JP2009035470A - Aqueous synthetic-resin emulsion for cement mortar admixture, re-emulsifiable powder for cement mortar admixture from aqueous synthetic resin emulsion, and cement mortar admixture using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous synthetic resin emulsion which, when used for a cement mortar admixture, imparts satisfactory flowability and workability, is reduced in fluctuation of physical properties, and attains improvements in bonding strength, etc. <P>SOLUTION: The aqueous synthetic resin emulsion for use as a cement mortar admixture contains a synthetic resin dispersed and stabilized with a polyvinyl alcohol resin [I] having an average degree of saponification of 85 mol% or higher and an average degree of polymerization of 50-3,000 and having 1-15 mol% of 1,2-diol bonds in side chains, the synthetic resin being one obtained from comonomer ingredients comprising (A) at least one monomer selected among acrylic monomers and styrene monomers and (B) at least one functional group-containing monomer selected from the group consisting of the following (i)-(vi), wherein (i) is monomers containing a glycidyl group, (ii) is monomers containing an allyl group, (iii) is monomers containing a hydrolyzable silyl group, (iv) is monomers containing an acetoacetyl group, (v) is monomers having two or more vinyl groups in the molecular structure, and (vi) is monomers containing a hydroxyl group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the present invention, a specific polyvinyl alcohol-based resin (hereinafter, polyvinyl alcohol may be abbreviated as PVA) is dispersed and stabilized as a protective colloid, and at least one monomer selected from an acrylic monomer and a styrene monomer is used. An aqueous synthetic resin emulsion for cement admixture copolymerized with a functional group-containing monomer, a re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture obtained by drying the emulsion, and a cement mortar admixture using the same Is.

  Conventionally, PVA-based resins have been used as protective colloid agents in order to impart mechanical stability and freeze stability to aqueous synthetic resin emulsions. However, in this case, generally, although the mechanical stability and freezing stability of the emulsion are improved, the polymerization stability is insufficient, and in particular, a high non-volatile content such that the resin content in the emulsion exceeds 50% by weight. It was not possible to polymerize.

  Therefore, when a PVA resin is used as a protective colloid agent for an aqueous synthetic resin emulsion obtained by polymerizing at least one monomer of an acrylic monomer and a styrene monomer, the resin content in the emulsion is less than 50% by weight. There was a problem in terms of productivity. In addition, the resulting emulsion has insufficient stability and has a problem of thickening with time.

  In addition, it is known that an aqueous synthetic resin emulsion using a PVA-based resin as a protective colloid agent is used for mixing with cement mortar. However, when such an emulsion is mixed, the fluidity of cement mortar deteriorates over time. However, there is a problem that workability is lowered.

  Therefore, when a PVA-based resin is used as a protective colloid agent for an aqueous synthetic resin emulsion, the development of a PVA-based protective colloid agent capable of polymerizing the resin content in the emulsion even at a high concentration of 50% by weight or more, and cement mortar There has been a demand for the development of an aqueous synthetic resin emulsion that does not deteriorate the fluidity and workability even when mixed with the above.

  On the other hand, the re-emulsifiable aqueous synthetic resin emulsion powder is produced by drying (for example, spray drying) the aqueous synthetic resin emulsion, and is easier to handle than the aqueous synthetic resin emulsion because it is a powder. It is. The product can be wrapped in paper bags, which is convenient for storage and transportation. In addition, since this re-emulsifiable aqueous synthetic resin emulsion powder can be re-dispersed and emulsified in water simply by adding it to water and stirring at the time of use, it can be applied to cement mortar products such as cement and mortar and gypsum products. As pre-mixed admixtures, it is further used as adhesives for wood and wood materials, paint binders, soil improvement binders, and the like. In particular, the water-based synthetic resin emulsion powder can be mixed in advance with an inorganic hydraulic composition such as cement mortar product or gypsum, so that cement mortar product or gypsum product such as mortar can be formed just by adding water on site. be able to.

  In general, many of the known water-based synthetic resin emulsion powders that can be re-emulsified in water need to be re-emulsified. Therefore, water-soluble polymers such as PVA resins are used as protective colloids for emulsion polymerization. It is obtained by drying the aqueous synthetic resin emulsion obtained. Therefore, the water resistance of the film is insufficient, and in particular, physical properties such as adhesive strength when wet are insufficient for mixing to modify cement mortar products and gypsum products.

  To cope with this, it is easy to return to the original emulsion level when re-emulsified in water. In particular, it is sufficient in the adhesive strength when wet to mix to modify cement mortar products and gypsum products. In addition, there has been a demand for the development of a re-emulsifiable aqueous synthetic resin emulsion powder that exhibits physical properties and that does not deteriorate fluidity and workability even when mixed with cement mortar.

As such a countermeasure, in aqueous synthetic resin emulsions, it has been proposed to use acetoacetyl (CH ₃ COCH ₂ CO-) group-containing PVA resin or modified PVA resin as an emulsifying dispersant, etc. Are listed.

  For example, Patent Document 1 contains an active hydrogen group such as an acetoacetate group, a mercapto group, a diacetone acrylamide group, a block character [η] larger than 0.6, and a saponification degree of 95.0 mol%. An aqueous emulsion in which higher and lower blocking PVA is attached to a polymer is disclosed, and it is stated that the resulting aqueous emulsion has good mechanical stability, freezing stability, and high-temperature storage stability. .

  Patent Document 2 discloses an ethylenically unsaturated monomer using a modified PVA resin produced by saponifying a vinyl acetate-ethylenesulfonic acid alkali salt copolymer containing an ethylenesulfonic acid alkali salt as an emulsifier. Is disclosed, and it is stated that the obtained emulsion has little change in viscosity over time and has excellent performance in standing stability and the like.

  Patent Document 3 discloses a stabilizer for emulsion polymerization comprising a modified PVA resin having an average degree of saponification of 90 mol% or less and a sulfonic acid group content of 0.1 to 20 mol%.

  Patent Document 4 discloses a styrene emulsion stabilizer comprising a modified PVA-based resin containing a hydrocarbon group having 4 or more carbon atoms and a sulfonic acid group or a sulfate ester group in the side chain. The emulsion exhibits excellent stability and has an appropriate viscosity, and is described as being used as an adhesive, a cement mortar admixture or the like.

  However, in Patent Document 1, although an aqueous emulsion having good mechanical stability, freezing stability, and high-temperature storage stability is obtained, the viscosity stability during long-term storage is still not satisfactory. Further, in Patent Documents 2 to 4, since the polymerization stability is insufficient or the graft ratio is low and the mechanical stability is inferior, the mixing stability is insufficient in cement mortar mixing applications, and is still satisfactory. It was not a thing.

  That is, in these documents concerning aqueous synthetic resin emulsions, when the nonvolatile content concentration is 50% or more for the purpose of actual production, the stability of the viscosity at the time of standing and the mechanical stability due to the high graft ratio are shown. The compatibility is not enough, and even when mixed with cement or mortar, fluidity and workability are good when cement or mortar is used immediately after mixing, but when using it after mixing, There has been a problem that the workability of the cement and mortar is lowered due to the lowered fluidity.

