the coating, and if the amount used exceeds 150 parts, it will be difficult to form a continuous film. are too soft and cannot exhibit their performance as a sealer.

Various commercially available plasticizers can be used as the plasticizer, such as phthalate esters and phosphate esters.

Examples include chlorinated paraffin or epoxy. Preferred plasticizers are those based on chlorinated paraffins and epoxies.

The amount of organic solvent used to dissolve the chlorinated polyolefin and plasticizer is 50 to 500 parts, preferably 100 to 3 parts, per 100 parts of the chlorinated polyolefin, etc.
It is 00 copies. If the amount used is less than 50 parts, the solution viscosity is high, resulting in poor emulsifying and dispersing properties and poor stability, while if it exceeds 500 parts, it poses health and safety problems as an emulsion sealer. Toluene is an organic solvent that can be used.

Xylene, solvent naphtha, Tsurpetz 100 and 150. Methanol 200 and 1ooo, ethyl acetate, butyl acetate, cellosolve acetate.

Methoxybutyl acetate, and other diluting solvents such as methanol, ethanol, and mineral spirits.

Examples include methylcyclohexane and ethylcyclohexane.

Preferred solvents include solvent naphtha, Tsurpetz 100 and 150, which are relatively high boiling point solvents that improve flammability, toxicity, and film-forming properties of chlorinated polyolefins.
．． Methanol 200 and 1000. Most preferably, methanol 2001 or methanol 1000, which has a low aromatic content. It is a mixture of Tsurupetsu 100 and non-aromatic.

The amount of emulsifier is 0.1 to 10 parts, preferably 0.5 to 5 parts, based on 100 parts of chlorinated polyolefin. If the amount used is less than 0.1 part, the emulsion stability of the emulsion will be poor, and if it exceeds 10 parts, the water resistance of the resin film will decrease.

Various surfactants can be used as emulsifiers, but nonionic surfactants are particularly suitable.

Various commercially available nonionic surfactants can be used, but in order to make a good oil-in-water emulsion, for example, polyoxyethylene alkylphenol ether, polyoxyethylene sorbitan alkyl ester, polyoxyethylene Preferably, sorbitan fatty acid esters or the like, used alone or in combination, have a 1-ILB of 15 or more. Alternatively, an anionic surfactant such as alkylbenzene sulfonate may be used in combination.

The amount of water is i for 100 parts of chlorinated polyolefin, etc.
oo~2000 parts, preferably 200~1000 parts
Department. If the amount used is less than 10,000 parts, safety such as flammability and toxicity cannot be obtained. If the amount exceeds 2,000 parts, the emulsion concentration decreases and a satisfactory film formation cannot be obtained, and the performance as a sealer is not exhibited.

The amount of the thickener is 0.2 to 4 parts, preferably 0.3 to 2 parts, based on 100 parts of the chlorinated polyolefin.

If the amount used is less than 0.2 parts, the low temperature stability of the emulsion will be insufficient, and if it exceeds 4 parts, the water resistance will be poor and neither will be sufficient as an emulsion for a sealer.

Thickeners play a very important role in emulsions. That is, the entire emulsion system can be protected by the performance of the thickener, such as prevention of sedimentation after addition, fluidity during application, prevention of coating film repellency, and long-term stability against temperature changes.

Conventional emulsion polymerization type emulsions have poor storage stability, particularly low-temperature stability, and tend to aggregate and become unusable without recovering to freeze-thaw reconstitution emulsions.

The chlorinated polyolefins used in the present invention have polarity, and sufficient consideration must be given to various stability aspects during emulsion and gelation.

That is, many types of so-called water-soluble polymers are commercially available as thickeners, and many of them have excellent thickening effects. However, low-temperature stability is not sufficient, and cellulose ethers, which are nonionic polymers of cellulose derivatives, in particular methyl cellulose and hydroxyethyl cellulose, can be used without impairing the performance of chlorinated polyolefins. It was recognized that it has excellent low temperature stability. Preferably, the methylcellulose derivatives hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, and hydroxyethylcellulose are used alone or more preferably in combination.

Depending on the purpose of use, various additives such as pigments, stabilizers, and antifoaming agents may also be used.

[For production]

In the present invention, when emulsifying chlorinated polyolefin or modified chlorinated polyolefin, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, and hydroxy ethyl cellulose, which are nonionic polymers among cellulose derivatives, are used singly or preferably in combination to achieve excellent low-temperature stability. The present inventors have discovered that the present invention exhibits excellent effects, and have completed the present invention.

