JPH02150457A - Emulsion and its resin composition for hydraulic silicate material - Google Patents

Abstract

PURPOSE:To obtain a fast-curing emulsion of high storage stability which is used in a hydraulic silicate resin composition by using a resin composition containing a polymerizable monomer for crosslinking and a polymer to be crosslinked, a basic substance and a nonionic surface active agent. CONSTITUTION:The emulsion is composed of (A) a polymerizable monomer- crosslinking type thermosetting resin composition of less than 9 acid value, containing A1: a polymerizable monomer for crosslinking such as styrene, A2: a polymer to be crosslinked such as an unsaturated polyester, a vinyl ester resin, preferably in addition, a curing catalyst and a curing accelerator, (B) 0.7 to 1.5 equivalent, based on an equivalent acid value of component A, of a basic substance such as triethanolamine or diethanolamine and (C) 1-15 pts.wt., per 100 pts.wt. of component A, of a surface active agent such as polyoxyethylene alkyl ether. The emulsion and the hydraulic silicate material are mixed to give the subject composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a hydraulic silicate material resin composition for polymer concrete, etc., consisting of, for example, cement and a resin emulsion, and an emulsion used therein.

[Conventional technology]

Conventionally, various proposals have been made regarding methods for producing emulsions of polymerizable monomer crosslinked thermosetting resins. In particular, there are many unsaturated polyester resin compositions because of their curability, ease of water solubilization technology such as curing agents and curing accelerators during curing at room temperature.

For example, a cured water-containing resin is obtained by forming an inverse emulsion (i.e., YK in oil, mold) in which water is dispersed as minute droplets in a vinyl-based heptamer-containing unsaturated polyester resin composition phase, and then hardening this after casting. Are known. In this method for producing an inverse emulsion of an unsaturated polyester resin composition containing a vinyl thread monomer, a surfactant having a high lipophilicity of about HLB 3 to 8 is added to the unsaturated polyester resin composition containing a vinyl monomer. A method of forming a water-in-oil emulsion by adding sorbitan derivatives such as sorbitan monostearate, sorbitan instearate, sorbitan monooleate, and sorbitan monobalmitate, and nonionic surfactants such as glycerin monostearate (especially In addition, graft polymers of vinyl monomers such as styrene and vinyl acetate and hydrophilic polymer compounds such as polyethylene glycol, polyethylene oxide, and polypropylene oxide are used as emulsifiers to produce water-in-oil. Method of forming mold emulsion (8)
artl, H, und II, davan 8onin,
Makromol, Chem.

57.74 (1962)), and as an alternative method, basic substances that can form salts with the terminal carboxyl groups of unsaturated polyester resins to become polyester salts, specifically triethanolamine, jetanolamine, and triethylamine. Symmetrical or asymmetrical alkylamines such as, diamines such as methylene diamine and ethylene diamine, nitrogen-containing basic substances such as ammonia, hydrazine, etc., alkali gold H hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. , a method of forming a water-in-oil emulsion using alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, etc. (Belgian patent 62203)
4). Among these emulsifiers, triethanolamine is said to be particularly preferred since it has the potential to form a structural film at the interface between the unsaturated polyester and water.

Since the cured resin obtained by the above method contains a large amount of water in the form of a dispersed liquid, in addition to the heat resistance of the resin itself, the resin has high specific heat, large latent heat of vaporization, and nonflammability of the water itself. In addition to significantly increasing the heat resistance of the polymer, a number of other benefits have been reported.

Furthermore, during the formation of this emulsion, a stable relatively low viscosity oil/water/oil or water/oil/water double emulsion can be obtained by using a cement hydrated supernatant liquid or a cement dispersion as the aqueous phase. A method has also been proposed in which the cured resin obtained by curing this emulsion contains water in the form of minute droplets and at the same time contains soluble and eluted components associated with the cement hydration reaction. Showa 5
5-29552).

However, both methods have problems with storage stability in the emulsion state, curing properties of the molded product, physical properties, etc. In particular, in terms of storage stability, water and crosslinking polymerizable monomer or crosslinked polymer Separation occurred, making it difficult to manufacture on a general commercial basis.

Furthermore, since the cured resin contains a large amount of water as a component, its manufacturing cost is low, and its mechanical strength is quite high, so it can be used as a structural material, a floor coating material, and a secondary product. However, when the cured product obtained by the above method is left in the air, moisture gradually escapes and shrinks, and sometimes the difference in the amount of moisture escaping from the surface of the cured product causes twisting, warping, and cranking. Therefore, it has the disadvantage that it cannot be used in products that require dimensional stability.

