WO2006132210A1

WO2006132210A1 - Synthetic resin emulsion composition

Info

Publication number: WO2006132210A1
Application number: PCT/JP2006/311277
Authority: WO
Inventors: Nobuyoshi Yoshimura
Original assignee: Nichigo-Mowinyl Co., Ltd.; The Nippon Synthetic Chemical Industry Co., Ltd.
Priority date: 2005-06-10
Filing date: 2006-06-06
Publication date: 2006-12-14
Also published as: CN101193972A; CN101193972B; TW200710151A

Abstract

Disclosed is a room temperature crosslinkable synthetic resin emulsion composition having excellent storage stability which is not gelatinized even when a polymer compound capable of forming a three-dimensional crosslinked structure and having 3 or more hydrazino groups in a structure is used as a crosslinking agent. This room temperature crosslinkable synthetic resin emulsion composition is excellent in various physical properties such as water resistance and coating film strength when it is applied to various applications through coating. Specifically disclosed is a synthetic resin emulsion composition containing a water-soluble polymer compound, a carbonyl group-containing acrylic resin, and a hydrazino group-containing polymer compound having a weight average molecular weight of not less than 5,000 while containing 3 or more hydrazino groups in a molecule. This emulsion composition is excellent in various physical properties such as water resistance.

Description

Specification

Synthetic resin emulsion composition

Technical field

TECHNICAL FIELD [0001] The present invention relates to a room temperature cross-linking type synthetic resin emulsion composition having excellent physical properties such as water resistance.

Background art

[0002] In the field of synthetic resin emulsions, it is known that a copolymer having a carbo group is crosslinked with a compound having a hydrazino group to improve various properties such as water resistance. . In particular, water-based synthetic resin emulsion is actively used as a means of improving physical properties. Since synthetic resin emulsion is dispersed in an aqueous medium by an emulsifier which is a hydrophilic component, there is a limit in improving water resistance alone. For this reason, the physical properties of the emulsion can be improved by forming a polymer cross-linked structure as described above. In particular, cross-linking between a carbonyl group and a hydrazino group is very effective because a cross-linked structure is easily formed at room temperature.

[0003] Specifically, such a room temperature crosslinking system is obtained by emulsion polymerization of a monomer having a carbonyl group in a structure such as diacetone acrylamide and another copolymerizable monomer. Synthetic resin emulsion is obtained, and mixed compositions prepared by mixing hydrazide compounds such as adipic acid dihydrazide are prepared for various applications such as paints and adhesives! When this mixture is dried to form a film, it is made into a resin having a crosslinked structure.

Conventionally, compounds having 1 or 2 hydrazino groups in their structures have been used as compounds having hydrazino groups used for such applications. Specific examples include hydrazine and adipic acid dihydrazide. For example, Japanese Patent Publication No. 1-60192 and Japanese Patent Application Laid-Open No. 2001-22040 disclose a synthetic resin emulsion composition in which an aqueous emulsion and a hydrazide compound are blended, and the hydrazide compound contains adipic acid. An example using dihydrazide is described. Furthermore, recently, polyhydrazide having a hydrazino group at both ends of a high molecular weight carbon compound has also been used.

[0005] However, in recent years, there has been a growing need for synthetic resins that do not use organic solvents in the factory. Therefore, the level of water resistance required for synthetic resin emulsions as a solvent-based substitute is very high. In order to cope with this, conventional carbol group-containing emulsions and hydrazino compounds may not be fully satisfactory.

[0006] In order to meet the needs of this market, instead of the low molecular weight hydrazide compounds described above, a polymer compound having three or more hydrazino groups in a structure capable of forming a three-dimensional crosslinked structure Has been developed. This polymer compound has a large number of hydrazino groups not only at both ends but also in the polymer side chain. By using this, a dense cross-linked structure can be formed, and a significant improvement in water resistance and film strength can be expected.

[0007] For example, in Japanese Patent Application Laid-Open No. 10-17746, a polymer compound having three or more hydrazino groups in such a structure and a polyvinyl alcohol polymer having a diacetone group are used as a dispersant, and ethylenically unsaturated. A synthetic resin emulsion composition comprising an aqueous emulsion having a monomer polymer as a dispersoid is disclosed.

However, a polymer compound having 3 or more hydrazino groups in such a structure may gel in a short period of time when mixed with a synthetic resin emulsion as in the past. In addition, it may be difficult to use due to poor storage stability. In addition, the polybutyl alcohol having a diacetone group as described above requires considerable labor for production, and its use is disadvantageous in terms of cost.

Disclosure of the invention

[0009] The present inventors have now combined a water-soluble polymer compound, a carbonyl group-containing acrylic resin, and a polymer compound having a weight average molecular weight of 5000 or more and having 3 or more hydrazino groups in the molecule. It was found that the synthetic resin emulsion composition prepared by this method is excellent in storability without galling. Further, this synthetic resin emulsion composition exhibited excellent effects in various physical properties such as water resistance and film strength when applied and used in various applications. The present invention is based on these findings.

[0010] Therefore, the present invention is excellent in storage stability without gelation even when a polymer compound having three or more hydrazino groups in the structure capable of forming a three-dimensional crosslinked structure is used as a crosslinking agent. In addition, when applied and used for various applications, it has excellent physical properties such as water resistance and film strength. The object is to provide a room temperature crosslinkable synthetic resin emulsion composition.

[0011] The present invention includes a water-soluble polymer compound, a carbonyl group-containing acrylic resin, and a hydrazino group-containing polymer compound having a weight average molecular weight of 5,000 or more and having three or more hydrazino groups in the molecule. The present invention relates to a synthetic resin emulsion composition.