In other words, further protection is provided by the interaction between the stability against various chemicals due to the nonionic nature of cellulose derivatives, the nonionic surfactant properties of methylcellulose that lowers the interfacial tension, and the remarkable stability of hydroxyethylcellulose at low temperatures. It is thought that colloidal properties were expressed.

The obtained emulsion was extremely stable at low temperatures, and the present invention was completed.

[Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Note that parts and percentages in the examples are parts by weight and percentages by weight. Moreover, all the test methods in the examples were conducted according to JIS A-6910.

(1) Low-temperature stability test A stability test after freezing and thawing of an emulsion is conducted to visually observe the absence of lumps and separation and aggregation of the composition. (-5℃/18 hours → Maximum temperature/6 hours) x 3 cycles (2) Water permeability test In a test of the sealing ability of the sealer to the base, a certain area of slate board coated with the sealer was left standing for 24 hours, Measure water permeability.

(3) Adhesion strength test The adhesion strength of the sealer to the emulsion paint surface for elastic tiles and the mortar surface is measured.

Standard condition: After applying an intermediate coating material on top of the sealer coating, leave it to cure for 14 days. The adhesion strength is then measured.

After flooding: After curing, leave the top 5m, and in that state, 1
Let stand for 0 days. After that, 50'C/1 day, roughly room temperature/
After leaving it for one day, measure the adhesion strength.

Repeated heating and cooling: After repeating the operation (20°C 718 hours → -20°C/3 hours → 50°C/3 hours) as one cycle 10 times, visually inspect the multi-layer coating material for peeling, cracks, and blisters. and then measure the adhesion strength.

(4) Repeated heating and cooling test Observe the changes in the elastic tile surface after the above heating and cooling cycles.

Judgment criteria: Peeling, cracking, blistering××・・・・・・Many×・・・・・・Medium△・・・・・・・Less O・・・・・・Very slight◎ ...... None Example 1 100 parts of chlorinated polyethylene (chlorine content 60%),
30 parts of chlorinated paraffin (Toyovarax A-40゜Toyo Soda Kogyo @J) in 130 parts of Tsurpets 1000 (Exxon Chemical ■) and 20 parts of methylcyclohexane,
Dissolve by heating at 50-60°C to obtain a transparent solution. This solution was preliminarily mixed with a nonionic surfactant (polyoxyethylene alkyl ether, nirasan nonion, -220, HLB=1).
8.2 NOF■) Dissolve 3 parts in 230 parts of water (some of which will be used for dispersing and dissolving titanium oxide and methylcellulose) and add to the solution heated to 50 to 60°C. While doing so, use a homomixer (special kikae industry ■1)
M type) was used to strongly emulsify. Next, while maintaining the temperature, a titanium oxide slurry prepared in advance and hydroxypropyl methylcellulose (Metrose 65S) as a thickener were added.
H, Shin-Etsu Chemical ■), 13 parts each in terms of solid content,
1.5 parts of the emulsion was added to the unthickened emulsion while stirring it using a conventional stirrer to obtain a uniformly thickened emulsion with a solid content of 28%.

Regarding the obtained emulsion, the above JIS A-69
10, the results are shown in Table 1.
The results were good as shown in the figure.

Example 2 100 parts of chlorinated polypropylene (chlorine content 66%),
30 parts of chlorinated paraffin (same as before).

10 parts of epoxidized soybean oil (Adekasizer 〇-13O3, Asahi Denka Kogyo ■) to 1 part of Swazol 200 (Marukubi Sekiyu ■)
Dissolve with heating in 50 parts to make a clear solution. This solution was preliminarily mixed with Manon P9 erosinemia 1 and Saliva ton one side activator (polyoxyethylene alkyl ether sodium sulfate, emal 2).
0C, Kao Soap ■) was dissolved in 300 parts of water (a portion of which was used for dispersing and dissolving titanium oxide and hydroxyethyl cellulose), and heated in the same manner as in Example 1 to emulsify and thicken. . Hydroxyethyl cellulose (Natrosol 250tlR, Vercules ■) was used as the thickener.

The low temperature stability results were good as shown in Table 1.

Examples 3 to 5 In Example 3, maleic anhydride-modified chlorinated polyethylene having a saponification value of 10 was used as the modified chlorinated polyolefin.