In addition, the amount of water escaping is affected by the external atmosphere, and in order to improve this drawback, for example, an integral skin layer is applied to the surface of the cured product using a suitable resin such as unsaturated polyester resin, or a water-in-oil emulsion is applied. At the time of formation, methods have been taken such as adding water-soluble resins such as polyacrylamide, polyvinyl alcohol, carboxymethyl cellulose, etc. to the aqueous phase to increase water retention. However, sufficient effects have not been obtained.

As a method to solve this fatal defect that the weight change is extremely large, it is preferable to make the water contained in the emulsion into a stable form, that is, to stabilize free water by converting it into bound water using cement. .

It is known that a cured product of an unsaturated polyester resin to which a cement composition that causes a hydration reaction is added tends to have a significantly smaller weight change. For example, a method of mixing cement with polymerizable monomer crosslinked thermosetting unsaturated polyester/water is described in JP-A-58-84813. This method concerns a polymer concrete composition, consisting of 8 to 20% polymerizable monomer crosslinked thermosetting unsaturated polyester resin composition, 60 to 80% aggregate,
0.75 to 10% water and the rest is a substance that can release divalent metal ions, which are the constituent components of cement, into an aqueous system.

This polymer concrete has a compressive strength of 1 after 1 hour of mixing.
The most important feature is fast curing properties of 40Kg/cd.

[Problem to be solved by the invention]

However, this method also has the following problems when the range of application is expanded.

(2) When the ratio of the resin composition containing a crosslinking polymerizable monomer to water is 0.135 or more, the water in the composition separates from other components.

■ If the ratio of the resin composition containing a crosslinking polymerizable monomer/water is 0.3 or more, the dispersibility of cement will be poor;
It causes agglomeration phenomenon and cannot be used.

(2) Since the resin composition containing the polymerizable monomer for crosslinking and water are each separated into two phases as liquid substances, working efficiency is poor because they are mixed and used.

■ Because the amount of water mixed in is small, costs cannot be reduced.

On the other hand, even if similar compositions were produced using the various vinyl monomer-containing unsaturated polyester resin emulsions described above and mixing cement, it would not be possible to obtain a product that would be of practical use.

The reason is as follows.

■ The storage stability of thermosetting resin emulsions is extremely poor. A short sample will separate into a resin phase and an aqueous phase within a few minutes, and a long sample will separate into a water phase within a few days.

■ Even if cement is mixed in, agglomeration occurs and a uniform composition cannot be created, causing water to separate.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present invention has intensively investigated a thermosetting emulsion that has excellent storage stability, fast curing properties, and excellent cement dispersibility, and a method for obtaining a composition for example, concrete using the same. As a result, the following invention was completed.

(a) A polymerizable monomer crosslinked thermosetting resin composition containing at least a polymerizable monomer for crosslinking and a polymer to be crosslinked and having thermosetting properties with an acid value of 9 or less; An emulsion containing a basic substance in an amount of 0.7 to 1.5 equivalents, and a surfactant including a nonionic surfactant with a Te of 816 or more; The present invention provides a hydraulic silicate material resin composition mixed with an acid salt material, which composition may be a wet surface coating.

The polymerizable monomer crosslinked thermosetting resin composition containing at least a crosslinking polymerizable monomer and a polymer to be crosslinked and having a thermosetting property with an acid value of 9 or less used in the present invention includes Examples include curable unsaturated polyester resin compositions and polymerizable monomer crosslinked thermosetting vinyl ester resin compositions.

The polymerizable monomer crosslinked thermosetting unsaturated polyester resin composition includes α,β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycol polymers. 30 to 80 parts by weight of an unsaturated polyester produced by condensation, optionally using an aliphatic or alicyclic saturated dibasic acid as an acid component, and α,β-unsaturated monomer as a crosslinking polymerizable monomer. Quantity 70-2
Examples include those obtained by dissolving 0 parts by weight. Also,
Polymerizable monomer crosslinked thermosetting vinyl ester resin compositions include those consisting of an unsaturated polyester whose ends are modified with vinyl and a polymerizable monomer for crosslinking, and epoxy resins whose ends of the epoxy skeleton (epoxy resin) are modified with vinyl. Examples include those consisting of a vinyl ester resin and a capping monomer for crosslinking. If necessary, in addition to a curing catalyst and a curing accelerator, a binder, a filler 1, a shrinkage reducing agent, etc. are added to these, and the addition of a curing catalyst and a curing accelerator is particularly preferred in terms of speeding up curing.