Regarding re-emulsifiable aqueous synthetic resin emulsion powder, Patent Document 5 proposes to use an acetoacetyl (CH ₃ COCH ₂ CO-) group-containing PVA resin as an emulsifying dispersant, but it is still satisfactory. However, there is a demand for a re-emulsifiable aqueous synthetic resin emulsion powder with improved physical properties during re-emulsification and further improved water resistance of the film. In particular, development of a re-emulsifiable aqueous synthetic resin emulsion powder that is improved in fluidity and workability when mixed with cement mortar and in which fluidity and workability do not deteriorate with time is desired.
JP 2003-277419 A JP-A-50-155579 Japanese Patent Laid-Open No. 10-060015 JP 58-063706 Japanese Patent No. 3225150

  An object of the present invention is to provide an acrylic or styrene cement mortar admixture that exhibits good fluidity and workability when used as a cement mortar admixture, has little variation in physical properties, and has improved adhesion strength. Another object of the present invention is to provide an aqueous synthetic resin emulsion for use, a re-emulsifiable aqueous synthetic resin emulsion powder for a cement mortar admixture obtained by drying the emulsion, and a cement mortar admixture using the same.

  However, as a result of intensive studies in view of such circumstances, the present inventor has an average saponification degree of 85 mol% or more, an average polymerization degree of 50 to 3000, and a 1,2-diol bond in the side chain of 1 to 15 mol%. Using PVA resin [I] as a protective colloid agent, a synthetic resin containing at least one monomer (A) of an acrylic monomer and a styrene monomer and a specific functional group-containing monomer (B) as a copolymerization component is dispersed. By being stabilized, when used as an admixture for cement mortar, it has been found that it exhibits excellent fluidity and workability, has little variation in physical properties, and is improved in adhesion strength and the like. Was completed.

That is, the gist of the present invention is an average saponification degree of 85 mol% or more, an average polymerization degree of 50 to 3000, and a polyvinyl alcohol resin [I] having 1 to 15 mol% of 1,2-diol bonds in the side chain. As a copolymerization component, at least one monomer (A) of an acrylic monomer and a styrene monomer and at least one functional group-containing monomer (B) selected from the group consisting of (a) to (f) below are used as a copolymerization component. The present invention relates to an aqueous synthetic resin emulsion for cement mortar admixture in which the synthetic resin is dispersed and stabilized, and a re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture obtained by drying the synthetic resin.
(A) A glycidyl group-containing monomer.
(A) Allyl group-containing monomer.
(C) Hydrolyzable silyl group-containing monomer.
(D) Acetoacetyl group-containing monomer.
(E) A monomer having two or more vinyl groups in the molecular structure.
(F) A hydroxyl group-containing monomer.

  The aqueous synthetic resin emulsion for cement mortar admixture according to the present invention has an average saponification degree of 85 mol% or more, an average polymerization degree of 50 to 3000, and 1 to 15 mol% of 1,2-diol bonds in the side chain. Using alcohol-based resin [I] as a protective colloid agent, at least one functional group selected from the group consisting of at least one monomer (A) of an acrylic monomer and a styrene monomer and the above (a) to (f) An aqueous synthetic resin emulsion for cement mortar admixture obtained by emulsion polymerization using a group-containing monomer (B) as a copolymerization component is preferable.

  Furthermore, the present invention also provides a cement mortar admixture containing the above-mentioned aqueous synthetic resin emulsion for cement mortar admixture or the above-mentioned re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture.

  The aqueous synthetic resin emulsion for cement mortar admixture of the present invention and the re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture obtained by drying the emulsion are excellent fluidity when used as a cement mortar admixture. It has excellent workability, small physical property variation, and improved adhesion strength. For cement mortar applications, it is used for repair mortars, base preparation coatings, self-leveling materials, and tile adhesive mortars. And as a modifier for gypsum-based materials.

The present invention is described in detail below.
In the present invention, when a PVA resin [I] having an average saponification degree of 85 mol% or more, an average polymerization degree of 50 to 3000, and having a 1,2-diol bond in the side chain of 1 to 15 mol% is used, copolymerization is performed. It is easier to obtain an aqueous synthetic resin emulsion having a higher reactivity with a reactive monomer and better polymerization stability and a higher non-volatile content. The drying property of the aqueous synthetic resin emulsion can be improved, and in particular, the heat source energy can be saved during spray drying.

  The PVA resin [I] having a 1,2-diol bond in the side chain used in the present invention is known, and usually contains a 1,2-diol structural unit represented by the following general formula (1). Resin.

  Such PVA-based resin [I] is, for example, (a) a method of saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (b) a method of vinyl acetate and vinyl ethylene carbonate. A method of saponifying and decarboxylating a copolymer, (c) a method of saponifying and deketalizing a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane, (d ) A method of saponifying a copolymer of vinyl acetate and glyceryl monoallyl ether, and the like.

  In the present invention, the average saponification degree of the PVA resin [I] is 85 mol% or more, preferably 90 to 99.8 mol%. If the average degree of saponification is less than the above range, the stability during polymerization of the aqueous synthetic resin emulsion will be reduced, and even if the polymerization is completed, the storage stability of the aqueous synthetic resin emulsion may not be good, and stable. It tends to be difficult to obtain an aqueous synthetic resin emulsion.

  In the present invention, the average saponification degree can be measured and determined by a conventional method. For example, it can be determined according to the saponification degree calculation method described in JIS K 6726.

  The average degree of polymerization of the PVA resin [I] is 50 to 3000, preferably 100 to 1700, more preferably 100 to 1000, and particularly preferably 200 to 500. If the average degree of polymerization is less than the above range, it is difficult to industrially produce a PVA resin, and if it exceeds the above range, the viscosity of the aqueous synthetic resin emulsion becomes too high, or the polymerization stability of the aqueous synthetic resin emulsion is low. There is a tendency to decrease.

  In the present invention, the average degree of polymerization can be measured and determined by a conventional method. For example, it can be determined according to the method for calculating the average degree of polymerization described in JIS K 6726.

  The amount of 1,2-diol bonded to the side chain of the PVA resin [I] is 1 to 15 mol%, preferably 1 to 12 mol%, more preferably 2 to 10 mol%, and particularly preferably 2 to 8 mol%. Mol%. If the 1,2 diol bond amount is less than the above range, the mechanical stability of the water-based synthetic resin emulsion and the water resistance of the film will decrease, and if it exceeds the above range, the stability during polymerization will decrease and the non-volatile content will decrease. It tends to be difficult to obtain a highly stable aqueous synthetic resin emulsion.

  In the present invention, the amount of the PVA resin [I] used as a protective colloid agent (dispersion stabilizer) is 100 parts by weight (hereinafter abbreviated as “part”) of the total amount of copolymerized monomers used. The amount is preferably 3 to 20 parts, more preferably 4 to 15 parts, and particularly preferably 5 to 10 parts. If the amount used is too small, the amount of protective colloid at the time of emulsion polymerization tends to be insufficient and the polymerization stability tends to be poor, and if too large, the viscosity of the aqueous synthetic resin emulsion increases and the stability decreases. Tend.