In Example 4, maleic anhydride-modified chlorinated polyethylene having a saponification value of 24 was used as the modified chlorinated polyolefin.

In Example 5, maleic anhydride-modified chlorinated polypropylene having a saponification value of 18 was used as the modified chlorinated polyolefin.

The low-temperature stability was good in all cases as shown in Table 1.

Comparative Examples 1 to 7 As in Comparative Example 1, the anionic surfactant and thickener were CM
For those using C, after freezing and thawing in the low temperature stability test, Table -
Layer separation occurred as shown in 2.

Comparative Example 2, which used a nonionic surfactant with an HLB of 10 or less as an emulsifier and sodium alginate as a thickener, caused separation and lumps in the low temperature stability test as shown in Table 2.

As in Comparative Example 3, a product using maleic anhydride-modified chlorinated polyethylene and an acrylic acid/acrylic acid ester copolymer as a thickener coagulated in the low temperature stability test.

Comparative Example 4, which used maleic anhydride-modified chlorinated polyethylene with a saponification value of 40 and a cationic surfactant, agglomerated in the low temperature stability test.

As in Comparative Example 5, an emulsion using maleic anhydride-modified chlorinated polypropylene having a saponification value exceeding 60 and CMC as a thickener coagulated when left at room temperature after emulsion.

Comparative Example 6 was a commercially available acrylic emulsion type sealer made by emulsion polymerization, but as shown in Table 2, it agglomerated and separated.

Regarding the systems with excellent low temperature stability of Examples 1 to 5, JIS
Table 3 shows the results of testing for suitability as a concrete sealer according to the A-6910 test method.

Comparative Example 7 is a dissolving type sealer in which the chlorinated polypropylene type used in Example 2 was prepared as a toluene solution and subjected to the test.

As shown in Table 3, it can be seen that the emulsion type according to the present invention is in no way inferior to the conventional solvent type.

In general, when compared with the emulsion type of Comparative Example 6 produced by the conventional emulsion polymerization method, it was found that the chlorinated polyolefin type, which essentially has water resistance, is superior.

〔Effect of the invention〕

Thus, according to the present invention, adhesion and water resistance.

Emulsifying a chlorinated polymer with excellent chemical resistance, etc.
After that, the product thickened with a cellulose derivative exhibited excellent performance in low temperature stability according to JIS A-6910 without impairing the original performance as described above.

The emulsion-type concrete sealer of the present invention containing this material greatly improves the safety and health hazards that could not be obtained with conventional solvent-type concrete sealers, improves functionality, and has stability that can greatly contribute to resource conservation. We have completed an excellent emulsion-type concrete sealer composition and its manufacturing method.

Procedural Amendment (Imported) April 24, 1985 1. Case Indication 1988 Patent Application No. 24288 @ 2. Name of the Invention Emulsion type concrete sealer with excellent stability Address 1-4 Marunouchi, Chiyoda-ku, Tokyo -5 name
(234) Sanyo Kokusaku Pulp Co., Ltd. 4, Agent address: 16 Kanda Kita Jorimono-cho, Chiyoda-ku, Tokyo 1
01 3rd floor of the British Building As shown in the attached document 1. Name of the invention: Emulsion-type concrete sealer composition with excellent stability and method for producing the same 2. Claims (1) A chlorinated polymer, a plasticizer, and a cellulose derivative. An emulsion-type concrete sealer composition that has a main component and complies with JIS A-6910 (low-temperature stability test).

(2) The emulsion type concrete sealer composition according to claim 1, wherein the chlorinated polymer is a chlorinated polyolefin or a modified chlorinated polyolefin.

(3) The chlorinated polyolefin is chlorinated polyethylene.

The emulsion type concrete sealer composition according to claim 2, which is a chlorinated polypropylene or a chlorinated ethylene-propylene copolymer.

(4) Chlorinated polyethylene in which modified chlorinated polyolefin is modified with one or more compounds selected from the group consisting of unsaturated polycarboxylic acids or their acid anhydrides;
The emulsion type concrete sealer composition according to claim 2, which is chlorinated polypropylene or chlorinated ethylene-propylene copolymer.

(5) The emulsion type concrete sealer composition according to claim 1, wherein the cellulose derivative is methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, and hydroxyethylcellulose.

(6) The main constituents are chlorinated polyolefin or modified chlorinated polyolefin, a plasticizer, and a cellulose derivative, in addition to which an organic solvent and an emulsifier.