Examples of the α,β-unsaturated dibasic acids or their acid anhydrides include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid, and esters thereof, and aromatic saturated dibasic acids Examples of basic acids or their acid anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and esters thereof. , aliphatic or alicyclic saturated dibasic acids include silicic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, respectively. Used alone or in combination. Glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1.3-butanediol, 1.4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol,
Tetraethylene glycol, 1.5-bentanediol, 1.6-hexanediol, bisphenol A, water
Bisphenol A1 ethylene glycol carbonate, 2,2-di(4-hydroxypropoxydiphenyl)propane, etc. are used alone or in combination, but other oxides such as ethylene oxide and propylene oxide can also be used. . Furthermore, polycondensates such as polyethylene terephthalate can also be used as part of the glycols and acid components. Furthermore, a resin obtained by reacting a terminal carboxyl group of an unsaturated alkyd resin synthesized from a glycol and an acid with a reactive heptamer having a glycidyl group can also be used. Typical reactive heptamers having a glycidyl group include glycidyl acrylate and glycidyl methacrylate.

Examples of the α1β-unsaturated monomer of the polymerizable heptamer for crosslinking include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl Vinyl monomers or vinyl oligomers that can be crosslinked with unsaturated polyesters such as vinyl compounds such as acrylate, methyl methacrylate, acrylonitrile, and methacrylonitrile, and allyl compounds such as diallyl phthalate, diallyl fumarate, diallyl succinate, and triallyl cyanurate. etc. are mentioned,
Styrene is used either alone or in combination.-Styrene is used for boat fishing.

More specifically, the above-mentioned polymerizable seven-proportion cross-linking thermosetting epoxy vinyl ester resin is a bisphenol type epoxy resin alone or a mixture of a bisphenol type epoxy and a novolak type epoxy resin. , whose average epoxy equivalent is 250 to 45
An epoxy vinyl ester obtained by reacting an epoxy resin in the range of
Refers to the resin obtained by dissolving the

Here, a typical bisphenol type epoxy resin is a glycidyl ether type epoxy resin that substantially has two or more epoxy groups in one molecule and is obtained by the reaction of epichlorohydrin with bisphenol A or bisphenol F. resin, a dimethyl glycidyl ether type epoxy resin obtained by the reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, or a fullkylene oxide adduct to bisphenol and shrimp chlorocitrin, or
It is an epoxy resin obtained from methyl epichlorocitrine. Typical examples of the novolac type epoxy resin include epoxy resins obtained by reacting phenol novolak or talesol novolak with shrimp chlorocitrin or methyl epichlorohydrin.

On the other hand, typical unsaturated basic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutyl maleate, sorbic acid, and mono(2-ethylhexyl) acid. )
There are malate etc.

It goes without saying that these -basic acids can be used alone or in combination of two or more.

The reaction between these epoxy resins and unsaturated basic acids is 6
It is carried out using an esterification catalyst at a temperature of 0 to 140°C, preferably 80 to 120°C. Such esterification catalysts include tertiary amines such as triethylamine, NN-dimethylbenzylamine, N,N-dimethylaniline or diazabicyclooctane; or diethylamine hydrochloride, dimethyl acetate, or dimethylamine sulfate. , known catalysts can be used as they are.

The epoxy vinyl ester resin thus obtained is dissolved in a known polymerizable vinyl hexamer to form a stable resin solution. Typical examples of the polymerizable vinyl hexamer include styrene. , vinyltoluene, t
- Styrene derivatives such as butylstyrene, chlorstyrene or divinylbenzene: 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2
-Hydroxyethyl (meth)acrylate or 2-
Low-boiling ester monomers of (meth)acrylic acid such as hydroxypropyl (meth)acrylate; or trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1. These include (meth)acrylates of polyhydric alcohols such as 6-hexanethiol di(meth)acrylate, and these may be used alone or as a mixture of two or more. The concentration of these polymerizable vinyl hexamers is not particularly limited, but is preferably 10 to 50% by weight in terms of workability, impregnation properties, and performance of the cured product.