  Here, the used PVA resin [I] is usually present in the whole amount in the aqueous synthetic resin emulsion formed by polymerization. That is, 3 to 20 parts, more preferably 4 to 15 parts, and still more preferably 5 to 10 parts of PVA-based resin [I] may be present in the emulsion with respect to 100 parts of the copolymer.

  In the present invention, PVA resin [I] having a 1,2-diol bond in the side chain is used as a protective colloid agent (dispersion stabilizer). A modified type part or a completely saponified PVA resin may be used in combination.

In the present invention, the PVA resin [I] is usually made into an aqueous solution using an aqueous medium, and this is used in the process of emulsion polymerization. Here, the aqueous medium refers to water or an alcoholic solvent mainly composed of water, preferably water.
The amount (nonvolatile content) of the PVA resin [I] in the aqueous solution is not particularly limited, but is preferably 5 to 30% by weight, particularly 5 to 20% by weight from the viewpoint of ease of handling.

  Moreover, you may use together the PVA-type resin containing an anionic group for PVA-type resin [I] used by this invention. Examples of the anionic group include a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group. Among these, a sulfone group can be obtained stably and strongly regardless of the pH in the emulsion. It is preferably an acid group.

  In the present invention, the PVA system means PVA itself or, for example, one modified by various modified species (in the present invention, other than modified species having a 1,2-diol bond) The degree of modification is usually 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less.

  Examples of such modified species include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid and the like. Unsaturated acids or salts thereof, mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, or Its salts, alkyl vinyl ethers, polyoxyethylene (meth) allyl ether, polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, polyoxyethylene (meth) acrylate, polyoxyethylene (meth) acrylate, Polyoxyalkylene (meth) acrylates such as oxypropylene (meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxyalkylene (meth) acrylamides such as polyoxypropylene (meth) acrylamide, polyoxyethylene [1- (meth) Acrylamide-1,1-dimethylpropyl] ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, N-acrylamidomethyltrimethylammonium chloride , Allyltrimethylammonium chloride, dimethyldiallylammonium chloride, dimethylallyl vinyl ketone, - vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like. In addition to the above, modified species containing active hydrogen such as acetoacetyl group modification, mercapto group modification, diacetone acrylamide modification and the like can also be mentioned.

  Next, an aqueous synthetic resin emulsion that is dispersed and stabilized by the PVA resin [I] having a 1,2-diol bond in the side chain will be described.

  The aqueous synthetic resin emulsion in the present invention comprises at least one monomer (A) of an acrylic monomer and a styrene monomer and a specific functional group-containing monomer (B) as a copolymerization component.

  The acrylic monomer is not particularly limited as long as it is known to those skilled in the art. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate , Aliphatic (meth) acrylates such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, , Aromatic (meth) acrylates such as phenoxy (meth) acrylate, trifluoroethyl (meth) acrylate, and the like, which are used alone or in combination of two or more. Of these, aliphatic (meth) acrylates having 1 to 18, preferably 1 to 10, more preferably 1 to 8 carbon atoms in the alkyl group are suitable.

  In the present invention, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acryl” means acryl or methacryl.

  Examples of the styrenic monomer include styrene and α-methylstyrene. These may be used alone or in combination of two or more.

  Among the above, a combination of at least one of methyl methacrylate and styrene having a high glass transition temperature and at least one of n-butyl acrylate and 2-ethylhexyl acrylate having a low glass transition temperature is easy to copolymerize, and It is particularly preferred in that it is a monomer that is generally used for paints and adhesives.

  In the present invention, when emulsion polymerization is performed, it is possible to copolymerize a specific functional group-containing monomer (B) together with at least one monomer (A) of the above acrylic monomer and styrene monomer. When used as, it is preferable in that it exhibits excellent effects such as little variation in physical properties and improved adhesion strength.

The functional group-containing monomer (B) is preferably at least one selected from the group consisting of (a) to (f) below.
(A) A glycidyl group-containing monomer.
(A) Allyl group-containing monomer.
(C) Hydrolyzable silyl group-containing monomer.
(D) Acetoacetyl group-containing monomer.
(E) A monomer having two or more vinyl groups in the molecular structure.
(F) A hydroxyl group-containing monomer.

  Specific examples of the glycidyl group-containing monomer (a) include glycidyl (meth) acrylate, glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is particularly preferable from the viewpoints of little variation in physical properties and, in addition, improvement in adhesive strength when wet.

  Specific examples of the allyl group-containing monomer (I) include, for example, a monomer having two or more allyl groups such as triallyloxyethylene, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, Examples include allyl glycidyl ether and allyl acetate. Of these, allyl glycidyl ether is preferred from the viewpoint of adhesive strength when wet.

  Specific examples of the hydrolyzable silyl group-containing monomer (c) include, for example, vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; vinylalkyldisilanes such as vinylmethyldimethoxysilane and vinylmethyldiethoxysilane. Alkoxysilane; γ- (meth) acryloxypropyltrialkoxysilane such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane; γ- (meth) acryloxypropylmethyldimethoxy Examples thereof include silane, γ- (meth) acryloxypropylalkyldialkoxysilane such as γ- (meth) acryloxypropylmethyldiethoxysilane; vinyltris (β-methoxyethoxy) silane and the like. Of these, vinyl trialkoxysilane, particularly vinyltrimethoxysilane is preferred from the viewpoint of adhesive strength when wet.

  Specific examples of the acetoacetyl group-containing monomer (d) include, for example, acetoacetate vinyl ester, acetoacetate allyl ester, diacetoacetate allyl ester, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, etc. Examples include acetoxyalkyl (meth) acrylate; acetoacetoxyalkyl crotonates such as acetoacetoxyethyl crotonate and acetoacetoxypropyl crotonate; 2-cyanoacetoacetoxyethyl (meth) acrylate and the like. Of these, acetoacetoxyalkyl (meth) acrylate, particularly acetoacetoxyethyl (meth) acrylate, is preferable from the viewpoints that, for example, there is little variation in physical properties and adhesion strength when wet is improved.

  Specific examples of the monomer (e) having two or more vinyl groups in the molecular structure include, for example, divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate; ethylene glycol di (meth) acrylate, 1, 2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di Examples include alkylene glycol (meth) acrylates such as (meth) acrylate; trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and the like.

  Specific examples of the hydroxyl group-containing monomer (f) include, for example, an alkyl group such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate having 1 to 1 carbon atoms. 10, especially 1 to 6 hydroxyalkyl (meth) acrylates. Of these, 2-hydroxyethyl methacrylate is preferred from the viewpoint of protective colloidal action during emulsion polymerization and improvement of miscibility with cement mortar blends.

  According to a preferred embodiment of the present invention, the functional group-containing monomer (B) is selected from the group consisting of a glycidyl group-containing monomer (a), a hydrolyzable silyl group-containing monomer (c), and an acetoacetyl group-containing monomer (d). In particular, it is preferable that at least one of the glycidyl group-containing monomer (a) and the acetoacetyl group-containing monomer (d) is used as a cement mortar admixture, resulting in variation in physical properties. It is particularly preferable in that it exhibits a superior effect such as a small amount and, in addition, an improvement in adhesive strength.