A method for producing an emulsion-type concrete sealer characterized by adding water.

3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a concrete sealer for constructing elastic tiles, and particularly to an emulsion type sealer.

Elastic tiles have been widely used in recent years for new or renovated buildings, as they are extremely effective in preventing water from seeping through cracks due to their aesthetic appearance, waterproofness, weather resistance, and especially the elasticity of the paint film. .

When installing these elastic tiles, the general specification is to apply a sealer treatment to the concrete surface.The present invention uses chlorinated polyolefin or modified chlorinated polyolefin, which has excellent adhesion, water resistance, and particularly low-temperature stability. This relates to emulsion type sealers.

[Conventional technology]

BACKGROUND ART Acrylic, epoxy, vinyl chloride, salt rubber, and other organic solvent-based sealers or emulsion-based sealers have conventionally been used as sealers for elastic tiles on surfaces such as concrete, mortar, and asbestos slate. However, solvent-based paints are not only toxic to the installer, but also pose a risk of fire, and because they volatilize a large amount of organic solvent into the atmosphere after application, they cause air pollution, which is a serious problem. Furthermore, it is a big loss from the point of view of resource conservation.

The emulsion type produced by the conventional emulsion polymerization method has extremely low safety and health risks, but has various drawbacks in terms of performance. Adhesive properties compared to solvent type.

It had poor water resistance, was unsatisfactory in terms of stability, and had major drawbacks, especially in low-temperature stability.

On the other hand, when renovating and painting the exterior walls of buildings, it is not only necessary to simply repair deteriorated and damaged parts, but also to improve durability by impregnating and reinforcing treated materials such as concrete and making them water repellent. More than anything else, sealers are required to have high durability.

Therefore, we use chlorinated polyolefin or modified chlorinated polyolefin, which has excellent durability and chemical resistance, and also has excellent performance on concrete surfaces, to achieve adhesion and water resistance with less danger in terms of health and safety. The emergence of an emulsion-type sealer with excellent low-temperature stability has been awaited.

(Problem to be solved by the invention) When applying a sealer in winter or in a cold region, it is desirable that the sealer does not freeze during storage, and even if it freezes, it is essential that it returns to its original normal emulsion when heated. It is.

However, even chlorinated polyolefins with polar groups do not have sufficient low-temperature stability, and emulsions of modified chlorinated polyolefins in particular do not aggregate and return to their original normal emulsion even after freezing and thawing, making them unusable. As a result, the original performance was not achieved, and a solution was strongly desired.

Various proposals have been made regarding emulsification using chlorinated polyolefin resins. For example, the special public service 1987-1987
According to No. 29, only an emulsion concentration of about 5 to 65% is proposed for use as a concrete sealer. According to Japanese Patent Application Laid-Open No. 153832/1983, a chlorinated polyethylene water-based paint is proposed for coating ships, bridges, tanks, etc.

Furthermore, according to Japanese Patent Publication No. 61-49276, a waterproofing method is proposed in which a chlorinated polyolefin is applied as an emulsion type sealer, and then a waterproofing agent is applied, and both methods provide detailed explanations on emulsion formation. is being done.

However, all of these are different from the problem that the present invention aims to solve, especially the improvement of low-temperature stability.

As a result of intensive studies on many emulsion formulations and their coating performance, the present inventors found that emulsion-type sealers made of chlorinated polyolefins or modified chlorinated polyolefins have low safety and health risks, and have good adhesion and water resistance. The present inventors have discovered that this material has excellent properties, particularly low-temperature stability, and has accomplished the present invention.

(Means for solving the problem) Emulsion molds are usually required to have the following performance.

(1) In the q-state, the emulsion is stable and does not separate and settle even after the addition of pigments, etc.

(2) No repellency during application.

(3) There is no breakage of the emulsion during coating by airless spraying, etc., and mechanical stability is good.

(4) Stable at low temperatures, especially without aggregation after freezing and thawing.

(5) It is easy to form a continuous coating film.

In order to have such performance, the present inventors created a sealer composition by dissolving chlorinated polyolefin or modified chlorinated polyolefin and a plasticizer in an organic solvent, dispersing it in water containing an emulsifier, and emulsifying it using an emulsifying machine. . However, the viscosity of the emulsion made here is low and it easily separates during storage, and it also causes cissing during coating.
When pigments were added, separation sedimentation was observed, which required thickening of the emulsion.