[0012] A carbonyl group-containing acrylic resin uses a water-soluble polymer compound as an emulsifier to emulsify a monomer having a carbonyl group and a monomer copolymerizable therewith. It is preferable to be obtained by polymerization.

[0013] The monomer having a carbonyl group is preferably diacetone acrylamide.

[0014] The copolymerizable monomer preferably contains a (meth) acrylic acid alkyl ester.

[0015] The water-soluble polymer compound is preferably polybulal alcohol.

[0016] Poly Bulle alcohols force Keni匕度85-99. 5 mole ^_0/0, and an average polymerization degree of 300 to 2

It ’s a power of 000! / ヽ.

[0017] The weight average molecular weight of the hydrazino group-containing polymer compound is preferably 10,000 or more.

[0018] The hydrazino group-containing polymer compound is preferably an aminopolyacrylamide derivative.

[0019] The hydrazino group-containing polymer compound preferably has 10 or more hydrazino groups in the molecule.

[0020] The carbonyl group strength in the monomer containing a carbonyl group is preferably 0.1 to 20 equivalents relative to the hydrazino group in the hydrazino group-containing polymer compound.

[0021] Preferably, the carbonyl group-containing acrylic resin is in the form of an aqueous emulsion dispersed in an aqueous medium, and the synthetic resin emulsion composition is liquid.

[0022] Further, the present invention provides a synthetic resin obtained by mixing an emulsion powder obtained by spray-drying the emulsion of carboxylic group-containing acrylic resin and a powder of a hydrazino group-containing polymer compound. The present invention relates to a redispersible powder of an emulsion composition.

[0023] The present invention provides (A) a first composition comprising a water-soluble polymer compound and a carboxylic group-containing acrylic resin, and (B) an average molecular weight of 5,000 or more and 3 in the molecule. A second composition comprising a hydrazino group-containing polymer compound having the above hydrazino group? A mixture of

[0024] A carbonyl group-containing acrylic resin uses a water-soluble polymer compound as an emulsifier to emulsion-polymerize a monomer having a carbonyl group and a monomer copolymerizable therewith. It is preferable that it is a synthetic resin emulsion.

[0025] The present invention includes a step of applying a liquid synthetic resin emulsion composition or a liquid composition obtained by redispersing a redispersible powder in water to a coated surface, and drying the applied liquid composition. The present invention relates to a process for forming a water-resistant crosslinked film.

[0026] The present invention also relates to a synthetic resin emulsion composition or an inorganic hydraulic composition comprising a redispersible powder and an inorganic hydraulic material.

BEST MODE FOR CARRYING OUT THE INVENTION

[0027] The synthetic resin emulsion composition according to the present invention includes a water-soluble polymer compound, a carbonyl group-containing acrylic resin, and a hydrazino group having a weight average molecular weight of 5,000 or more and having three or more hydrazino groups in the molecule. Containing a polymer compound.

[0028] In the present invention, the carbonyl group-containing acrylic resin used in the present invention uses a water-soluble polymer compound as an emulsifier, a monomer having a carboxylic group, and other monomers copolymerizable therewith. The polymer is preferably obtained by emulsion polymerization of the monomer in an aqueous medium.

[0029] The water-soluble polymer compound used as the emulsifier is not particularly limited as long as it can be used in ordinary emulsion polymerization. For example, polyvinyl alcohol (hereinafter sometimes referred to as "PVA"). ), Cellulose derivatives, starch derivatives, polyacrylic acid and salts thereof, polyacrylamide and derivatives thereof, styrene-Z maleic acid copolymers, water-soluble oligomers, and the like. These can be used alone or in combination of two or more. Of these, polyvinyl alcohol is preferred from the viewpoints of polymerization stability and supply.

[0030] As the polybulal alcohol, modified polyvinyl alcohols such as ethylene modification, mercapto group modification, acetoacetyl group modification, sulfonic acid modification, and carboxyl group modification can also be used. By using the modified polybulal alcohol, it is possible to improve the polymerization stability and to improve the redispersibility when making the emulsion powder. For example, mercapto group-modified polybulal alcohol or acetocetyl group-modified polybulal alcohol It is useful for smoothly polymerizing acrylic monomers. In addition, by using a acetoacetyl-modified polybulual alcohol, a carbol group is contained in the polybulualcohol skeleton, and a synthetic resin emulsion containing a carbol group simply by emulsion polymerization is usually obtained. It is advantageous in that it is obtained.

[0031] Poly Bulle alcohol is preferably Keni匕度is 85 to 99.5 mole ^_0/0, the average degree of polymerization 300 to 2000. From the viewpoint of water resistance, a chain degree of 90 mol% or more is more preferred. From the viewpoint of stability during polymerization, an average degree of polymerization of 100 to 2000 is more preferred.

[0032] In the present specification, the degree of saponification and the average degree of polymerization can be measured and determined by conventional methods. For example, it can be obtained according to the method for calculating the key degree described in JIS K6726.

[0033] In the present invention, when polybulal alcohol is used as the water-soluble polymer compound, the amount used is usually based on the total amount of monomers used in the production of the synthetic resin emulsion composition. It is preferably 3 to 15% by weight, more preferably 5 to 10% by weight. If the amount of PVA used is too small, the amount of emulsifier during emulsion polymerization will be insufficient, and the polymerization stability tends to be poor. On the other hand, if the amount of PVA used is too large, the polymerization will not proceed stably and gelation may not be achieved to obtain a good emulsion. In this case, the water resistance in the application may be lowered.