  It is preferable that the usage-amount of a functional group containing monomer (B) is 0.01 to 10 weight% of the whole copolymerizable monomer, More preferably, it is 0.05 to 5 weight%, Especially preferably, it is 0.1 to 5 % By weight, more preferably 0.1 to 1% by weight. If the amount used is too small, when used as a cement mortar admixture, there is a tendency for the effects such as little variation in physical properties and improvement of adhesion strength to be insufficient, and if too much, poor polymerization results. There is a tendency to become.

  In addition, these functional group containing monomers (B) can be used individually or in combination of 2 or more types.

  Further, in the present invention, a copolymerizable monomer other than those described above can be used in combination as long as the object of the present invention is not impaired. For example, vinyl acetate, vinyl propionate, vinyl laurate, vinyl versatate, etc. Vinyl monomers such as vinyl carboxylates and alkyl vinyl ethers such as methyl vinyl ether; olefins such as ethylene, propylene, 1-butene and isobutene, halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride, ethylene sulfonic acid And diene monomers such as butadiene-1,3,2-methylbutadiene, 1,3 or 2,3-dimethylbutadiene-1,3, 2-chlorobutadiene-1,3, and the like. .

  Moreover, as functional group containing monomers other than the above, nitrile monomers such as (meth) acrylonitrile; (meth) acrylamide, N, N-dimethylacrylamide, t-butylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, Amide-modified such as diacetone acrylamide and carboxyl group-modified acrylic monomers such as (meth) acrylic acid; and (anhydrous) itaconic acid, (anhydrous) maleic acid, etc. and unsaturated dicarboxylic acids of these esters or their ester systems Monomers and the like can also be used.

  In the aqueous synthetic resin emulsion according to the present invention, in addition to the copolymerizable monomer component such as at least one monomer (A) of the acrylic monomer and styrene monomer and the specific functional group-containing monomer (B), it is necessary. Other components can be further used accordingly. Such other components are not particularly limited as long as the properties as an aqueous synthetic resin emulsion are not lowered, and can be appropriately selected according to the purpose. Examples of other components include a polymerization initiator, a polymerization regulator, an auxiliary emulsifier, a plasticizer, and a film forming aid.

  Any polymerization initiator can be used without particular limitation as long as it can be used for ordinary emulsion polymerization. For example, inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; organic peroxides, azo initiators Agents, peroxides such as hydrogen peroxide and butyl peroxide; and redox polymerization initiators combining these with reducing agents such as acidic sodium sulfite and L-ascorbic acid. These may be used alone or in combination of two or more. Among these, ammonium persulfate and potassium persulfate are preferable from the viewpoint of easy polymerization without adversely affecting the film properties and strength enhancement.

  There is no restriction | limiting in particular as a polymerization regulator, It can select suitably from well-known things. Examples of such a polymerization regulator include a chain transfer agent and a buffer.

  Here, examples of the chain transfer agent include alcohols such as methanol, ethanol, propanol and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, furfural and benzaldehyde; and dodecyl mercaptan, lauryl mercaptan, and normal mercaptan. And mercaptans such as thioglycolic acid, octyl thioglycolate, and thioglycerol. These may be used alone or in combination of two or more. The use of a chain transfer agent is effective in terms of stabilizing the polymerization, but in order to reduce the polymerization degree of the synthetic resin, when used as a cement mortar admixture, the water resistance of the resulting film is reduced. There is a tendency for the physical property variation to increase and the adhesive strength and the like to decrease. For this reason, when using a chain transfer agent, it is desirable to keep the amount used as low as possible.

  Here, examples of the buffer include sodium acetate, ammonium acetate, dibasic sodium phosphate, and sodium citrate. These may be used alone or in combination of two or more.

  Any auxiliary emulsifier can be used as long as it is known to those skilled in the art as being usable for emulsion polymerization. Therefore, auxiliary emulsifiers are, for example, known anionic, cationic and nonionic surfactants, water-soluble polymers having protective colloid ability other than PVA resin [I], and water-soluble oligomers. Can be appropriately selected.

  Here, preferable specific examples of the surfactant include, for example, anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and those having a pluronic type structure and those having a polyoxyethylene type structure. Nonionic surfactants such as Moreover, the reactive surfactant which has a radically polymerizable unsaturated bond in a structure can also be used as a surfactant. These may be used alone or in combination of two or more.

The use of a surfactant makes the emulsion polymerization proceed smoothly and is easy to control (effect as an emulsifier). In addition, there is an effect of suppressing the generation of coarse particles and block-like substances generated during the polymerization.
However, if many of these surfactants are used as emulsifiers, the graft rate tends to decrease. For this reason, when using a surfactant, it is desirable that the amount used is an auxiliary amount with respect to the PVA resin, that is, as small as possible.

  Here, examples of the water-soluble polymer having protective colloid ability other than PVA-based resin [I] include PVA-based resins other than PVA-based resin [I], hydroxyethylcellulose, polyvinylpyrrolidone, methylcellulose, and the like. These may be used alone or in combination of two or more. These are effective in that the viscosity is changed by increasing the viscosity of the emulsion or changing the particle size of the emulsion. However, since the water resistance of the film may be lowered depending on the amount used, it is desirable to use a small amount when used.

  Here, as the water-soluble oligomer, for example, a polymer or copolymer having a hydrophilic degree such as a sulfonic acid group, a carboxyl group, a hydroxyl group, and an alkylene glycol group and having a degree of polymerization of about 10 to 500 is preferably exemplified. Specific examples of water-soluble oligomers include, for example, amide copolymers such as 2-methacrylamide-2-methylpropanesulfonic acid copolymer, sodium methacrylate-4-styrenesulfonate copolymer, styrene / maleic acid copolymer. Examples thereof include a polymer, a melamine sulfonic acid formaldehyde condensate, and a poly (meth) acrylate. Specific examples include monomers having a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkylene glycol group, and water-soluble oligomers obtained by previously copolymerizing a radical polymerizable reactive emulsifier alone or with other monomers. It is done. These may be used alone or in combination of two or more. In the present invention, among these, 2-methacrylamido-2-methylpropanesulfonic acid copolymer, sodium methacrylate-4-styrenesulfonate copolymer are preferable in view of the stability of mixing with fillers such as pigments and charcoal cal. Coalescence is preferred. As the water-soluble oligomer, those previously polymerized before starting the emulsion polymerization may be used, or commercially available products may be used.

As the plasticizer, an adipate plasticizer, a phthalic acid plasticizer, a phosphoric acid plasticizer, or the like can be used. A film-forming aid having a boiling point of 260 ° C. or higher can also be used.
The amount of these other components used is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately selected according to the object.

Next, production of the aqueous synthetic resin emulsion of the present invention will be described.
As described above, the aqueous synthetic resin emulsion according to the present invention uses at least one monomer (A) of an acrylic monomer and a styrene monomer and a specific functional group using a specific PVA resin [I] as a protective colloid agent. It can manufacture by carrying out emulsion polymerization of the copolymerizable monomer containing group-containing monomer (B).

  The method for emulsion polymerization is not particularly limited. For example, a monomer dropping emulsion polymerization method in which water and PVA resin [I] are charged into a reaction can and the temperature is raised and a copolymerizable monomer and a polymerization initiator are dropped. And an emulsion monomer dropping type emulsion polymerization method in which the monomer to be dropped is dispersed and emulsified in advance with PVA resin [I] and water and then dropped. The monomer dropping method is convenient.