However, although they generally have a thickening effect, they are still insufficient because some have a significant drop in water resistance or cause emulsion aggregation at low temperatures.

Therefore, as a result of repeated studies on various thickening effects, the inventors found that among water-soluble polymers, nonionic cellulose derivatives do not impair adhesion or water resistance, and are particularly stable at low temperatures. The present invention has been completed based on this discovery.

That is, the present invention uses 5 to 150 parts of plasticizer, 50 to 500 parts of organic solvent, 50 to 2000 parts of water, and 0.1 part of emulsifier to 100 parts by weight of chlorinated polyolefin or modified chlorinated polyolefin (hereinafter referred to as parts). ~10 parts, thickener 0.
This invention relates to an emulsion type sealer characterized in that it consists of 2 to 4 parts.

The solvent composition of the emulsion type sealer of the present invention is such that a part or most of the conventional solvent type organic solvent such as toluene is replaced with water, and the organic solvent is a higher boiling point solvent than the conventional solvent such as toluene. Furthermore, the aromatic solvent portion of the organic solvent used is reduced as much as possible, resulting in significant improvements in flammability, toxicity during construction, air pollution, and resource conservation.

In addition, the significance of using some organic solvents in this emulsion type is that if organic solvents are not used, it is difficult to make an emulsion, and even if it is made into an emulsion, a continuous coating film will not be formed, and the performance as a sealer will not be achieved. This is because it cannot be done.

Next, each component of the present invention will be specifically described.

The chlorinated polyolefin used in the present invention is high density or low density polyethylene.

Included are crystalline or non-crystalline polypropylene, chlorinated ethylene-propylene copolymers, and the like. The chlorination may be carried out by any method, but it is preferably obtained by a solution method by blowing chlorine gas into the solution under irradiation with a catalyst or ultraviolet rays.

The chlorinated polyolefin used in the present invention, which is obtained by chlorinating a polyolefin modified with one or more compounds selected from the group consisting of unsaturated polycarboxylic acids and their acid anhydrides, is produced by a known method. can do.

One example of its manufacturing method is polyolefin resins, such as high-density or low-density polyethylene.

Crystalline or non-grade polypropylene, ethylene-propylene copolymer, etc. are thermally melted singly or in combination of two or more, and if necessary, the molten polyolefin resin is reduced in viscosity by thermal decomposition, and the molten resin is produced in a batch or continuous process. is obtained by modifying the polycarboxylic acid with an unsaturated polycarboxylic acid and its acid anhydride in the presence of a radical generator, and then reacting with the same chlorination method as described above.

Examples of the radical generator used in the modification reaction include di-tert-butyl peroxide.

These include peroxides such as tert-butyl hydroperoxide and benzoyl peroxide, and azonitrile such as azobisisobutyronitrile and azobisisopropionitrile. Examples of unsaturated polycarboxylic acids and their acid anhydrides used in the modification reaction include maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, and fumaric acid.

The saponification value of the polyolefin modified with the unsaturated polycarboxylic acid and its acid anhydride used in the present invention is 6 to 60.
It is preferably 10 to 40.

If the saponification value is less than 6, no modification effect will be observed, and if the saponification value exceeds 60, the stability of the emulsion will deteriorate and it will be difficult to form an emulsion.

In addition, the chlorine content of the chlorinated product used in the present invention is 40
~75% by weight, preferably 45 to 70% by weight.a If the chlorine content is less than 40% by weight, the resin will be too soft, and if the chlorine content exceeds 75% by weight, the resin will be too hard. Cracks tend to occur in the coating film, and neither performs well as a sealer.

On Plasticizer Day, chlorinated polyolefin or modified chlorinated polyolefin (hereinafter abbreviated as chlorinated polyolefin, etc.)
5 to 150 parts per 100 parts, preferably 10 parts
~100 copies. If the amount used is less than 5 parts, it will be difficult to form a continuous coating, and even if a film is formed, the resin will be too hard and the coating will easily crack, and if the amount used exceeds 150 parts, The resins are too soft and do not exhibit their performance as sealers.

Various commercially available plasticizers can be used as the plasticizer, such as phthalate esters and phosphate esters.

Examples include chlorinated paraffin or epoxy. Preferred plasticizers are those based on chlorinated paraffins and epoxies.