Furthermore, when producing the above-mentioned polymerizable monomer crosslinked thermosetting epoxy vinyl ester resin composition, a polymerization inhibitor is used for the purpose of preventing gel value and adjusting the storage stability or curability of the resulting resin. It is recommended to do so.

Typical examples of the polymerization inhibitor used here include hydroquinones such as hydroquinone, pt-butylcatechol, or mono-1-butylhydroquinone; hydroquinone monomethyl ether or di-t-butyl - Phenols such as p-cresol; quinones such as p-benzoquinone, naphthoquinone or p-torquinone; or copper salts such as copper naphthenate.

Polymerizable 7-mer cross-linked thermosetting unsaturated polyester resin composition used in the present invention, polymerizable 7-mer cross-linked type? ! The acid (11i) in a thermosetting resin composition such as a curable vinyl ester resin composition has a great influence on the properties and characteristics of the emulsion obtained by emulsification.

As a means to reduce the acid value, in the case of a polymerizable 7-mer crosslinked thermosetting unsaturated polyester resin composition,
It becomes a polymer. (Dibasic acids such as isophthalic acid and linear adipic acid, which are particularly susceptible to steric hindrance, tend to improve the degree of M condensation.)

(2) As described above, the terminal carboxyl group of the heated polymer is reacted with a monomer having a glycidyl group.

(2) Furthermore, the acid value is low because the end of the vinyl ester resin is reacted with an epoxy resin and an unsaturated basic acid in a reaction similar to (1) above.

In any case, resins with reaction methods such as (1) and (2) tend to have low acid values and are accepted as crosslinked polymers of the present invention.

Here, the acid value is the number of milligrams of potassium necessary to neutralize the carboxyl groups contained in 1 g of resin, and indicates the number of terminal groups.

The acid value indicates the amount of acid remaining at the terminal as described above, specifically, the amount of remaining carboxyl group.

Since carboxyl groups are generally hydrophilic groups, they tend to bond with the hydrophilic side of an emulsifier, and the number of carboxyl groups is thought to affect the properties of the emulsion produced.

Furthermore, the acid value of the polymerizable vinyl monomer crosslinked thermosetting resin composition used in the present invention is an important factor in producing compositions for hydraulic silicate materials, such as cement. The emulsion type of the present invention differs depending on the acid value of the polymerizable vinyl heptamer crosslinked thermosetting resin composition.

That is, when a resin composition with an acid value greater than 9 is used, it becomes an oil-in-water type, and when it is less than 9, it becomes a water-in-oil type. In the former case, when cement is added, the dispersibility deteriorates significantly, and furthermore, when a hardening agent such as peroxide is added, hardening is significantly inhibited.

Regardless of whether the emulsion type is oil-in-water or water-in-oil, adding the same liquid as the continuous phase to the emulsion will dilute the emulsion uniformly6.For example, if a drop of emulsion is dropped into water, it will be When it is diluted and spread out, it is an oil-in-water droplet, and when a single droplet remains on the water surface, it is a water-in-oil droplet.

When emulsifying a polymerizable vinyl heptamer framework type thermosetting resin composition by changing the acid 1i, if the acid value is 11 or more, only an emulsion with extremely poor storage stability can be produced; The type of the droplet becomes an oil-in-water type (07 type). When the acid value is greater than 9 and less than 10, the state is intermediate between the 0/W type and the W2O type (water-in-oil type). If the acid value is 9 or less -7
Becomes type 0.

There is no theoretical support as to why various emulsion types are created depending on the acid value of the polymerizable monomer crosslinked thermosetting resin composition. However, considering that emulsions consist of a delicate balance of hydrophilic groups and lipophilic groups, the number of carboxyl groups, which are hydrophilic groups, is
Q: I can understand to some extent that it is related to quantity.

The basic substance used in the present invention can also act as an emulsifier, and can be a substance that can react with the terminal carboxyl group of the crosslinked polymer of the polymerizable vinyl 7-mer crosslinked thermosetting resin composition to form a salt. Various amines and alkaline earth metal compounds are often used.