[0034] In the present invention, polybulal alcohol is usually made into an aqueous solution using an aqueous medium, and this is used in the process of emulsion polymerization. The amount of polybutyl alcohol in this aqueous solution (in terms of non-volatile content) is not particularly limited, but is preferably 5 to 30% by weight from the viewpoint of ease of handling. If the amount of PVA in the aqueous solution is too small, the non-volatile content of the polymerized synthetic resin emulsion may become too low. Tend to be difficult

Here, in the present specification, the aqueous medium refers to water or an alcoholic solvent mainly composed of water, and water is preferably used in the present invention.

[0036] The monomer having a carbo group includes a carbo group and a synthetic resin emma. There are no particular restrictions as long as it can be used as a monomer for forming a lugeon. Examples include schitil (meth) acrylate. These may be used alone or in combination of two or more. Of these, diacetone acrylamide is also preferable in terms of copolymerization with other monomers.

In the present invention, the monomer having a carbonyl group is preferably 50% by weight or less, more preferably 20% by weight or less, based on the total monomers. . If the amount used is too large, the stability during polymerization tends to decrease.

[0038] The monomer copolymerizable with the monomer having a carbonyl group can be used without particular limitation as long as it can be used in ordinary emulsion polymerization. Specific examples include methyl acrylate, (Meth) acrylic acid alkyl esters such as til acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl (meth) acrylate, styrene, Monomers having aromatic groups such as methylstyrene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid; and hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl Monomers containing a hydroxyl group such as (meth) acrylate and hydroxybutyl (meth) acrylate; Monomers containing an amide group such as (meth) acrylamide; Monomers containing a tolyl group such as acrylonitrile; Bull esters such as vinyl acetate, propionic acid butyl and versatic acid vinyl; ethylene, chlorochloride, etc. Is mentioned. Furthermore, monomers having two or more unsaturated bonds in the structure such as dibulene benzene, triallyloxetane, tetraoxyethane, etc .; unsaturated monomers having an alkoxysilyl group such as vinyl silane; In addition, a functional monomer capable of forming a known cross-linked structure such as glycidyl (meth) acrylate can also be used as a copolymerizable monomer.

[0039] Among the copolymerizable monomers, those containing a (meth) acrylic acid alkyl ester as a main component are preferable from the viewpoint of improving various physical properties such as weather resistance and durability. Specifically, methyl methacrylate / butyl acrylate, methyl methacrylate Z 2-ethylhexyl acrylate, methyl methacrylate Z butyl acrylate Preferred examples of copolymerizable monomers include 2-ethylhexyl acrylate, butyl acrylate, butyl acetate, butyl acrylate, butyl acetate, Z versatate, etc. It is done.

[0040] The amount of copolymerizable monomer used is preferably 50% by weight or more, more preferably 80% by weight or more, based on the total amount of monomers. If the amount of copolymerizable monomer used is too small, the stability during polymerization tends to decrease.

[0041] In the polymerization of the carbonyl group-containing acrylic resin, in addition to the water-soluble polymer compound, the monomer having a carbonyl group, and the copolymerizable monomer component, if necessary, Other ingredients can be further used. Such other components can be appropriately selected according to the purpose without any particular limitation as long as the properties as a synthetic resin emulsion are not deteriorated. Examples of such other components include a polymerization initiator, a reducing agent, a polymerization regulator, and a surfactant.

[0042] The polymerization initiator can be used without particular limitation as long as it can be used in ordinary emulsion polymerization. For example, inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; organic peroxidation And peroxides such as hydrogen peroxide and butyl peroxide. Two or more of these may be used in combination. In the present invention, among these, ammonium persulfate is preferable because it does not adversely affect the physical properties of the skin and the strength enhancement and is easily polymerized.

[0043] The reducing agent is preferably a reducing organic compound (for example, L-ascorbic acid, tartaric acid, citrate, glucose, formaldehyde sulfoxylate metal salt, etc.) or a reducing inorganic compound (for example, sodium thiosulfate). Sodium sulfite, acidic sodium sulfite, sodium metabisulfite and the like. More preferably, the reducing agent is selected from the group consisting of L-ascorbic acid, tartaric acid, citrate, glucose, formaldehyde sulfoxylate metal salt, sodium thiosulfate, sodium sulfite, acidic sodium sulfite, and sodium metabisulfite. One or more types. From the viewpoint of stability during polymerization, sodium acid sulfite is more preferable.

[0044] The polymerization regulator can be appropriately selected from known ones without particular limitations. Examples of such polymerization regulators include chain transfer agents and notfers. It is.

Here, examples of the chain transfer agent include alcohols such as methanol, ethanol, propanol, and butanol; acetone, methyl ethyl ketone, cyclohexane, acetophenone, acetoaldehyde, propionaldehyde, n-butyl. C2-C8 ketones and aldehydes such as aldehyde, furfural and benzaldehyde; and mercaptans such as dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid, octylglycolate and thioglycerol It is done. These may be used alone or in combination of two or more. The use of a chain transfer agent reduces the degree of polymerization of the monomer having a carboxylic group, which is effective from the standpoint of stable polymerization. And may impede improvement of durability. Therefore, in the present invention, it is desirable to avoid the use of a chain transfer agent or to keep the amount used as low as possible even when it is used.

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

[0047] In the present invention, a surfactant may be further used as an auxiliary emulsifier. Any auxiliary emulsifier can be used as long as it is known to those skilled in the art as being usable for emulsion polymerization. For example, the auxiliary emulsifier can be appropriately selected from the known medium strengths such as ionic, cationic, and nonionic surfactants.