The amount of organic solvent used to dissolve the chlorinated polyolefin and plasticizer is 50 to 500 parts, preferably 100 to 3 parts, per 100 parts of the chlorinated polyolefin, etc.
It is 00 copies. If the amount used is less than 50 parts, the solution viscosity is high, resulting in poor emulsifying and dispersing properties and poor stability, while if it exceeds 500 parts, it poses health and safety problems as an emulsion sealer. Toluene is an organic solvent that can be used.

Xylene 2. Solvent naphtha, Tsurpetz 100 and 150. Methanol 200 and 1ooo, ethyl acetate, butyl acetate, cellosolve acetate.

Methoxybutyl acetate, and other diluting solvents such as methanol, ethanol, and mineral spirits.

Examples include methylcyclohexane and ethylcyclohexane.

Preferred solvents include Nrubento naphtha, Tsurpetz 100 and 150, which are relatively high boiling point solvents that improve flammability, toxicity, and film-forming properties of chlorinated polyolefins.
．． Methanol 200 and 1000. Most preferably, methanol 200 with a low aromatic content,
Or methanol 1000. It is a mixture of Tsurupetsu 100 and non-aromatic.

The amount of emulsifier is 0.1 to 10 parts, preferably 0.5 to 5 parts, based on 100 parts of chlorinated polyolefin. If the amount used is less than 0.1 part, the emulsion stability of the emulsion will be poor, and if it exceeds 10 parts, the water resistance of the resin film will decrease.

Various surfactants can be used as emulsifiers, but nonionic surfactants are particularly suitable.

Various commercially available nonionic surfactants can be used, but in order to make a good oil-in-water emulsion, for example, polyoxyethylene alkyl phenol ether, polyoxyethylene sorbitan alkyl ester, polyoxyethylene It is preferable to use sorbitan fatty acid esters alone or in combination with H2S of 15 or more. Alternatively, an anionic surfactant such as alkylbenzene sulfonate may be used in combination.

The amount of water is 1 per 100 parts of chlorinated polyolefin, etc.
00 to 2000 parts, preferably 200 to 1000 parts
Department. If the amount used is less than 100 parts, safety such as flammability and toxicity cannot be obtained. If the amount exceeds 2,000 parts, the emulsion concentration decreases and a satisfactory film formation cannot be obtained, and the performance as a sealer is not exhibited.

The amount of the thickener is 0.2 to 4 parts, preferably 0.3 to 2 parts, based on 100 parts of the chlorinated polyolefin.

If the amount used is less than 0.2 parts, the low temperature stability of the emulsion will be insufficient, and if it exceeds 4 parts, the water resistance will be poor and neither will be sufficient as an emulsion for a sealer.

Thickeners play a very important role in emulsions. That is, the entire emulsion system can be protected by the performance of the thickener, such as prevention of sedimentation after addition, fluidity during application, prevention of coating film repellency, and long-term stability against temperature changes.

Conventional emulsion polymerization type emulsions have poor storage stability, particularly low-temperature stability, and tend to aggregate and become unusable without recovering to freeze-thaw reconstitution emulsions.

The chlorinated polyolefins used in the present invention have polarity, and sufficient consideration must be given to various stability issues during emulsification.

That is, many types of so-called water-soluble polymers are commercially available as thickeners, and many of them have excellent thickening effects. However, low-temperature stability is not sufficient, and cellulose ethers, which are nonionic polymers of cellulose derivatives, in particular methyl cellulose and hydroxyethyl cellulose, can be used without impairing the performance of chlorinated polyolefins. It was recognized that it has excellent low temperature stability. Preferred are methylcellulose derivatives, such as hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, and hydroxyethylcellulose, used alone or more preferably in combination.

Depending on the purpose of use, various additives such as pigments, stabilizers, and antifoaming agents may also be used.

[Function] In the present invention, when emulsifying chlorinated polyolefin or modified chlorinated polyolefin, among cellulose derivatives, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, and hydroxy ethyl cellulose, which are nonionic polymers, are particularly preferably used alone. It was discovered that the combined use shows an extremely excellent effect on low-temperature stability, and the present invention was completed.

In other words, further protection is provided by the interaction between the stability against various chemicals due to the nonionic nature of cellulose derivatives, the nonionic surfactant properties of methylcellulose that lowers the interfacial tension, and the remarkable stability of hydroxyethylcellulose at low temperatures. It is thought that colloidal properties were expressed.

The obtained emulsion was extremely stable at low temperatures, and the present invention was completed.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. In addition, parts and percentages in the examples are parts by weight and percentages by weight. Moreover, the test methods in the examples were conducted in accordance with JIS A-6910.