The amines include aliphatic, alicyclic, and aromatic primary and secondary amines.
, tertiary amines, etc., such as triethanolamine, dimethylethanolamine, jetanolamine, etc.
Monoethanolamine, triethylamine, diethylamine, monoethylamine, other alkylamines containing a single methyl, propyl, butyl, or isobutyl group or multiple groups of various types in the same molecule, various alkylamines including ethylenediamine, diethylenetriamine , polyvalent amines such as triethylenetetramine, various organic amines including olefinic amines, and nitrogen-containing basic substances such as ammonia and hydrazine. Furthermore, as the alkali metal and alkaline earth metal compounds, hydroxides are commonly used. Examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, and the like. Preferred among these basic substances are triethanolamine, dimethylethanolamine, and the like.

The amount of the basic substance used as an emulsifier depends on the amount of water to be emulsified, the composition of the polymerizable monomer crosslinked thermosetting resin composition that becomes a continuous phase and also serves as an activator, and especially the terminal carboxyl content of the crosslinked polymer. It greatly affects the group concentration (i.e. acid value).

The amount of the emulsifier of the present invention added is 0.7 to 1.5 equivalents per acid value 1 equivalent of the polymerizable monomer crosslinked thermosetting resin composition;
It is preferably used in an amount of 0.9 to 1.3 equivalents. The formula for calculating the amount added is as follows.

N Category R: Weight of polymerizable monomer crosslinked thermosetting resin composition AN = Polymerizable 7% - Acid value K of crosslinked thermosetting resin composition: Constant (0.7 to 1.5) In the present invention The amount of the basic substance used is correlated with the pH value. As the amount added increases, the pH value increases and 1. As the amount added decreases, the pH value decreases and becomes more acidic.

If the amount added is less than the above 0.7 equivalent, the pH value will be 6.
If the amount is less than 1, it has a significant adverse effect on the curability of the resin, and if the amount is more than 1.5 equivalents, the pH value will be 10 or more, and the physical properties such as heat resistance of the cured product will deteriorate when the resin is cured.

The basic substance may be added to the polymerizable monomer crosslinked thermosetting resin composition together with a nonionic surfactant and other additives, but it is preferable to add other additives to the resin composition. It is better to mix it alone at the initial stage apart from additives.

A known mixing method is used.

The nonionic surfactants with an HLB of 16 or more used in the present invention are known examples such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether,
These include polyoxyethylene derivatives, polyoxyethylene oxyprobylene bronoch polymers, sorbitan fatty acid esters, polyoxyethylene sorbicun fatty acid esters, fatty acid monoglycerides, polyethylene glycol fatty acid esters, and the like.

If the HLB of the nonionic surfactant used is 14 or less, it is difficult to obtain a uniform emulsion; if the HLB is thicker than 14 and smaller than 16, it is possible to produce an emulsion, but it may cause agglomeration during cement dispersion. and it is not possible to obtain a uniform composition.

Nonionic surfactants may be used in combination with different compositions or with different HLB values, but when used in combination, the weighted average of the HLB values should be taken and the value should be 16 or more. Must.

In general, nonionic surfactants with a high LB value of 1 (LB) are often in solid form such as flakes at room temperature, so it is preferable to add them in the form of a solution in water.

The amount of the on-based surfactant used in the present invention is 1 to 15 parts by weight, preferably 3 parts by weight, based on the polymerizable monomer crosslinked thermosetting resin composition too and ii parts. ~10 parts by weight. If it is less than 1 part by weight, emulsification will be difficult, and if it is more than 15 parts by weight, the physical properties of the composition will be poor.

As the surfactant used, anionic, cationic, or amphoteric surfactants may be used in combination as long as the dispersibility of the hydraulic silicate material such as cement is not deteriorated. Furthermore, it may be used in combination with other methods for producing emulsions of polymerizable vinyl heptamer crosslinked thermosetting resins.

For example, there is a method in which unsaturated alkyd itself is used as an emulsifier. In this type, a surfactant is incorporated into the molecules of an unsaturated alkyd through an esterification reaction, so that the unsaturated alkyd itself functions as a type of surfactant.

There is also a method in which a thermoplastic resin is used as a third component in addition to the resin and water to form an emulsion.

The main thermoplastic resins used include acrylic esters, methacrylic acid, copolymer resins of these monomers and other monomers, butadiene copolymers such as butadiene-acrylonitrile, and polyurethane prepolymers. be.

As the elasticity-imparting material, synthetic rubber and polyurethane are used to obtain good results.

The method of adding an emulsifier such as a nonionic surfactant of the present invention is preferably carried out in the form of an aqueous solution;
The concentration of the liquid is preferably 10 to 50%. Even if it is smaller than 10% or larger than 50%, an oil-in-water type emulsion is likely to be formed.