[0048] Preferable specific examples of the surfactant include ionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and those having a pull nick type structure or polyoxyethylene type structure. Nonionic surfactants such as those having As the surfactant, a reactive surfactant having a radical polymerizable unsaturated bond in the structure can also be used. However, if many of these surfactants are used as an emulsifying agent, they will gel when mixed with a high molecular weight hydrazine compound, or when used as an emulsion powder, the particles will not form when the emulsion emulsion is dried. Adhesion may occur and the redispersibility may decrease. Therefore, when a surfactant is used, the amount used is an auxiliary amount for the water-soluble polymer compound. That is, it is desirable to reduce as much as possible.

[0049] In the present invention, the carboxylic group-containing acrylic resin contains other monomers capable of copolymerization with a monomer having a carbonyl group using a water-soluble polymer compound as a demulcent. The monomer can be obtained by emulsion polymerization in an aqueous medium.

[0050] The method of emulsion polymerization is not particularly limited. For example, batch type emulsion in which water, an emulsifier, and a monomer are all charged into a polymerization can, and the temperature is raised, and a polymerization initiator is appropriately added to proceed the polymerization. Polymerization method: Monomer in which water and emulsifier are charged in a polymerization can, and the temperature is increased, and the monomer is dropped. Dropping emulsion polymerization method; and the monomer to be dropped is pre-emulsified with an emulsifier and water, and then the added emulsion monomer is dropped. Examples thereof include a drop type emulsion polymerization method.

[0051] The monomer and other components used in the polymerization can be appropriately selected from the above-described monomer and Z or component force. Usually, the emulsion polymerization is carried out using other components as described above such as a polymerization initiator, a polymerization regulator, and an auxiliary emulsifier as necessary in addition to the emulsifier and the monomer component. The polymerization reaction conditions can be appropriately selected according to the type and purpose of the copolymer component that is not particularly limited.

[0052] The polymerization process of the carbonyl group-containing acrylic resin in the present invention will be described with specific examples as follows. First, a polyvinyl alcohol as a protective colloid component and other components as necessary are charged into a reaction can, and after raising the temperature (for example, 50 to 90 ° C.), an ethylenic monomer such as (meth) acrylic acid ester is used. The emulsion and polymerization initiator are added here to perform emulsion polymerization. Next, the monomer components are added all at once or dropwise, and emulsion polymerization is allowed to proceed while adding a polymerization initiator as necessary. When it is determined that the polymerization reaction is completed, the reaction can is cooled, and the target synthetic resin emulsion of carbonyl group-containing acrylic resin can be taken out.

[0053] In the present invention, the synthetic resin emulsion of the carboxylic group-containing acrylic resin obtained by emulsion polymerization is typically uniform milky white and has an average particle size of 0. 05-3. O / zm (preferably 0.5-2. O / zm). Here, the average particle diameter of the emulsion can be measured by a conventional method, for example, a laser analysis Z-scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.).

[0054] In the present invention, the carboxylic group-containing acrylic resin after polymerization may be used as necessary. Additives may be further added. Examples of such additives include organic pigments, inorganic pigments, water-soluble additives, pH adjusters, preservatives, and acid-fouling inhibitors.

[0055] The water-soluble additive improves redispersibility in water when it is used as a redispersible emulsion powder obtained by spray-drying a synthetic resin emulsion of a carbonyl group-containing acrylic resin according to the present invention. It is added for the purpose. When a water-soluble additive is used, the water-soluble additive is usually added to an aqueous synthetic resin emulsion after emulsion polymerization and before drying (hereinafter sometimes simply referred to as a synthetic resin emulsion or an aqueous emulsion). . The amount of the water-soluble additive used is preferably 5 to 50% by weight based on the non-volatile content of the aqueous synthetic resin emulsion before drying. If the amount used is too large, the water resistance of the redispersible emulsion powder tends to be insufficient, and if it is too small, the redispersibility tends not to be improved sufficiently.

[0056] Examples of water-soluble additives include polybutyl alcohol, hydroxyethyl cellulose, methyl cellulose, starch derivatives, polybutylpyrrolidone, polyethylene oxide, water-soluble alkyd resin, water-soluble phenol resin, and water-soluble urea. Oil, water-soluble melamine resin, water-soluble guanamine resin, water-soluble naphthalene sulfonic acid resin, water-soluble amino resin, water-soluble polyamide resin, water-soluble acrylic resin, water-soluble polycarboxylic acid resin, water-soluble Examples thereof include polyester resin, water-soluble polyurethane resin, water-soluble polyol resin, and water-soluble epoxy resin. Two or more of these may be used in combination.

[0057] Among them, polybulal alcohol is effective for improving redispersion. The polybulu alcohol used may be the same as that used as an emulsifier in the polymerization process, or may be different. During polymerization, poly (vinyl alcohol) having a high degree of polymerization cannot be used for its polymerization stability, but such polyvinyl alcohol can be used without any problem as long as it is added after polymerization. However, those with low solubility in water may adversely affect redispersibility, so it is desirable to use them after confirming their solubility in water beforehand.

[0058] In the present invention, a carbo-group-containing acrylic resin synthetic resin emulsion obtained by emulsion polymerization is dried to obtain an emulsion powder that can be used as a raw material for a redispersible powder composition. Can do. [0059] 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 preferred from the viewpoint of production cost, energy saving, and re-emulsification of the resulting powder.

[0060] In the case of spray drying, the spraying form can be carried out by a form such as a disk type or a nozzle type without any particular limitation. Examples of the heat source for spray drying include hot air and heated steam. The conditions for the spray drying can be appropriately selected according to the size and type of the spray drying group, the concentration of the emulsion, the viscosity, the flow rate, and the like. The temperature of spray drying is typically about 80 to 150 ° C.

[0061] The spray drying process will be further described with specific examples. First, the non-volatile content in the synthetic resin emulsion of the carbonyl group-containing acrylic resin is adjusted, and this is continuously supplied from the nozzle of the spray dryer. The mist is pulverized with warm air.