  Usually, emulsion polymerization is carried out using the above-mentioned other components such as a polymerization initiator, a polymerization regulator, and an auxiliary emulsifier as needed in addition to the PVA resin [I] and the copolymerizable monomer component. . The polymerization reaction conditions are not particularly limited, and can be appropriately selected according to the type and purpose of the copolymerizable monomer.

The emulsion polymerization process will be described more specifically as follows.
First, water, a PVA resin [I], and an auxiliary emulsifier as necessary are charged into a reaction can. After the temperature is raised (usually 65 to 90 ° C.), a part of the copolymerizable monomer component and a polymerization initiator are added. Add to the reaction can and perform initial polymerization. Next, the remaining copolymerizable monomer components are added to the reaction can in one batch or dropwise, and polymerization is allowed to proceed while further adding a polymerization initiator as necessary. When it is determined that the polymerization reaction is completed, the reaction can is cooled, and the target aqueous synthetic resin emulsion can be taken out.

In the present invention, the aqueous synthetic resin emulsion obtained by emulsion polymerization is typically uniform milky white, and the average particle size of the synthetic resin in the aqueous synthetic resin emulsion is preferably 0.2 to 2 μm. More preferably, the thickness is 0.3 to 1.5 μm.
Here, the average particle diameter can be measured by a conventional method, for example, a laser analysis / scattering particle size distribution measuring apparatus “LA-910” (manufactured by Horiba, Ltd.).

  In addition, the glass transition temperature of the synthetic resin in the aqueous synthetic resin emulsion is not particularly limited, but when it is used as a cement mortar admixture of −20 to + 30 ° C., there is little variation in physical properties. It is preferable at the point that adhesive strength etc. improve, and it is preferable that it is -15- + 20 degreeC especially. If the glass transition temperature is too low, the adhesive strength tends to decrease. If the glass transition temperature is too high, a plasticizer such as dibutyl phthalate is added to reduce the film forming temperature of the aqueous synthetic resin emulsion. There is a tendency for the adhesive strength to decrease.

  In addition, in this invention, the glass transition temperature in the said synthetic resin is a value calculated by the formula of Fox based on the main monomer component except a functional group containing monomer (B) as a copolymerization monomer component.

  Furthermore, in the present invention, it is determined that at least a part of the PVA-based resin [I] is grafted to the above synthetic resin, so that the storage stability and adhesive strength of the resulting aqueous synthetic resin emulsion itself before drying are measured. This is preferable in that the variation of the measured value in the case is reduced.

  When the PVA resin [I] is grafted to the synthetic resin, the value (W) represented by the following formula (2) is preferably 50% by weight or more, more preferably 65% by weight or more. More preferably, it is 70% by weight or more. This value is a measure of the degree of grafting, and if this value is too low, the degree of grafting is low, the protective colloid action during emulsion polymerization is lowered, the polymerization stability is lowered, There is a tendency for miscibility with fillers to decrease.

The value (W) of equation (2) is calculated as follows.
That is, the target emulsion or the like is dried at 40 ° C. for 16 hours to form a film having a thickness of about 0.5 mm, and left for 2 days at 23 ° C. and 65% RH. The film is extracted in boiling water for 8 hours and then extracted in acetone for 8 hours to remove ungrafted resin and the like. In this case, the absolute dry weight of the film before extraction is w ₁ (g), and the absolute dry weight of the film after extraction is w ₂ (g).

W (% by weight) = (w ₂ ) / (w ₁ ) × 100 (2)
w ₁ : Absolute dry weight of film before extraction (g)
w ₂ : absolute dry weight of the film after extraction (g)
In addition, the film dry weight (w ₁ ) before extraction is obtained by previously drying a sample different from the extraction test sample at 105 ° C. for 1 hour and calculating the film dry weight of the sample before extraction. The film absolutely dry weight (w ₂ ) is the weight when the sample after extraction is dried at 105 ° C. for 1 hour. Since the calculation of the weights of w ₁ and w ₂ uses different samples, both samples are corrected by the volatile content ratio accompanying drying of both samples in order to handle under the same conditions. The absolute dry weight of the film was calculated.

  As a method of adjusting the value (W) of the above formula (2) to the above range, the emulsion polymerization temperature is slightly higher than conventional, or a very small amount of reducing agent (for example, a persulfate used as a polymerization catalyst) Acid soda sulfite, etc.).

  In the present invention, various additives may be further added to the aqueous synthetic resin emulsion after emulsion polymerization, if necessary. Examples of such additives include organic pigments, inorganic pigments, water-soluble additives, pH adjusters, preservatives, and antioxidants.

  Thus, although the aqueous synthetic resin emulsion for cement mortar admixtures of this invention is obtained, when using it, it is preferable to adjust to 40 to 60 weight% normally as a non volatile matter.

  In the present invention, a re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture can be obtained by drying the aqueous synthetic resin emulsion obtained by the emulsion polymerization.

  The obtained re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture can be used as it is, or it can be re-emulsified in water and used as an aqueous synthetic resin emulsion.

  The drying method is not particularly limited, and examples thereof include spray drying, freeze drying, and hot air drying after coagulation. Among these, spray drying is preferable from the viewpoint of production cost and energy saving.

  In the case of spray-drying, the spraying form is not particularly limited, and for example, it can be carried out by a disk type, nozzle type or the like. Examples of the heat source for spray drying include hot air and heated steam. The conditions for spray drying can be appropriately selected according to the size and type of the spray dryer, the nonvolatile content of the aqueous emulsion, the viscosity, the flow rate, and the like. The spray drying temperature is usually preferably 80 to 150 ° C, more preferably 100 to 140 ° C. If the drying temperature is too low, it takes time to dry, which may cause problems in production. If it is too high, the resin itself tends to be altered by heat.

  The spray drying process will be further explained with specific examples. First, the non-volatile content in the aqueous synthetic resin emulsion is adjusted, and this is continuously supplied from the nozzle of the spray dryer, and the mist is dried with warm air. To powder. In some cases, it is also possible to preheat the adjusted spray liquid before spraying, continuously supply it from the nozzle, and dry the atomized liquid with warm air to form a powder. Heating increases the drying speed and enables highly non-volatile differentiation of the spray liquid as the viscosity of the spray liquid decreases, contributing to a reduction in production costs.

  In the present invention, the anti-caking agent is mixed with the aqueous synthetic resin emulsion, mixed with the resin emulsion powder after spray drying, or sprayed from a different nozzle from the aqueous synthetic resin emulsion at the time of spray drying. Can be used together.

  By adding an anti-caking agent, it is possible to prevent particles from caking and agglomerating and blocking during storage in a state where the resin emulsion powder is coated with the anti-caking agent.

  As the anti-caking agent, known inert inorganic or organic powders, for example, calcium carbonate, talc, clay, dolomite, anhydrous silicic acid, alumina white and the like can be used as the inorganic powder. These may be used alone or in combination of two or more. Among these, anhydrous silicic acid, calcium carbonate, clay and the like are preferable. As the organic powder, a resin emulsion powder obtained by spray-drying an aqueous emulsion having a glass transition temperature of 70 ° C. or higher of a synthetic resin can also be used as an anti-caking agent. It is preferable that the usage-amount of an anti-caking agent is about 5 to 30 weight% with respect to the resin emulsion powder obtained.