The emulsion of the present invention can be produced by a known method. At that time, various additives for improving various physical properties of the hydraulic silicate material polymer composition such as the final composition, such as the cement polymer composition, such as antifoaming agents, dispersants, wetting agents, antifreeze agents, Preservatives, film-forming aids, etc. may be added in advance.

Hydraulic silicate material polymer compositions such as the emulsion or cement polymer compositions of the present invention are generally cured in the same manner as polymerizable monomer crosslinked unsaturated polyester resin compositions.

As a curing agent, an organic peroxide such as a ketone peroxide type 1. Hydroperoxide-based, diacyl peroxide-based, peroxyketal-based, alkyl perester-based, and bar carbonate thread rings are used.
It is selected appropriately depending on the temperature during use. The amount added is a commonly used amount, preferably 0.01 to 4 parts by weight per 100 parts by weight of the polymerizable monomer crosslinked thermosetting resin composition.
Parts by weight.

The above curing agents may be used in combination.

In addition, curing accelerators, that is, substances that decompose the organic peroxide of the curing agent through a redox reaction and facilitate the generation of active radicals, include metal soaps such as cobalt-based, vanadium-based, and manganese-based soaps, Examples include tertiary amines, quaternary ammonium salts, and mercaptans.

In addition, in consideration of workability, the curing agent and curing accelerator must be added in advance to a polymerizable monomer crosslinked thermosetting type (H fat composition). The thermosetting resin composition and water are separated, and for example, a basic emulsifier and a curing accelerator are added to the polymerizable 7-mer crosslinked thermosetting resin composition side, and a nonionic surfactant and a curing accelerator are added to the water side. A curing agent is added and both are mixed at the time of use.

The present invention provides a hydraulic silicate polymer composition, wherein the hydraulic silicate material used herein has a CaO%
5i02, for example, 45-70% and 15-30%, respectively.
For example, hydraulic cement may be mentioned, and a typical example thereof is Portland cement.

Other types of Portland cement such as early strength, super early strength, medium H heat, and sulfate resistant can also be used. Mixed cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used. Additionally, special cements such as white cement, alumina cement, calewell cement, colloidal cement, high sulfate slag cement, rapid hardening cement, geothermal cement, etc. can also be used.

The amount of the hydraulic silicate material such as cement mixed into the emulsion of the present invention is 130 to 500 parts by weight, preferably 200 parts by weight, based on 100 parts by weight of water in the emulsion.
~300 parts by weight.

A cement swelling agent may be used alone or in combination with cement or the like in the hydraulic silicate material polymer composition of the present invention for the purpose of preventing shrinkage during hardening. As a cement swelling agent, ■ Free lime (Cab)
, substances such as magnesia (MgO) that cause an increase in volume through a digestive reaction with water, ■ 3C in Portland cement
aO・ Hachiji! Ettringite crystals (3CaO-A I
■Cab: A I20
5:C (ls04) in a molar ratio of 3:1:3 to 4:1:3 and calcined in the same manner as Portland cement, which produces ettringite through a hydration reaction.

In addition to the above-mentioned hydraulic silicate materials such as cement, the emulsion obtained by the present invention may be used in combination with mortar and various aggregates used for concrete. silica sand,
Fine aggregate such as natural sand and coarse aggregate such as crushed stone may be used semi-ordinarily or in combination.

Further, pearlite, various balloons, etc. may be used as lightweight aggregates, and iron sand etc. may be used as high specific gravity fillers. In addition, glass fiber, silica fiber, carbon fiber,
Asbestos fibers, vinylon fibers, metal fibers, etc. may also be used. Other auxiliary additive components such as a blowing agent, a combustion agent, and a coloring agent can also be added.

The emulsion of the present invention can be of the water-in-oil type,
The component polymerizable monomer crosslinked thermosetting resin composition has a limited acid value, a basic composition as an emulsifier, and 81%
Since 6 or more nonionic surfactants are used in combination, the emulsion has excellent storage stability and can be cured in a short time by radical polymerization like general unsaturated polyesters.

Utilizing this feature, it can be used for architectural structures and concrete primers that are often used on wet surfaces, and paints for marine structures.