[0062] In the present invention, an anti-blocking agent can be used in combination. The blocking inhibitor can be used by mixing into emulsion powder after spray drying, or spraying it from a different nozzle from the synthetic resin emulsion of carbonyl group-containing acrylic resin at the time of spray drying. As the anti-blocking agent, known inert inorganic or organic powders such as calcium carbonate, talc, clay, anhydrous silicic acid, aluminum silicate, white carbon, alumina white and the like can be used. Among these, anhydrous silicic acid, aluminum silicate, calcium carbonate and the like having an average particle size of about 0.01-0.5 μm are preferable. The amount of the antiblocking agent used is preferably about 2 to 30% by weight based on the obtained redispersible emulsion powder.

[0063] The hydrazino group-containing polymer compound used in the present invention is a polymer compound having an average molecular weight of 5,000 or more and having three or more hydrazino groups in the molecule.

[0064] The weight-average molecular weight of the hydrazino group-containing polymer compound is 5,000 or more, preferably 10,000 or more, more preferably 20,000 or more. The upper limit is usually 210,000. If the weight average molecular weight is less than 5,000, a sufficiently strong film may not be formed. Further, the number of hydrazino groups in the molecule is 3 or more, preferably 5 or more, more preferably 10 or more. When the number of hydrazino groups in the molecule is less than 3, the film strength and water resistance tend to decrease. [0065] The hydrazino group-containing polymer compound is not particularly limited as long as the polymer compound has a weight average molecular weight of 5,000 or more and has 3 or more hydrazino groups in the molecule. That is, an aminopolyacrylamide derivative is preferred. According to a preferred embodiment of the present invention, the hydrazino group-containing polymer compound has a structure represented by the following structural formula.

[0066] [Chemical 1]

— (CH ₂ -CH) n— (CH ₂ -CH) _m ―

o = c C = 0 (I)

I I

NHNH ₂ NH ₂

[0067] In the formula (I), n is 3 or more, m is appropriately within a range where n is 3 or more and the weight average molecular weight of the hydrazino group-containing high molecular compound is 5000 or more. You can choose.

[0068] For example, m can range from 5 to 500, and n can range from 3 to 2000. Preferably, m is in the range of 10 to 400, more preferably m is in the range of 20 to 300. N is preferably in the range of 5 to 1500, and more preferably in the range of 10 to: LOOO.

[0069] In the present invention, the hydrazino group-containing polymer compound is in the form of a powder at room temperature, and is typically used by being dissolved in water when mixed with a liquid synthetic resin emulsion. Further, the hydrazino group-containing polymer compound can also be used as a high-concentration aqueous solution having a high solubility in water of 40 to 50%. Conventionally, many compounds such as adipic acid dihydrazide used as a compound having a hydrazino group (low molecular weight compound) are soluble in water only at a concentration of 10% or less. For this reason, in the present invention, a hydrazino group-containing polymer compound having high solubility in water is used, so that the non-volatile content of the synthetic resin emulsion composition after mixing can be kept high, and as a result, coating was performed. It is possible to dry the composition as soon as possible.

[0070] Production of synthetic resin emulsion composition

The synthetic resin emulsion composition according to the present invention comprises a water-soluble polymer compound (A) and It can be obtained by mixing and stirring a synthetic resin emulsion containing a carbonyl group-containing acrylic resin and a hydrazino group-containing polymer compound (B). For example, the mixing and stirring operations can be carried out by gradually adding an aqueous solution of a hydrazino group-containing polymer compound while stirring the synthetic resin emulsion using a conventional stirrer.

Therefore, according to one embodiment of the present invention, the carboxylic group-containing acrylic resin is in the form of an aqueous emulsion dispersed in an aqueous medium, and the synthetic resin emulsion composition is liquid.

[0072] Further, according to another aspect of the present invention, a monomer having a carbo group and another copolymerizable monomer are contained in an aqueous medium using a water-soluble polymer compound as an emulsifier. There is provided a method for producing a synthetic resin emulsion composition, which comprises mixing an aqueous solution of a hydrazino group-containing polymer compound with a synthetic resin emulsion obtained by emulsion polymerization in (1) and stirring.

[0073] The synthetic resin emulsion composition of the present invention may be a redispersible powder. As used herein, “redispersible” powder refers to a powder that can form an emulsion when redispersed in an aqueous medium (eg, water). The redispersible powder may be obtained by spray-drying a liquid synthetic resin emulsion composition as described above. However, an emulsion obtained by spray-drying the emulsion of the carboxyl group-containing acrylic resin is used. It can also be obtained by mixing (powder mixing) the powder and powder of the hydrazino group-containing polymer compound.

[0074] Therefore, according to another embodiment of the present invention, an emulsion powder obtained by spray-drying the carboxylic group-containing acrylic resin emulsion is mixed with a hydrazino group-containing polymer compound powder ( There is provided a redispersible powder of the synthetic resin emulsion composition of the present invention obtained by powder mixing). From the viewpoint of production efficiency, when the carboxylic group-containing acrylic resin emulsion is spray-dried, it can be sprayed simultaneously from another nozzle and mixed simultaneously with drying.

[0075] The blending ratio of the carbonyl group-containing acrylic resin and the hydrazino group-containing polymer compound in the synthetic resin emulsion composition according to the present invention is such that the carbonyl group of the monomer containing a carbonyl group and the hydrazino group-containing polymer are high. Determined by focusing on the ratio of molecular compounds to hydrazino groups It is desirable to do. Therefore, it is preferable that the hydrazino group in the hydrazino group-containing polymer compound is blended in such an amount that the carboxylic group power of the monomer containing the carbo group is 0.1 to 20 equivalents. More preferably, 0.5 to: blended in such an amount as to give an LO equivalent.