  In order to further improve the re-emulsification property of the re-emulsifiable aqueous synthetic resin emulsion powder in water, a water-soluble additive can be blended. Usually, the water-soluble additive is added to the aqueous synthetic resin emulsion before drying. This addition amount is 2 to 50 parts with respect to 100 parts of the nonvolatile content of the aqueous synthetic resin emulsion before drying. If the amount added is too small, there is a tendency that the re-emulsification property to water cannot be sufficiently improved. If the amount is too large, it will greatly improve the re-emulsification property to water, but the water resistance of the film will decrease, and the expected physical properties May not be able to be demonstrated.

  Examples of water-soluble additives include PVA resins, hydroxyethyl celluloses, methyl celluloses, polyvinyl pyrrolidone, starches, dextrins, water-soluble alkyd resins, water-soluble amino resins, water-soluble acrylic resins, and water-soluble polycarboxylic acid resins. And water-soluble resins such as water-soluble polyamide resins. These may be used alone or in combination of two or more. Among these, PVA-based resins are preferable.

  As said PVA-type resin, polyvinyl alcohol with an average saponification degree of 85 mol% or more is desirable, and it is more preferable that it is 87 mol% or more. The upper limit of the average saponification degree is not particularly limited, but is preferably 99.5 mol% or less, and more preferably 95 mol% or less. If the average saponification degree is too small, the water resistance of the film tends to be remarkably lowered. If it is too large, the water resistance is improved, but the re-emulsification property to water tends to be deteriorated.

The average degree of polymerization is preferably 50 to 3000, more preferably 200 to 2000, and still more preferably 300 to 600. If the average degree of polymerization is too small, the water resistance tends to decrease, and if it is too large, the re-emulsification property tends to decrease.
Those that are not easily soluble in water may adversely affect the re-emulsification properties, so it is desirable to use them after confirming the solubility in water in advance.

  Thus, the aqueous synthetic resin emulsion for cement mortar admixture of the present invention and the re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture obtained by drying the emulsion have good fluidity when used as a cement mortar admixture. It exhibits workability, exhibits excellent effects such as little variation in physical properties, and improved adhesion strength. And as cement mortar use, it is useful as modifiers for repair mortars, for base preparation coating materials, self-leveling materials, tile adhesion mortars, mortar sealers / primers, mortar curing agents, and gypsum-based materials.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.

<Production example of aqueous synthetic resin emulsion>
[Example 1 / Emulsion 1]
In a 2 L stainless steel reaction vessel equipped with a stirrer and a reflux condenser, 670 parts of water and PVA having a 1,2-diol bond in the side chain as a protective colloid (degree of polymerization: 300, degree of saponification: 99.1) 46 parts of mol%, content of 1,2-diol bond of side chain 8 mol% / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 2 g of sodium acetate, and 1 g of sodium acid sulfite were charged, and the reaction vessel was heated to 85 ° C. The PVA was dissolved by heating. Next, the temperature of the reaction vessel was kept at 80 ° C., and the premixed mixed monomer [358 parts of butyl acrylate / 293 parts of methyl methacrylate / 6.5 parts of acetoacetoxyethyl methacrylate = 54.4 / 44] .6 / 1 (weight ratio)] was added, 30% of an aqueous ammonium persulfate solution obtained by dissolving 1.6 g of ammonium persulfate in 30 g of water was added as a polymerization initiator, and an initial polymerization reaction was performed for 1 hour. Subsequently, the remaining mixed monomer and 60% of the ammonium persulfate aqueous solution as a polymerization initiator were dropped into the reaction vessel over 4 hours to proceed the polymerization. After completion of dropping, 10% of the aqueous ammonium persulfate solution was added and aged at the same temperature for 1 hour to obtain an aqueous synthetic resin emulsion (emulsion 1) having a nonvolatile content of 50.1% (average particle size: 0.43 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 80% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin having the main monomer composition [butyl acrylate / methyl methacrylate = 358/293 = 55/45 (weight ratio)] is obtained by setting the Tg of each homopolymer to −52. It was about -1 degreeC when it was referred to as +105 degreeC.

[Example 2 / Emulsion 2]
Emulsion 2 (nonvolatile) in the same manner as Emulsion 1 except that the type and composition ratio of the mixed monomer were changed to butyl acrylate / styrene / acetoacetoxyethyl methacrylate = 54.4 / 44.6 / 1 (weight ratio). Min 49.8%) (average particle size: 0.40 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 75% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin composed of this main monomer composition [butyl acrylate / styrene = 55/45 (weight ratio)] is that Tg of each homopolymer is −52 ° C. and + 100 ° C. The temperature was about -2 ° C.

[Example 3 / Emulsion 3]
Emulsion 3 (nonvolatile content 50) was the same as Emulsion 1 except that the type and composition ratio of the mixed monomer were changed to butyl acrylate / styrene / glycidyl methacrylate = 44.6 / 54.4 / 1 (weight ratio). 0.2%) (average particle size: 0.42 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 77% by weight.
In addition, the calculated glass transition temperature (Tg) of the synthetic resin composed of this main monomer composition [butyl acrylate / styrene = 45/55 (weight ratio)] is that Tg of each homopolymer is −52 ° C. and + 100 ° C. The temperature was about + 12 ° C.
However, for the purpose of adjusting the minimum film-forming temperature, 3% of dibutyl phthalate as a plasticizer was added to the resin content.

[Example 4 / Emulsion 4]
The same as emulsion 1 except that the type and composition ratio of the mixed monomer were changed to butyl acrylate / methyl methacrylate / styrene / acetoacetoxyethyl methacrylate = 55.5 / 22/22 / 0.5 (weight ratio). Emulsion 4 (nonvolatile content 50.2%) was obtained (average particle size: 0.45 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 75% by weight.
In addition, the calculated glass transition temperature (Tg) of the synthetic resin having the main monomer composition [butyl acrylate / methyl methacrylate / styrene = 55.8 / 22.1 / 22.1 (weight ratio)] is When the Tg of the polymer was -52 ° C, + 105 ° C, and + 100 ° C, it was about -3 ° C.

[Example 5 / Emulsion 5]
Emulsion 5 (non-volatile content 49.50) was the same as Emulsion 1 except that the type and composition ratio of the mixed monomer were changed to methyl methacrylate / 2-ethylhexyl acrylate / glycidyl methacrylate = 48/51/1 (weight ratio). 9%) (average particle size: 0.44 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 73% by weight.
In addition, the calculated glass transition temperature (Tg) of the synthetic resin comprising this main monomer composition [methyl methacrylate / 2-ethylhexyl acrylate = 48.5 / 51.5 (weight ratio)] is the Tg of each homopolymer. It was about -10 degreeC when it was set as +105 degreeC and -70 degreeC.