Furthermore, since the emulsion of the present invention has excellent dispersibility with hydraulic silicate materials such as cement, compositions made of these materials or with aggregates added thereto can be used as fast-curing and high-strength polymers. Can be used as a material for concrete. Its characteristics include the fast curing and high strength of conventional hardening resin concrete, and the hardness and adhesion on wet surfaces of thermoplastic resin emulsion cement.

Utilizing these properties, it can be used in compositions for mortar, concrete, etc. for various buildings and civil engineering structures. For example, it can be used as a composition for tunnels, sprayed mortar for bedrock, lightweight concrete, concrete for composite pipes (FRPM pipes), fillers for various concrete gaps, road repair materials, permeable concrete, and the like. It can also be used as a paint such as a primer for concrete, etc., and is particularly suitable as a paint for wet surfaces.

Example Next, examples will be described in detail.

Examples 1-12, Comparative Examples [~6 (al) Preparation of polymerizable 7-mer crosslinked thermosetting resin composition.

Polymerizable heptamer crosslinked thermosetting resin compositions were synthesized using a known synthesis method to obtain A-D shown in Table 1.

The specific manufacturing method is shown below.

■ Preparation of A resin composition 3.15 mol of propylene glycol, orthophthal #L
, 5 mol, fumar [15 mol, toluhydroquinone 50
ppm was heated and condensed at 200 to 205°C, and when the acid value reached 26, the reaction was terminated to synthesize an unsaturated polyester. 3 parts by weight of styrene monomer for 65 parts by weight of the resin
A If, which is a thermosetting unsaturated polyester resin composition containing 5 parts by weight of a polymerizable monomer and having an acid value of 25, by stirring and dissolving.
A fat composition was prepared.

■ Preparation of B resin composition 3.15 mol of neopentyl glycol, isophthalic M2
mol, fumaric acid 1 mol, toluhydroquinone 50 pp
m is heated and condensed at 200 to 205°C to form the acid 1ilIi15
The reaction was terminated at the point where the unsaturated polyester was synthesized. 45 parts by weight of styrene mono-2 was stirred and melted against 55 parts by weight of the resin to prepare Resin Composition B, which is a polymerizable 7-mer crosslinked thermosetting unsaturated polyester resin composition having an acid value of 12.

■Preparation of C resin composition A cross-tub type thermosetting unsaturated polyester resin composition with a polymerizable 7% ratio of acid 1i1 [i8 A C+)J fat composition was prepared.

■ Preparation of D resin composition A polymerizable heptamer crosslinked thermosetting unsaturated polyester resin composition with an acid value of 4 was prepared in the same manner as in the preparation of the above ■ A resin composition with the formulation shown in DIIIiil in Table 1. D resin composition I prepared something.

(2) Preparation of IJJI resin composition Composition E was prepared as a polymerizable monomer crosslinked thermosetting epoxy vinyl ester resin composition in the following manner.

Epiclone with an epoxy equivalent of 189 obtained by the reaction of bisphenol A and epichlorohydrin (Dainippon Ink Chemical Industry ft1!! 485 g), methacrylic acid 21
5G, 0.35 g of hydroquinone, and 2.1 g of triethylamine were added, the temperature was raised to 110°C, and the reaction was continued for 6 hours. A fi6 vinyl ester resin was obtained.

To this, 30 g of styrene monomer was added to prepare E resin composition, which is a polymerizable 7-mer crosslinked thermosetting epoxy vinyl ester resin composition having an acid value of 4.

Note that the acid value was measured by the following method.

Weigh Sample No. 2~Log into a 200~300ml Erlenmeyer flask, and add about 50ml of a mixed solvent of methanol:toluene/30N0 to dissolve the resin. If solubility is poor, a small amount of acetone may be added.

Using a mixed drug of 0.1% bromothymol blue and phenol red, titrate with a pre-standardized N/10 strength potassium-alcohol solution, and calculate the acid value using the following calculation from the amount of alcoholic potassium solution consumed. .

Acid value/KOH (number of ml) XN
Preparation of emulsion The water shown in the table was gradually added and stirred at about 200 revolutions/minute for 10 minutes. Examples 1 to 12 shown in Table 2 and Comparative Example 1 shown in Table 3.
~6 emulsions were obtained.

(C) Emulsion evaluation■ Emulsion stability test 400g of sample was taken into a 500cc glass bottle.
It was stored in a 0°C constant temperature bath for one week, and its condition was visually observed and evaluated as follows.

0...No change.

△: A slight water separation phenomenon is observed.