[0076] Applications

The synthetic resin emulsion composition according to the present invention is of a room temperature bridge type having excellent physical properties such as water resistance. For this reason, the emulsion composition according to the present invention comprises cement 'mortar admixture, cement' mortar coating agent, civil engineering materials, paint, adhesive, pressure-sensitive adhesive (pressure-sensitive adhesive), fiber processing agent, paper processing material, inorganic substance. It can be suitably used for binders, resin modifiers such as vinyl chloride, solidifying stabilizers for viscous soils such as sludge and industrial waste, releasable coating materials for surface protection, and cosmetic applications.

[0077] Further, the redispersible powder according to the present invention can be used in various applications such as an additive to a hydraulic material, a powder coating material, and an adhesive. Preferably, it can be used as an additive to hydraulic materials such as various cements and gypsum.

[0078] The synthetic resin emulsion composition or the redispersible powder according to the present invention can be mixed with the inorganic hydraulic material as it is, and with other materials added, the water is kneaded on-site as a powder product. Can only be used. When the synthetic resin emulsion composition according to the present invention is added to a hydraulic material, not only the normal adhesive strength but also the wet adhesive strength can be improved. For this reason, it is possible to further expand the range of use of the single-material product.

Therefore, according to the present invention, there is provided an inorganic hydraulic composition comprising the synthetic resin emulsion composition or redispersible powder according to the present invention and an inorganic hydraulic material. Here, examples of the inorganic hydraulic material include various cement-based materials such as Portland cement, early-strength cement, and fast-curing cement, various gypsum-based materials such as anhydrous gypsum, hemihydrate gypsum, and calcined gypsum, and blast furnace slag. Etc. Here, the inorganic hydraulic composition may further contain other materials. Examples of such other materials include silica sand, fly ash, limestone powder, calcium hydroxide, slaked lime, and calcium carbonate.

[0080] The content of the redispersible powder according to the present invention in the inorganic hydraulic composition is preferably about 1 to 30 parts by weight with respect to 100 parts by weight of the inorganic hydraulic material. Than Preferably it is 5-20 weight part. If the amount is too small, the adhesive strength tends to be insufficiently improved. If the amount is too large, the inherent performance of the hydraulic material tends to be insufficient.

[0081] According to another aspect of the present invention, there is provided a combination comprising the following components (A) and (B):

(A) a first composition comprising a water-soluble polymer compound and a carboxylic group-containing acrylic resin;

(B) A mixture comprising a second composition comprising a hydrazino group-containing polymer compound having an average molecular weight of 5,000 or more and having 3 or more hydrazino groups in the molecule. Carbyl group-containing acrylic resin uses a water-soluble polymer compound as an emulsifier to emulsion-polymerize a monomer having a carbonyl group and a monomer copolymerizable therewith. It is preferable to be a synthetic resin emulsion.

[0082] When the combination according to the present invention is used, the first composition and the second composition can be prepared separately and mixed as needed at the site where they are used. The first composition and the second composition can be made into a liquid (or an aqueous solution) or a powder as necessary.

Example

[0083] In the following, the ability to explain the examples of the present invention is not limited by these examples without departing from the gist of the present invention. In the examples, “part” and “%” mean “part by weight” and “% by weight”, respectively.

[0084] Manufacture of synthetic resin emulsion

Synthetic resin emulsion 1:

In a separable flask (reaction vessel) equipped with a stirrer, thermometer, condenser, and dropping funnel, 250 parts of water and polyvinyl alcohol having an average polymerization degree of 300 and a saponification degree of 98.0 to 99.0% ( (Product name: PVA103, manufactured by Kuraray Co., Ltd.) 7 parts were charged, and the reaction vessel was heated to 80 ° C. to dissolve the polybutyl alcohol in water. Next, keep the temperature of the reactor at 80 ° C, and add 5 parts of butyl acrylate, 5 parts of methyl methacrylate, and 0.1 part of diacetone acrylamide as copolymerizable monomers to the reactor. As a buffer, 0.36 parts of sodium acetate, 0.1 part of ammonium persulfate as a polymerization initiator, and as a reducing agent The initial polymerization reaction was carried out for 1 hour using 0.2 parts of acidic sodium sulfite. Next, 70 parts of butyl acrylate and 20 parts of methyl methacrylate and 0.9 part of diacetone acrylamide were added dropwise to the reaction vessel over about 4 hours as monomer components, and ammonium persulfate was used as a polymerization initiator. The dropping polymerization reaction was allowed to proceed while further adding 2 parts. After completion of the dropwise addition, the mixture was aged and cooled to complete the reaction. As a result, a synthetic resin emulsion 1 of a carboxylic group-containing acrylic resin having a nonvolatile content concentration of about 30% was obtained.

[0085] Synthetic resin emulsion 2:

Synthetic resin emulsion 1 was used except that the addition amount of diacetone acrylamide was changed to 1 part in the initial polymerization reaction and 2 parts in the drop polymerization reaction. As a result, synthetic resin emulsion 2 having a nonvolatile content concentration of about 30% was obtained.

[0086] Synthetic resin emulsion 3:

The same procedure as in Synthetic Resin Emulsion 1 except that the water charged in the reaction vessel was 260 parts, and the addition amount of diacetone acrylamide was changed to 3 parts for the initial polymerization reaction and 7 parts for the drop polymerization reaction. As a result, synthetic resin emulsion 3 having a nonvolatile content concentration of about 30% was obtained.