[Example 6 / Emulsion 6]
Emulsion 6 (nonvolatile) in the same manner as Emulsion 1 except that the type and composition ratio of the mixed monomer were changed to butyl acrylate / methyl methacrylate / vinyltrimethoxysilane = 54.4 / 44.6 / 1 (weight ratio). Min. 50.1%) (average particle size: 0.42 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 74% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin having the main monomer composition [butyl acrylate / methyl methacrylate = 55/45 (weight ratio)] was about −1 ° C. as in the case of the emulsion 1. .

Example 7 / Emulsion 7
Emulsion 7 (nonvolatile) in the same manner as Emulsion 1 except that the type and composition ratio of the mixed monomer were changed to butyl acrylate / methyl methacrylate / ethylene glycol dimethacrylate = 54.4 / 44.6 / 1 (weight ratio). Min. 50.0%) (average particle size: 0.43 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 71% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin having the main monomer composition [butyl acrylate / methyl methacrylate = 55/45 (weight ratio)] was about −1 ° C. as in the case of the emulsion 1. .

[Example 8 / Emulsion 8]
Emulsion 8 (nonvolatile content) was the same as Emulsion 1 except that the type and composition ratio of the mixed monomer were changed to butyl acrylate / methyl methacrylate / allyl glycidyl ether = 54.4 / 44.6 / 1 (weight ratio). (49.8%) was obtained (average particle size: 0.43 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 72% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin having the main monomer composition [butyl acrylate / methyl methacrylate = 55/45 (weight ratio)] was about −1 ° C. as in the case of the emulsion 1. .

[Example 9 / Emulsion 9]
As protective colloid, PVA having 1,2-diol bond in the side chain (polymerization degree 300, saponification degree 99.1 mol%, content of 1,2-diol bond in the side chain 3 mol% / Nippon GOHSEI Emulsion 9 (non-volatile content: 50.3%) was obtained (average particle size: 0.40 μm) in the same manner as Emulsion 1 except that the product was changed to “made by Co., Ltd.”.
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 76% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin having the main monomer composition [butyl acrylate / methyl methacrylate = 55/45 (weight ratio)] was about −1 ° C. as in the case of the emulsion 1. .

[Comparative Example 1 / Emulsion 10]
Emulsion 10 (nonvolatile content) was the same as Emulsion 1 except that the type and composition ratio of the mixed monomer were changed to butyl acrylate / methyl methacrylate = 55/45 (weight ratio) and further changed to 665 parts of water. (50.3%) was obtained (average particle size: 0.43 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 78% by weight.
In addition, the calculated glass transition temperature (Tg) of the synthetic resin composed of this main monomer composition [butyl acrylate / methyl methacrylate = 55/45 (weight ratio)] is the Tg of each homopolymer at −52 ° C. and + 105 ° C. The temperature was about -1 ° C.

[Comparative Example 2 / Emulsion 11]
The emulsion 1 and the emulsion 1 except that the protective colloid was changed to acetoacetyl group-modified PVA (degree of polymerization 300, degree of saponification 97.0 mol%, degree of acetoacetylation 0.5 mol% / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Similarly, an emulsion 11 (non-volatile content: 50.0%) was obtained (average particle size: 0.44 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 78% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin composed of this main monomer composition [butyl acrylate / methyl methacrylate = 55/45 (weight ratio)] is the Tg of each homopolymer at −52 ° C., +105 It was about -1 degreeC when it was set as degreeC.

[Comparative Example 3]
As protective colloids, 37 parts of PVA having an average polymerization degree of 500 and an average saponification degree of 88 mol% (GOHSENOL GL05 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and PVA having an average polymerization degree of 1400 and an average saponification degree of 88 mol% (GOHSENOL) Polymerization was carried out in the same manner as Emulsion 1 except that it was changed to 9 parts of GM14 / manufactured by Nippon Gosei Kogyo Co., Ltd. However, gelation occurred during polymerization, and an aqueous synthetic resin emulsion was not obtained.

[Comparative Example 4 / Emulsion 12]
In the emulsion 1, 28 parts of nonionic active agent (Emulgen 1135S-70 / manufactured by Kao Corporation) and 26 parts of anionic activator (hosta pearl BVconc / Clariant Japan Co., Ltd.) are used as emulsifiers instead of protective colloids. used. Specifically, 20% of these activators and 200 parts of water to be used were charged into a reaction can, and an emulsified monomer was prepared from the remaining activator, about 435 parts of water and a mixed monomer, and subjected to polymerization. An emulsion 12 having a nonvolatile content of 50.2% was obtained (average particle size: 0.07 μm).
The value (W) calculated by the above formula (2) of the obtained aqueous synthetic resin emulsion was 43% by weight.
Further, the calculated glass transition temperature (Tg) of the synthetic resin composed of this main monomer composition [butyl acrylate / methyl methacrylate = 55/45 (weight ratio)] is the Tg of each homopolymer at −52 ° C., +105 It was about -1 degreeC when it was set as degreeC.

<Production example of re-emulsifiable aqueous synthetic resin emulsion powder>
[Example 10 / resin powder 1]
7 parts of PVA (GOHSENOL GL05 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) having an average degree of polymerization of 500 and an average degree of saponification of 88 mol% are added to 100 parts of the non-volatile content of emulsion 1 obtained in Example 1, and water is added. The non-volatile content was adjusted to 40%. A re-emulsifiable aqueous synthetic resin emulsion powder 1 was obtained by spray drying under hot air at 140 ° C. using a nozzle-type spray dryer in the presence of calcium carbonate as an anti-caking agent.

[Examples 11 to 18 / resin powders 2 to 9]
About each emulsion 2-9 obtained in Examples 2-9, it carried out similarly to the resin powder 1, and obtained the re-emulsifiable aqueous | water-based synthetic resin emulsion powder 2-9.

[Comparative Examples 5-7 / Resin powder 10-12]
For each of the emulsions 10-12 obtained in Comparative Examples 1, 2, and 4, re-emulsifiable aqueous synthetic resin emulsion powders 10-12 were obtained in the same manner as resin powder 1.

  About the said Example and comparative example, evaluation was performed as follows.

<Emulsion polymerization stability>
In the above polymerization, the scaling to the polymerization can and the presence or absence of coarse particles were observed and evaluated according to the following criteria.
(Evaluation criteria)
○ ・ ・ ・ Scaling is small and there are almost no coarse particles. △ ・ ・ ・ Scaling is partly and there are a few coarse particles. × ・ ・ ・ Scaling is large and there are many coarse particles.