×...Water and other components separate into two layers.

■ Cement dispersibility In addition, the following formulation was stirred with a stirrer and the dispersion state and hardening state were visually observed.

Each emulsion obtained in the above (b) 100. ! Parts by weight Portland cement 200 parts by weight ifl Antifoaming agent (trade name Nopco NXZ) Q, 1 part by weight Benzoyl peroxide 2.0 parts by weight Dimethylamine
Evaluation of the 0.5 overlap area was performed as follows.

○...Good.

△: A cloudy liquid appears on the surface.

×: Cement coagulated and separated after stirring for 1 to 2 minutes.

The results of this test are shown in Table 2.3.

Example 13.14, Comparative Example 7.8 Mortar materials as hydraulic silicate material resin compositions were prepared and evaluated.

■ Preparation of mortar As shown in Table 4, a curing agent, a curing accelerator, and an antifoaming agent were added to the emulsion of each example and the polymerizable monomer crosslinked thermosetting resin composition (commercially available) for the comparative example. were stirred and mixed, and cement and sand were added thereto and mixed with stirring WA1 to produce mortar.

(2) Mortar evaluation method Each mortar obtained in (1) was subjected to compressive strength and bending strength tests based on J15-R-5021 physical test method for cement and JIS-^-6203. However, N.3° (Hot water strength retention rate) Based on the above test method, a 4 x 4 x 15 cm mortar is immersed in 80'ci water for about one month, taken out, subjected to a bending test, and determined from the following formula.

However, in Comparative Example 7, the test specimen was immersed after 28 days, and in the other cases, 1
After 8 days, the test specimen was immersed and used.

(Adhesion) JIS-A6910 multi-layer pattern spray material 6.3.2 (2)
The adhesion strength test method after immersion in water was applied.

That is, the JIS sidewalk slab was left in water for a month and a half, and each mortar obtained above was applied to about 5 fins on the wet surface (13-15% as measured by Kerato high-frequency moisture meter CH-2 model). It was applied to a certain thickness and an adhesion test was conducted one week after application.

Table 4 shows the above evaluation results.

In addition, in Tables 2 to 4, the basic substance is acid (it
Equivalents to the current version and others indicate ff11 parts.

Table 2 (Emulsion regulations) Table 3 (Emulsion dispute) Table 4 (Mortar The materials used in the table are as follows.

PG: Polypropylene glycol BPh-^: Bisphenol^ ethylene oxide 2 mole adduct NPG: Neobentyl glycol OP: Orthophthalic acid IPA: Isophthalic acid FA: Fumaric acid MA: Maleic acid Neugen EA190D: HLB 19 manufactured by Dai-Kogyo Seiyaku Co., Ltd.
Neugen ET170: #HLB 17 Neugen EA150: ”HLB
15 Neugen E↑80E: nt
．． a 8 Bonco) 550: Dainippon Ink Chemical Industry ■
Acrylic emulsion antifoaming agent Nobucon NXZ rsan 21fu Co., Ltd. Nizing agent BPO
: benzoyl peroxide curing accelerator DMA dimethylamine [Effects of the invention] According to the present invention, the acid value of a polymerizable heptamer crosslinked thermosetting unsaturated resin composition, its neutralization with a basic substance, and HLB
By using a nonionic surfactant of 16 or more, it is possible to provide a highly stable emulsion of a polymerizable monomer crosslinked thermosetting unsaturated resin composition, and moreover, it is possible to provide a polymerizable monomer crosslinked thermosetting unsaturated resin composition emulsion with a conventional polymerizable monomer crosslinked thermosetting resin composition. The curability of unsaturated resins can be maintained. As a result, a composition mixed with a hydraulic silicate material such as cement can maintain its dispersed state stably, and since there is no separation of water during molding, it does not inhibit curing and is quick. It can be made curable.

December 1, 1988

Claims (2)

[Claims] (1) (a) A polymerizable monomer crosslinked thermosetting resin composition containing at least a crosslinking polymerizable monomer and a crosslinkable polymer and having thermosetting properties with an acid value of 9 or less; (b) the above (a) 0.7 to 1 per equivalent of acid value of component
．． 5 equivalents of a basic substance; and (c) a surfactant containing a nonionic surfactant with an HLB of 16 or more. (2) A hydraulic silicate material resin composition comprising the emulsion according to claim 1 and a hydraulic silicate material.