(1) Low-temperature stability test A stability test after freezing and thawing of an emulsion is conducted to visually observe the absence of lumps and separation and aggregation of the composition. (-5°C/18 hours → Room temperature/6 hours>X3 cycles (2) Water permeability test In a test of the sealing ability of the sealer to the base, the amount of water permeation from a certain area of slate board coated with the sealer after standing for 24 hours Measure.

(3) Adhesion strength test The adhesion strength of the sealer to the emulsion paint surface for elastic tiles and the mortar surface is measured.

Standard condition: After applying sealer and intermediate coating material 14
Leave to cure for a day. The adhesion strength is then measured.

After immersing in water, leave the upper part 5- after 2N, and in that state, 1
Let stand for 0 days. After that, 50℃/1 day, roughly room temperature/1 day
After standing for a day, measure the adhesion strength.

Repeated heating and cooling: (20℃/18 hours → -20℃/3 hours → 50℃/3 hours) was repeated 10 times, and the multi-layer coating material was inspected for peeling, cracks, and blisters. Visually observe and then measure adhesion strength.

(4) Repeated heating and cooling test Observe the changes in the elastic tile surface after the above heating and cooling cycles.

Judgment criteria: Peeling, cracking, blistering XX... Much X... Moderate △...... Few 0... Very slight ◎ ......None Example 1 100 parts of chlorinated polyethylene (chlorine content 60%) and 30 parts of chlorinated paraffin (Toyobarax A-40゜Toyo Soda Kogyo ■) were mixed with Nrubetsuso 1000 (Exxon Chemical ■)
) in 130 parts and 20 parts of methylcyclohexane, from 50 to
Dissolve by heating at 60°C to make a clear solution. This solution was preliminarily mixed with a nonionic surfactant (polyoxyethylene alkyl ether, nirasan nonion -220, HLB=16.2.
230 parts of 3 parts of NOF ■) (However, some of it is used for dispersing and dissolving titanium oxide and methylcellulose)
The mixture was dissolved in water and added to the solution heated to 50 to 60°C, while strongly emulsifying the mixture using a homomixer (1M type manufactured by Tokushu Kikae Industries). Next, while maintaining the temperature, a titanium oxide slurry prepared in advance and a thickener hydroxypropyl methyl cellulose (Metrose 653H,
13 parts of Shin-Etsu Chemical ■), 1.
5 parts of the emulsion was added to the unthickened emulsion while stirring with a conventional stirrer to obtain a uniformly thickened emulsion with a solid content of 28%.

Regarding the obtained emulsion, the above JIS A-69
10, the results are shown in Table 1.
As shown in the figure, the results were good.

Example 2 100 parts of chlorinated polypropylene (chlorine content 66%),
30 parts of chlorinated paraffin (same as before).

Add 10 parts of epoxidized soybean oil (ADEKASIZER 〇-13O3, Asahi Denka Kogyo @) to Swazol 200 (Marukubi Sekiyu ■)
) in 150 parts by heating to make a clear solution. This solution was mixed in advance with a nonionic surfactant and an anionic surfactant (polyoxyethylene alkyl ether sodium sulfate, emal 2).
0C, Kao Soap ■) was dissolved in 300 parts of water (a portion of which was used for dispersing and dissolving titanium oxide and hydroxyethyl cellulose), and heated in the same manner as in Example 1 to emulsify and thicken. . Hydroxyethyl cellulose (Natrosol 250HR, Vercules ■) was used as the thickener.

The low temperature stability results were good as shown in Table 1.

Examples 3 to 5 In Example 3, maleic anhydride-modified chlorinated polyethylene having a saponification value of 10 was used as the modified chlorinated polyolefin.

In Example 4, maleic anhydride-modified chlorinated polyethylene having a saponification value of 24 was used as the modified chlorinated polyolefin.

In Example 5, maleic anhydride-modified chlorinated polypropylene having a saponification value of 18 was used as the modified chlorinated polyolefin.

The low-temperature stability was good in all cases as shown in Table 1.

Comparative Examples 1 to 6 As in Comparative Example 1, the anionic surfactant and thickener were CM
For those using C, after freezing and thawing in the low temperature stability test, Table -
Layer separation occurred as shown in 2.