<Re-emulsification of resin powder>
While stirring, 50 g of re-emulsifiable aqueous synthetic resin emulsion powder was added to 50 g of deionized water, and then re-emulsified by stirring at 1000 rpm for 10 minutes. This re-emulsified liquid was placed in a glass container having a volume of 250 cc and left at room temperature for 1 week. The re-emulsification property at this time was evaluated according to the following criteria.
(Evaluation criteria)
◎ ・ ・ ・ A state where a uniform re-emulsified liquid is obtained and only slight sedimentation of the resin powder is observed ○ ・ ・ ・ A state where a uniform re-emulsified liquid is obtained and a slight amount of sedimentation of the resin powder is observed △ ・ ・ ・Phase separation is slightly observed in the re-emulsified liquid and the resin powder is sedimented x: Phase separation is observed in the re-emulsified liquid and the resin powder is largely sedimented

<Cement mortar fluidity>
A mortar mixing test is performed according to JIS A6203.
Cement mortar was prepared by stirring 500 g of ordinary Portland cement, 1500 g of Toyoura cinnabar, 111 g of 45% non-volatile emulsion (non-volatile content 50 g) and 289 g of kneaded water for 3 minutes using a Hobart mixer. The fluidity of the cement mortar is as follows. The cement mortar is stuffed into a flow cone with a bottom diameter of 100 mm installed on a flow table, and the flow cone is pulled out. Was measured. This was evaluated as an initial flow. Further, after being left for 1 hour, the mixture was stirred with a Hobart mixer for 30 seconds, and the same measurement was performed. This was defined as a flow after 1 hour.
In the case of a re-emulsifiable aqueous synthetic resin emulsion powder, 50 g of this resin powder was pre-prepared with cement and Toyoura cinnabar before use. In this case, the mixing water was 350 g.
The amount of water (W) relative to the cement mortar (C) of the aqueous synthetic resin emulsion and the re-emulsifiable aqueous synthetic resin emulsion powder, that is, W / C is both constant at 70%.

<Adhesive strength of cement mortar>
In accordance with JIS A 6203, the cement mortar was subjected to a normal bond strength test and evaluated according to the following criteria.
Preparation of Specimen: A cement mortar substrate (70 × 70 × 20 mm / JIS R 5201 compliant) was polished using No. 150 polishing paper defined in JIS R 6252. Each test cement mortar was filled to 40 × 40 × 10 mm on the substrate using a mold, and molded and cured to prepare a specimen.
Curing conditions: After molding, after 48 hours at a temperature of 20 ± 2 ° C and a relative humidity of 90% or more, after demolding, it was cured in water at a temperature of 20 ± 2 ° C for 5 days, and further at a temperature of 20 ± 2 ° C, relative Cured for 21 days at a humidity of 60 ± 10%.
The wet adhesion strength was measured by immersing the specimen subjected to the above-described curing in room temperature water for 24 hours, and then immediately taking it out and measuring the adhesive strength in a wet state.
The measurement was performed with a universal measuring machine (manufactured by Shimadzu Corporation).
(Evaluation criteria)
◎ ・ ・ ・ Adhesion strength 1.5 N / mm ² or more ○ ・ ・ ・ Adhesion strength 1.0 N / mm ² or more, less than 1.5 N / mm ² △ ・ ・ ・ Adhesion strength 0.8 N / Mm ² or more, less than 1.0 N / mm ² × ・ ・ ・ Adhesive strength less than 0.8 N / mm ²

  The respective evaluation results of the aqueous synthetic resin emulsions obtained in Examples and Comparative Examples and the re-emulsifiable aqueous synthetic resin emulsion powders obtained from these emulsions were as shown in Tables 1 and 2.

  When the amount of water (W / C) relative to cement mortar is 70% (Table 1), the flow values of cement mortar in Comparative Examples 1 and 2 are smaller than those in Examples 1 and 2. Therefore, in order to compare the fluidity level of the cement mortars of Comparative Examples 1 and 2 at substantially the same level as in Examples 1 and 2, the amount of water in Comparative Examples 1 and 2 is increased, that is, the amount of water relative to cement mortar W / C) was set to 75% and subjected to a fluidity test and a cement mortar bond strength test.

  These evaluation results were as shown in Table 3.

  From the above results, all the examples are excellent in the polymerization stability of the emulsion and the re-emulsification property of the resin powder, have little variation in physical properties, and have good fluidity and adhesive strength in normal and wet conditions. Excellent results were obtained. Although the emulsion 5 of Examples 5 and 14 and the corresponding resin powder 5 and the resin powder 7 of Example 16 showed slightly lower adhesive strength, the aqueous synthetic resin emulsion and re-emulsifiable aqueous synthesis of the present invention were shown. It could be used satisfactorily as a resin emulsion powder.

  On the other hand, it can be seen that the emulsion 10 of Comparative Examples 1 and 5 and the corresponding resin powder 10 and the emulsion 12 of Comparative Example 4 are inferior in adhesive strength when wet. Further, the emulsions 11 and the corresponding resin powders 11 of Comparative Examples 2 and 6 are inferior in fluidity, and even if the water content is increased to improve fluidity, the adhesive strength is inferior. It can be seen that the physical properties cannot be obtained. Furthermore, since Comparative Example 3 gelled during the polymerization, the emulsion itself was not obtained. And it turns out that the resin powder 12 of the comparative example 7 is inferior in all of re-emulsification property, adhesive strength, and fluidity | liquidity.

  The aqueous synthetic resin emulsion for cement mortar admixture of the present invention and the re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture obtained by drying the emulsion are excellent fluidity when used as a cement mortar admixture. It has excellent workability, small physical property variation, and improved adhesion strength. For cement mortar applications, it is used for repair mortars, base preparation coatings, self-leveling materials, and tile adhesive mortars. And as a modifier for gypsum-based materials.

Claims (6)

Polyvinyl alcohol resin [I] having an average saponification degree of 85 mol% or more and an average polymerization degree of 50 to 3000 and having a 1,2-diol bond of 1 to 15 mol% in the side chain, A synthetic resin comprising at least one monomer (A) and at least one functional group-containing monomer (B) selected from the group consisting of (a) to (f) below as a copolymerization component is dispersed and stabilized. An aqueous synthetic resin emulsion for cement mortar admixture characterized by comprising:
(A) A glycidyl group-containing monomer.
(A) Allyl group-containing monomer.
(C) Hydrolyzable silyl group-containing monomer.
(D) Acetoacetyl group-containing monomer.
(E) A monomer having two or more vinyl groups in the molecular structure.
(F) A hydroxyl group-containing monomer. An acrylic monomer using a polyvinyl alcohol resin [I] having an average saponification degree of 85 mol% or more and an average polymerization degree of 50 to 3000 and having a 1,2-diol bond in the side chain of 1 to 15 mol% as a protective colloid agent. And emulsion polymerization of at least one monomer (A) of a styrene monomer and at least one functional group-containing monomer (B) selected from the group consisting of the following (A) to (F) as a copolymerization component: The aqueous synthetic resin emulsion for cement mortar admixture according to claim 1, wherein
(A) A glycidyl group-containing monomer.
(A) Allyl group-containing monomer.
(C) Hydrolyzable silyl group-containing monomer.
(D) Acetoacetyl group-containing monomer.
(E) A monomer having two or more vinyl groups in the molecular structure.
(F) A hydroxyl group-containing monomer.   The aqueous synthetic resin emulsion for cement mortar admixture according to claim 1 or 2, wherein the amount of the functional group-containing monomer (B) used is 0.01 to 10% by weight of the total monomer components.   The amount of the polyvinyl alcohol-based resin [I] used is 3 to 20 parts by weight with respect to 100 parts by weight of all monomer components, and the cement mortar admixture according to any one of claims 1 to 3 Aqueous synthetic resin emulsion.   A re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture, which is obtained by drying the aqueous synthetic resin emulsion for cement mortar admixture according to any one of claims 1 to 4.   The aqueous synthetic resin emulsion for cement mortar admixture according to any one of claims 1 to 4, or the re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture according to claim 5 is contained. Cement mortar admixture.