[0087] Synthetic resin emulsion 4:

270 parts of water to be charged into the reaction can, and polyburu alcohol into polyburu alcohol (trade name: GL05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) with an average polymerization degree of 500 and a saponification degree of 86.5 to 89.0% In the same manner as in the synthetic resin emulsion 1, except that the addition amount of diacetone acrylamide was changed to 2 parts in the initial polymerization reaction and 3 parts in the drop polymerization reaction. As a result, synthetic resin emulsion 4 having a nonvolatile content of about 30% was obtained.

[0088] Synthetic resin emulsion A (comparative example):

Except that the water charged in the reaction can was 240 parts and polyvinyl alcohol was changed to 7 parts Emarzogen EPN287 (trade name) (70% by weight solution: Clariant Japan Co., Ltd.), a nonionic surfactant. The same as the synthetic resin emulsion 1. As a result, a synthetic resin emulsion A having a nonvolatile content of about 30% was obtained.

[0089] Synthetic resin emulsion B (comparative example):

240 parts of water to be charged into the reactor, and polyvinyl alcohol is a nonionic surfactant, Emarzogen EPN287 (trade name) (manufactured by Clariant Japan Co., Ltd.) 1. 4 parts Emulsogen EPA073 (trade name) (30% by weight solution: manufactured by Clariant Japan Co., Ltd.), a char-on surfactant, 3. The same procedure as in Emulsion 1 was made except that the amount was changed to 3 parts. As a result, synthetic resin emulsion B having a nonvolatile content concentration of about 30% was obtained.

[0090] Synthetic resin emulsion C (comparative example):

The same procedure as in Synthetic resin emulsion 3 except that the amount of water charged in the reaction vessel was 260 parts, and polybulal alcohol was changed to 6.6 parts of Emulsogen EPA07 3 (trade name) (manufactured by Clariant Japan KK). As a result, synthetic resin emulsion C having a non-volatile concentration of about 30% was obtained.

[0091] Table 1 shows the compositions and physical properties of the synthetic resin emulsions 1 to 4 and the synthetic resin emulsions A to C.

[0092] Synthetic resin emulsion powder

Emulsion powder 1-3:

100 parts of synthetic resin emulsion 1 is mixed with 50 parts of a 10% solution of polybulualcohol (trade name: AH-17, manufactured by Nippon Synthetic Chemical Industry), and this is mixed with an anti-caking agent (trade name: Hyde). Emulsion powder (Emulsion powder 1) was obtained by spray drying in the presence of Locarb, PLUSS-STAUFER (Switzerland), calcium carbonate.

[0093] Emulsion powders 2 and 3 were obtained in the same manner as described above, except that the synthetic resin emulsion 1 was changed to the synthetic resin emulsion 2 or 3, respectively.

[0094] Compound containing hydrazino group to be used (hydrazine compound)

A commercially available product was used as the compound containing a hydrazino group to be used. As a comparative example, adipic acid dihydrazide (ADH) was used. Table 2 summarizes the compounds used.

[0095] Production of synthetic resin emulsion composition

Example 1:

A 50% by weight aqueous solution of hydrazine compound APA-P950 (trade name) (a polymer compound containing a hydrazino group with a molecular weight of about 90,000: manufactured by Otsuka Chemical) in synthetic resin emulsion 1 The mixture was added with stirring so that the ratio was 1, and mixed.

[0096] Examples 2-8: In the same manner as in Example 1, synthetic resin emulsions 1 to 4 were mixed according to the composition shown in Table 3.

[0097] Example 9:

Emulsion powder 1 In 100 parts of hydrazine compound APA-P950 (trade name) (molecular weight hydrazino group-containing polymer compound: Otsuka Chemical Co., Ltd.), molar ratio of hydrazine compound to diacetone acrylamide Was added and mixed to make a powder composition. 100 parts of this powder composition was added to a container containing 200 parts of water with sufficient stirring, stirred until a uniform emulsion state was obtained, and subjected to an evaluation test.

[0098] Example 10: L 1:

In the same manner as in Example 9, emulsion powders 2 and 3 were mixed according to the composition shown in Table 4 to obtain a powder composition, which was then re-emulsified and subjected to an evaluation test.

[0099] Comparative Example 1:

Synthetic resin emulsion 1 In 100 parts, a 5% aqueous solution of adipic acid dihydrazide (ADH) as a hydrazine compound was added and mixed with stirring so that the molar ratio of hydrazine compound to diacetone acrylamide was 1. .

[0100] Comparative Examples 2 to 8:

In the same manner as in Comparative Example 1, synthetic resin emulsions 2 to 4 and synthetic resin emulsions A to C were mixed according to the composition shown in Table 5.

[0101] Evaluation test

Evaluation A: Mixing stability test

The obtained synthetic resin emulsion composition was allowed to stand for 7 days under the condition of 40 ° C., respectively, and it was evaluated on the basis of the following criteria whether there was any alteration such as gelling if the viscosity increased. Judgment criteria:

◯: When the viscosity increase rate is 1 to 2 times

X: When the viscosity increase rate is more than double

[0102] The results were as shown in Tables 3-5.

The numerical values in the table represent the molar ratio of the hydrazine compound to the carboxylic group-containing monomer (diacetone acrylamide) used in each synthetic resin emulsion composition.

[0103] Evaluation B: Film tensile strength test The square polyethylene film was attached to a glass plate Paste cellophane tape made of 100 X 100 mm ² frame, pouring the synthetic resin Emma Rujon composition 10 parts by weight of the nonvolatile content 20% by weight therein And dried at 40 ° C. for 16 hours to form a film. After drying, each film was cut into a size of 1. Ocm X 3. Ocm, and 5 pieces of each were prepared. These were measured for tensile strength at the time of cutting using a tensile tester (trade name: Shimadzu Autograph IM-100, manufactured by Shimadzu Corporation) (tensile speed: 30 cmZlmin). The measured value was obtained as an average value of five test pieces for each synthetic resin emulsion composition.