Comparative Example 2, which used a nonionic surfactant with an HLB of 10 or less as an emulsifier and sodium alginate as a thickener, caused separation and lumps in the low temperature stability test as shown in Table 2.

As in Comparative Example 3, a product using maleic anhydride-modified chlorinated polyethylene and an acrylic acid/acrylic acid ester copolymer as a thickener coagulated in the low temperature stability test.

Comparative Example 4, which used maleic anhydride-modified chlorinated polyethylene with a saponification value of 40 and a cationic surfactant, agglomerated in the low temperature stability test.

As in Comparative Example 5, an emulsion using maleic anhydride-modified chlorinated polypropylene having a saponification value exceeding 60 and CMC as a thickener coagulated when left at room temperature after emulsion.

Comparative Example 6 was a commercially available acrylic emulsion type sealer made by emulsion polymerization, but as shown in Table 2, it agglomerated and separated.

Regarding the systems with excellent low temperature stability of Examples 1 to 5, JIS
Table 3 shows the results of testing for suitability as a concrete sealer according to the A-6910 test method.

Comparative Example 7 is a solvent-type sealer in which the chlorinated polypropylene type used in Example 2 was made into a toluene solution and subjected to the test.

As shown in Table 3, it can be seen that the emulsion type according to the present invention is in no way inferior to the conventional solvent type.

In general, when compared with the emulsion type of Comparative Example 6 produced by the conventional emulsion polymerization method, it was found that the chlorinated polyolefin type, which essentially has water resistance, is superior.

〔Effect of the invention〕

Thus, according to the present invention, adhesion and water resistance.

Emulsifying a chlorinated polymer with excellent chemical resistance, etc.
After that, the product thickened with a cellulose derivative exhibited excellent performance in low temperature stability according to JIS A-6910 without impairing the original performance as described above.

The emulsion-type concrete sealer of the present invention containing this material greatly improves the safety and health hazards that could not be obtained with conventional solvent-type concrete sealers, improves functionality, and has stability that can greatly contribute to resource conservation. We have completed an excellent emulsion-type concrete sealer composition and its manufacturing method.

Procedural amendments (self-proposal) May 20, 1985, Japan Press Secretary Akio Kuroda (exported detailed procedural amendments) July 21, 1988, Commissioner of the Japan Patent Office No. Al1 Actual Beta Huo En 1. Indication of the incident 1988 Patent Application No. 24288 2. Name of the invention Emulsion type concrete sealer with excellent stability Address 1-4-5 Marunouchi, Chiyoda-ku, Tokyo Name
(234) Sanyo Kokusaku Pulp Co., Ltd. 4, Agent address: 16 Kanda Kita Jorimono-cho, Chiyoda-ku, Tokyo 1
01 Ei Building 3rd Floor 5, Detailed Description of the Invention in the Specification Subject to Amendment The following matters will be corrected in the Detailed Description of the Invention in the Specification.

(1) On page 26, line 6 of the specification There is rcMcJ Corrected to "Polyethylene oxide (hereinafter abbreviated as PEO)" (2) Statement box, page 23, line 3 There is rcMcJ Corrected with rPEOj (3) On page 26 of the specification, line 7 from the bottom (thickener section) It says rCMCJ. rPEOJ and correction

Claims (6)

[Claims] (1) An emulsion-type concrete sealer composition containing a chlorinated polymer, a plasticizer, and a cellulose derivative as main components and conforming to JISA-6910 (low-temperature stability test). (2) The emulsion type concrete sealer composition according to claim 1, wherein the chlorinated polymer is a chlorinated polyolefin or a modified chlorinated polyolefin. (3) The emulsion type concrete sealer composition according to claim 2, wherein the chlorinated polyolefin is chlorinated polyethylene, chlorinated polypropylene, or chlorinated ethylene-propylene copolymer. (4) Chlorinated polyethylene in which modified chlorinated polyolefin is modified with one or more compounds selected from the group consisting of unsaturated polycarboxylic acids or their acid anhydrides;
The emulsion type concrete sealer composition according to claim 2, which is chlorinated polypropylene or chlorinated ethylene-propylene copolymer. (5) The emulsion type concrete sealer composition according to claim 1, wherein the cellulose derivative is methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, and hydroxyethylcellulose. (6) A method for producing an emulsion-type concrete sealer, characterized in that the main components are chlorinated polyolefin or modified chlorinated polyolefin, a plasticizer, and a cellulose derivative, and an organic solvent, an emulsifier, and water are added thereto.