[0104] Adipic acid dihydrazide having two hydrazino groups in the structure were blended so as to have the same molar ratio as the hydrazide compound used in Example 1 to L 1 and Comparative Examples 1 to 8, respectively. Each example was compared with the maximum tensile strength of the film. The results were evaluated according to the following criteria.

Judgment criteria:

: 1. 50 times or more

0: 1. 20 times or more, 1. less than 50 times

△: 0.9. More than 90 times, 1. Less than 20 times

X: 0.9 Less than 90 times

[0105] The results were as shown in Tables 3-5.

[0106] [Table 1]

^

2¾

note:

Polyvinyl alcohol (1) PVA1 03Z made by Kuraray Co., Ltd.

Polyvinyl alcohol (2) Gosensenol GL 05 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

Surfactant (1) Emulsogen EPN 287 (70 wt% solution) / Clariant Japan KK Surfactant (2) Emulsogen EPA073 (30 wt% solution) / Clariant Japan KK

Table 2

Where m n is an integer in the following structural formula

— (CH CH) _n — (CH ₂ — CH) _m — o = cc = o

I!

NHNH ₂ NH ₂

[]

Table 3

Table 4

Table 5

ADVANTAGE OF THE INVENTION According to this invention, the inorganic hydraulic composition containing the synthetic resin emulsion composition excellent in the storage stability which is not gelatinized, or its redispersible powder, and an inorganic hydraulic material can be provided. The synthetic resin emulsion composition of the present invention comprises a liquid type in which an aqueous synthetic resin emulsion is mixed with a hydrazino group-containing polymer compound, and a redispersible synthetic resin emulsion powder obtained by spray-drying an aqueous synthetic resin emulsion. It can be provided in two forms of powder type in which hydrazino group-containing polymer compound powder is mixed. The liquid type is excellent in storage stability, and it is applied with a paste that does not gel even after mixing the two components. When a film is formed by drying, a dense cross-linked film is obtained at room temperature. Is excellent in various physical properties such as water resistance. In the case of powder type

When redispersed in water, the film can be easily redispersed, and if the redispersed composition is applied and dried, a film having excellent physical properties as in the liquid type can be obtained.

Claims

The scope of the claims

[I] Synthetic resin emulsion composition comprising a water-soluble polymer compound, a carbonyl group-containing acrylic resin, and a hydrazino group-containing polymer compound having a weight average molecular weight of 5,000 or more and having three or more hydrazino groups in the molecule object.

[2] A carbonyl group-containing acrylic resin emulsifies a monomer having a carbonyl group and a monomer copolymerizable therewith using a water-soluble polymer as an emulsifier The synthetic resin emulsion composition according to claim 1, which is obtained by polymerization.

[3] The synthetic resin emulsion composition according to claim 1 or 2, wherein the monomer having a carbonyl group is diacetone acrylamide.

[4] The synthetic resin emulsion composition according to claim 2 or 3, wherein the copolymerizable monomer contains an alkyl (meth) acrylate.

[5] The synthetic resin emulsion composition according to any one of claims 1 to 4, wherein the water-soluble polymer compound is polybulal alcohol.

[6] Poly Bulle alcohols force Keni匕度85-99. 5 mole ^_0/0, and an average polymerization degree of 300 to 2

The synthetic resin emulsion composition according to claim 5, which is 000.

[7] The synthetic resin emulsion composition according to any one of claims 1 to 6, wherein the hydrazino group-containing polymer compound has a weight average molecular weight of 10,000 or more.

[8] The synthetic resin emulsion composition according to any one of [1] to [7], wherein the hydrazino group-containing polymer compound is an aminopolyacrylamide derivative.

[9] The synthetic resin emulsion composition according to any one of claims 1 to 8, wherein the hydrazino group-containing polymer compound has 10 or more hydrazino groups in the molecule.

[10] The carbonyl group power in the monomer containing a carbonyl group is 0.1 to 20 equivalents relative to the hydrazino group in the hydrazino group-containing polymer compound. Synthetic resin emulsion composition.

[II] The synthetic resin emulsion according to any one of claims 1 to 10, wherein the carbonyl group-containing acrylic resin is in the form of an aqueous emulsion dispersed in an aqueous medium, and the synthetic resin emulsion composition is liquid. Composition.

[12] Claims obtained by mixing an emulsion powder obtained by spray-drying an aqueous emulsion of a carbonyl group-containing acrylic resin with a powder of a polymer compound containing a hydrazino group Claims 1 to 11 /! Redispersible powder of synthetic resin emulsion composition as described in any of

[13] (A) a first composition comprising a water-soluble polymer compound and a carboxylic group-containing acrylic resin, and (B) an average molecular weight of 5,000 or more and three or more hydrazino groups in the molecule A mixture comprising the second composition comprising a hydrazino group-containing polymer compound.

[14] Emulsion polymerization of carbonyl group-containing acrylic resin using a water-soluble polymer compound as an emulsifier and a monomer having a carbonyl group and a monomer copolymerizable therewith 14. The mixture according to claim 13, which is a synthetic resin emulsion.

[15] The liquid synthetic resin emulsion composition according to claim 11 or the liquid composition obtained by redispersing the redispersible powder according to claim 12 in water is applied to the coated surface. A method for forming a water-resistant crosslinked film, which comprises a step of applying and a step of drying the applied liquid composition.

[16] The synthetic resin emulsion composition according to any one of claims 1 to 11 or the redispersible powder according to claim 12, and an inorganic hydraulic material. An inorganic hydraulic composition comprising.